COIL-4:1 Chlorometallate Ionic Liquids Revisited Kenneth R ...

COIL-4:1
Chlorometallate Ionic Liquids Revisited
Kenneth R. Seddon (1) , quill@qub.ac.uk, The QUILL Research Centre, Belfast Northern
Ireland, United Kingdom ; Julien Estager (1) ; Małgorzata Swadźba-Kwaśny (1) . (1) The
QUILL Research Centre, The Queen’s University of Belfast, Belfast Northern Ireland,
United Kingdom
Research on chloroaluminate(III) ionic liquids, the first well-examined class of roomtemperature
ionic liquids, resulted in a vast number of papers, patents and even fullscale
industrial processes. However, following the discovery of the moisture-stable ionic
liquids in 1992, many scientists focussed on those exciting new media, often deserting
the research on the moisture-sensitive chloroaluminates(III). Also, research on other
chlorometallate systems had been partially abandoned. The combination of the
scattered recent work on chlorometallate ionic liquids with older publications (viewed
with new insight) results in a fascinating picture of their wide applicability and new
emerging possibilities. Properties of chlorometallate ionic liquids, prepared usually by
reaction of an organic chloride salt with a metal chloride, depend strongly on anionic
speciation, reliant in turn both on the metal used, its oxidation state, and on the reactant
ratio. In our recent work, we have studied speciation of several chlorometallate systems,
demonstrating how it relates to their fundamental properties (e.g. Lewis acidity), and
thereby facilitates tailoring of their catalytic activity. Furthermore, looking at how the
'mainstream' ionic liquids have developed from electrolytes to catalytic media, and
subsequently to multifunctional materials applicable from biochemistry, through polymer
science to the automotive industry, we revisited the opportunities offered by the
chlorometallate systems and demonstrated how chlorometallates have evolved from
'retro' solvents to very interesting, multipurpose media.
COIL-4:2
Natural Fiber Welding - Ionic Liquid Facilitated Biopolymer Mobilization and
Reorganization
Paul C. Trulove (1) , trulove@usna.edu, 572M Holloway Road, Annapolis MD 21402,
United States ; Luke M. Haverhals (1) ; Robert W. Burdon (1) ; Matthew P. Foley (1) ; W.
Matthew Reichert (2) ; Hugh C. De Long (3) . (1) Department of Chemistry, United States
Naval Academy, Annapolis MD 21409, United States (2) Department of Chemistry,
University of South Alabama, Mobile AL 36688, United States (3) Directorate of Math,
Information, and Life Sciences, Air Force Office of Scientific Research, Arlington VA
22203, United States
Throughout history, man has expended much effort to exploit the remarkable properties
of biopolymers such as cellulose and silk. In modern times, these natural materials still
possess properties that rival the most advanced synthetic polymers. Recent work has
shown ionic liquids to be excellent solvents for a wide variety of biopolymers. In the past

decade, extensive research has been conducted whereby biopolymer materials are
dissolved and reconstituted to create novel composite materials. Unfortunately, full
dissolution denatures the native micro and macro structures, often with deleterious
consequences to the physical and chemical properties. Very recently we have
demonstrated a methodology we call “natural fiber welding” which allows complex
composite materials to be created while simultaneously retaining selected amounts of
biopolymer in the native state. The key feature of natural fiber welding is its ability to
open up and mobilize biopolymer structures to enable chemistry; this allows the
manipulation and modification of natural materials and makes possible the imparting of
new functionalities. Furthermore, dramatic enhancement and modification of physical
and chemical properties can be realized without disruption to many of the desirable
properties intrinsic to natural materials. By precisely regulating process variables such
as the purity, type, amount, and placement of ionic liquid solvent as well as the time and
temperature of treatment, we have demonstrated controlled reorganization of natural
material hydrogen bonding networks. We are currently carrying out fundamental studies
that are directed towards the characterization and development of the fiber welding
process. These systematic studies are forming the foundation from which we will be
developing advanced methods for processing and modification of materials using
natural fiber welding.
COIL-4:3
Rational Design of Ionic Liquids for Lipase-catalyzed Reactions
Toshiyuki Itoh (1) , titoh@chem.tottori-u.ac.jp, 4-101 Koyama-minami, Tottori City Tottori
Prefecturte 680-8552, Japan . (1) Chemistry and Biotechnology, Tottori University,
Tottori City Tottori Prefecture 680-8552, Japan
Lipases are the most widely used enzymes applicable for organic synthesis, however,
the reaction rates are significantly dependent on the reaction media and very slow
reactions or poor enantioselective reactions are sometimes obtained. Therefore,
development of a protocol to improve lipase reaction performance is desirable. We have
been investigating the use of ILs for biochemical reactions. Ionic liquid has a certain
advantage over conventional organic solvents, because the solvent makes it possible to
use the enzyme repeatedly and has less-volatile and less-flammable properties.
We also established a powerful means of activating enzyme using ionic liquid
coating.1 Our ionic liquid coated-enzyme (IL-PS) 2
showed excellent reactivity in conventional organic solvent systems and IL-PS
displayed excellent reactivity in several ionic liquids. 3 In my talk, I will
speak the details of results of our investigation for rational design of ionic liquids for
lipase-catalyzed reactions: a very rapid transesterification of secondary alcohols
accomplished when IL1-PS was used as catalyst in 2-methoxyethoxymethyl(tri-nbutyl)phosphonium
bis(trifluoromethanesulfonyl)amide
([P444MEM][TFSA])4 or diethyl(2methoxyethoxymethyl)ammonium
bis(trifluoromethanesulfonyl)amide
([N221MEM][TFSA]) as solvent while perfect enantioselectivity was

maintaining. References 1. (1) Itoh, T.; Matsushita, Y.; Abe, Y.; Han, S-H.;
Wada, S.; Hayase, S.; Kawatsura, M.; Takai, S.; Morimoto, M.; Hirose, Y. Chem.
Eur. J. 2006, 12,9228-9237. (b) Abe, Y.; Hirakawa, T.; Nakajima,
S.; Okano, N.; Hayase, S.; Kawatsura, M.; Hirose, Y.; Itoh, T. Adv. Synth.
Catal. 2008 , 350, 1954. 2. This enzyme (IL-PS) is commercial
available from Tokyo Chemical Industry (B3028). 3. Abe, Y.; Kude, K.; Hayase, S.;
Kawatsura, M.; Tsunashima, K.; Itoh, T.J. Mol. Catalysis B: Enzymatic
2008, 51, 81. 4. Abe, Y.; Yoshiyama, K.; Yagi, Y.; Hayase, S.; Kawatsura,
M.; Itoh, T. Green Chem. 2010, 12, 1976.
COIL-4:4
Molecular Interactions of Ionic liquids: Solutions, Suspensions and Surfaces
Agilio A.H. Padua (1) , agilio.padua@univ-bpclermont.fr, 24 avenue des Landais, BP
80026, Aubiere 63171, France ; Ana Catarina Mendonça (1) ; Ajda Podgorsek (1) ; Alfonso
S. Pensado (1) ; Catherine C. Santini (2) ; José N. Canongia Lopes (3) ; Margarida F. Costa
Gomes (1) . (1) Laboratoire Thermodynamique et Interactions Moleculaires, Universite
Blaise Pascal Clermont-Ferrand & CNRS, Aubiere 63171, France (2) Laboratoire
Chimie, Catalyse, Polymeres, Procedes, CPE Lyon & CNRS, Villeurbanne 69622,
France (3) Centro de Quimica Estrutural, Instituto Superior Tecnico & ITQB, Lisbon
1049-001, Portugal
From the point of view of physical chemistry, ionic liquids are exciting because of their
complexity and they often surprise us with unexpected behavior. The ultimate goal in
this field is to understand how the molecular structures and interactions of ionic liquids
determine their properties, knowledge that is essential for the development of new
materials, devices and processes. Features at the molecular level such as asymmetry,
conformational flexibility, electrostatic charge delocalization and the presence of non
charged and charged moieties in the ions are already challenges in terms of
establishing structure-property relations for liquid systems. Furthermore, ionic liquids
are heterogeneous fluids, both in terms structure and dynamics of the liquid phases.
This introduces an additional level of complexity, at the scale of the nanometer, which
affects solvation and transport phenomena. But this persistent, strong structuring has an
important advantage: it allows functionalization of the ionic liquids for specific
applications without radically changing their essential properties (such as a wide liquid
range and a low volatility). We have worked on the description of molecular interactions
in ever more complex systems based on ionic liquids. We started by studying the
solvation of molecular compounds (role of size, polarity, nature of the interactions) and
the effects of functionalizing the ionic liquids on the thermodynamic and solvation
properties. Examples of applications include ionic liquids for the absorption of carbon
dioxide, biodegradable ionic liquids and media for catalysis. Recent developments focus
on more complex solutes and interfaces, such the synthesis and stabilization of metallic
nanoparticles and the interactions of ionic lubricants with surfaces.
COIL-4:5

Ionic Liquid Based Electrolytes for Lithium and Magnesium Batteries
M. Forsyth (1) , maria.forsyth@deakin.edu.au, Burwood Highway, Burkwood Victoria
3125, Australia ; D. R. MacFarlane (2) ; P. Howlett (1) . (1) ITRI, Deakin University, Burwood
Campus, Burwood Highway, Australia (2) School of Chemistry, Monash University,
Australia
The ability to reversibly plate and strip metals such as lithium in an ionic liquid with a
high degree of efficiency and reversibility has led to significant research activity in the
use of ionic liquids as the electrolyte solvent in lithium metal batteries. Low mass
transport and undesirable ion speciation still plagues these materials when it comes to
achieving rapid charge/discharge and higher energy density characteristics in devices.
This has led to the development of alternative approaches such as the use of small,
highly delocalised anions (eg. fluorosulfonamide, or dicyanamide) and a variety of
molecular additives all of which have a significant beneficial effect on the rate and cycle
life characteristics. These recent developments will be discussed in this talk. Ionic liquid
based electrolytes have also been developed for Mg and Zn based metal/air batteries in
our recent work. The effect of electrolyte chemistry and composition on
physicochemical, transport and electrochemical properties in these systems will be
presented and the behaviour of the batteries based on these materials also discussed.
COIL-4:6
Solidification and Solid State Structures of Ionic Liquids
Anja-Verena Mudring (1) , anja.mudring@rub.de, NCDF 04/398, Bochum NRW 44780,
Germany . (1) Anorganische Chemie I - Festkörperchemie und Materialien, Ruhr-
Universität Bochum, Bochum NRW 44780, Germany
Ionic liquids (ILs) have lately become an important class of solvents and soft materials.
Despite being salts built by discrete cations and anions, many of them are liquid at room
temperature and below. ILs have been used in a wide variety of applications and it has
been realized that the true advantage of ILs is their modular character. Each specific
cation–anion combination is characterized by a unique, characteristic set of properties.
Although ILs have been known for roughly a century, still a vast number of possible ion
combinations has to be exploited and one fundamental question remains inadequately
answered: why do ILs have such a low melting point and do not crystallize readily?
Practical techniques, strategies and methods for crystallization of ionic liquids will be
discussed and the formation of ideal crystals but also of plastic crystals and liquid
crystals by ionic liquid compounds will be discussed. A.-V. Mudring: Crystallization of
Ionic Liquids: Theory and Techniques, Aust. J. Chem. 2010, 63, 544. Work is
supported by the Deutsche Forschungsgemeinschaft in the Priority Program 1191 "Ionic
Liquids".
COIL-4:7

Electron-Transfer in and from Ionic Liquids
Edward W Castner (1) , ed.castner@rutgers.edu, 610 Taylor Road, Piscataway NJ
08854-8066, United States ; Cherry S. Santos (1) ; Heather Y. Lee (1) ; James F. Wishart (2) ;
Tatiana A. Fadeeva (1) . (1) Department of Chemistry and Chemical Biology, Rutgers, The
State University of New Jersey, Piscataway NJ 08854-8066, United States (2)
Department of Chemistry, Brookhaven National Laboratory, Upton NY 11973-5000,
United States
Electron-transfer reactions in ionic liquids (ILs) display different rates and mechanisms
in ionic liquids than in neutral solvents. In this talk, we explore several reasons for such
differences. We note that free energies can differ by more than 1.0 eV for a reaction in
an IL relative to a neutral solvent such as CH3CN. Bimolecular electron-transfer rates
will normally depend strongly on the solvent viscosity, but also on differences in selfdiffusion
rates. To explore these ideas, we compare the temperature dependence of
electron-transfer rates measured using time-resolved fluorescence methods with selfdiffusion
coefficients obtained from pulse gradient spin echo NMR experiments.
Systems studied include both neutral and anionic electron-donors and several photoexcited
fluorophores. The ratio of self-diffusion coefficients for neutral to anionic donors
is about 2.5. Bimolecular rates for some photo-acceptors scale linearly with the
measured self-diffusion, but other acceptors do not show this trend. Photoinduced
intramolecular electron-transfer reactions in donor-bridge-acceptor molecules such as
DMPD-Pro-C343 show rather different electron-transfer behavior in ILs than in neutral
solvents. Our results show that for the DMPD-Pro-C343 system, many of the key
electron-transfer parameters differ significantly between ILs and neutral solvents.
Notably, the driving force for reductive quenching of C343* changes by more than 1.0 V
in going from two ILs to CH3CN and CH3OH. The distribution of observed electrontransfer
rates is much broader for the ILs than for neutral solvents. This work was
supported by the US-DOE Office of Basic Energy Sciences under contract DE-FG02-
09ER16118 at Rutgers and #DE-AC02-98CH10886 at Brookhaven.
COIL-4:8
Transfer of the Fundamental Particles, Electrons and Protons, in Ionic Liquid
Media: from Redox Systems to Superacidic and (Superprotonic) Ionic Liquids
Charles Austen Angell (1) , austenangell@gmail.com, PO Box 871064, Tempe AZ
85287-1604, United States ; Younes Ansari (1) ; Kazuhide Ueno (1) . (1) Chemistry &
Biochemistry, Arizona State University, Tempe AZ 85287-1604, United States
Using various measures of the strength of individual Bronsted acids and bases we
construct a generalized proton energy level diagram 1 . We compare it with the energy
level diagram for oxides of transition metals that is known to broadly determine the
redox behavior of solutions of oxides in oxidic solvents 2 . The only differences in energy
levels from those obtained at a standard concentration in a common solvent, are due to
differences in free energies of solvation in that solvent 3 , which are rarely large. Now we

use this diagram to direct us to the conditions in which a given level of ionicity,
determined by the energy gap across which the proton jumps in forming the protic ionic
liquid) can be placed in different domains of acidity. Of particular interest are domains of
superacidity and superbasicity, of which only the former have so far been explored 4 .
Results for superacidic ionic liquids will be described, with particular attention to
quasifree states of protons that have been observed by means of conductivity-viscosity
comparisons of the Walden form shown in the figure. The superacidic
tetrachloroaluminate of the protonated base [BH + ] has an excess conductivity as large
as that of phosphoric acid, which is presumed due to quasi-free protons. References 1
Belieres, J.-P. & Angell, C. A. Protic ionic liquids: Preparation, characterization , and the
proton transfer energy level diagram. J. Phys. Chem.B 111, 4926-4937 (2007). 2 Wong,
J. & Angell, C. A. Glass: Structure by Spectroscopy. (Marcel Dekker, 1976). 3 Angell, C.
A. Electron free energy levels in oxidic solutions: relating oxidation potentials in
aqueous and non-aqueous systems. J. Solid State Electrochemistry (Bockris
Festschrift) 13, 981 (2009). 4 Belieres, J.-P., .Cherry, B. R., Holland, G. P., Yarger, J. L.
& Angell, C. A. Pure Ionic Liquid Superacids. To be published (2011).
COIL-4:9
Heat Capacity of Ionic Liquids: Experimental Determination and Critical Analysis
Yauheni U. Paulechka (1) , paulechka@bsu.by, Leningradskaya 14, Minsk -, Belarus ;
Andrey V. Blokhin (1) ; Gennady J. Kabo (1) ; Andrey G. Kabo (1) ; Marina P. Shevelyova (1) .
(1) Chemistry Faculty and Reseach Institute for Physical Chemical Problems,
Belarusian State University, Minsk 220030, Belarus
Heat capacity is one of the basic thermodynamic properties of room-temperature ionic
liquids (ILs). The temperature dependence of thermodynamic properties of a compound
such as entropy, enthalpy, and Gibbs energy is calculated from its heat capacity. The
effect of temperature on reaction enthalpies and equilibrium constants is also evaluated
using heat capacities of the participants. Heat capacity of nine ILs was measured in an
adiabatic calorimeter over the temperature range from Tfus (Tg) to 370 K. With the use of
the set of 19 ILs for which the reliable heat capacity data and the density data are
available, it was found that the quotient of heat capacity at constant pressure to volume
remains constant within ±5 % at a given temperature and linearly changes with
temperature in the temperature range of (258 to 370) K. It was demonstrated that the
selection of an IL for technical applications is limited not by its heat capacity but by the
other parameters. At present, experimental data on heat capacity are available for about
one hundred ILs. All these data were compiled and critically evaluated. The factors
affecting the uncertainty of the reported data including sample purity, instrument type
and experimental procedure were analyzed. It was demonstrated that in most works on
heat capacity of ILs the authors underestimate the uncertainty of their measurements.
Using the most reliable data, parameters of correlating equations for temperature
dependence of the heat capacities for 23 compounds of this class were developed. The
recommended data were used to follow general trends in the heat capacity of ILs.

COIL-4:10
Thermal and Catalytic Decomposition of Energetic Ionic Liquids on Pt-Based
Catalysts
Charles J. KAPPENSTEIN (1) , Charles.Kappenstein@univ-poitiers.fr, Chemistry building
B27, Faculty of Sciences, 40 Avenue du Recteur Pineau, POITIERS not applicable
86022, France ; Rachid BRAHMI (1) ; Kamal FARHAT (1) ; Mohammed SAOUABE (1) ; Yann
BATONNEAU (1) ; Niklas WINGBORG (2) ; Carsten SCHARLEMANN (3) ; Alexander
WOSCHNAK (3) . (1) Department of Chemistry, LACCO UMR CNRS 6503, University of
Poitiers, Poitiers 86022, France (2) Department of Energetic Materials, Swedish
Defence Research Agency, FOI, TUMBA 14725, Sweden (3) Department of Aerospace
Engineering - FOTEC, University of Applied Sciences Wiener Neustadt for Business
and Engineering Ltd., Wiener Neustadt 2700, Austria
New monopropellants based on blends of ionic liquid (oxidizers), ionic or molecular
fuels and water (solvent) are currently proposed to replace toxic hydrazine with the
objectives to reduce the environmental concerns and the costs, and to increase the
performance. Among the possible oxidizers we can cite: - Hydroxylammonium nitrate
(HAN), [NH3OH] + [NO3] - - Ammonium dinitramide (ADN), [NH4] + [N(NO2)2] - - Ammonium
nitrate (AN), [NH4] + [NO3] - The decomposition has been followed using different tools:
thermal analysis apparatus (TGA, DTA), dedicated constant volume reactor (pressure
and temperature profiles) and dynamic flow reactor with online mass spectrometer
analysis of the gaseous products associated with Raman spectroscopy and acid base
titration for the trapped products. The figure displays the evolution of the gaseous
products detected by mass spectrometry after the catalytic decomposition of pulses of
aqueous solutions of ADN (50 wt.-%) on a Pt-based catalyst preheated at 150 °C. In the
same conditions, we observe a very limited thermal decomposition of ADN. The
analysis show the formation of major nitrogen N2, minor nitrogen oxide NO and nitrous
oxide N2O and traces of nitrogen dioxide NO2, but oxygen formation was not detected.
Surprisingly, the second major product is nitric acid trapped after the reactor. The
influence of different possible fuels on catalytic or thermal decomposition will be

discussed. This work is
carried out in the frame of the project GRASP funded by the European Community
(Framework Program FP7).
COIL-4:11
Catalytic Ignition of Ionic Liquids for Propellant Applications
Julia Shamshina (1)(2) , shams002@gmail.com, 3100 Fresh Way, SW, Huntsville AL
35805, United States ; H. Waite H. Dykes (1) ; Alton J. Reich (1) ; Roberto DiSalvo (1) ; Marcin
Smiglak (2) ; Robin D Rogers (2) . (1) Streamline Automation, LLC, Huntsville AL 35805,
United States (2) Department of Chemistry and Center for Green Manufacturing, The
University of Alabama, Huntsville AL 35805, United States
There exists a high demand for the development of new and improved propellants as
traditional ones face environmental and safety concerns. Use of ionic liquids (ILs, salts
with melting points below 100 o C) in propellant applications could increase safety by
reducing the hazards currently associated with handling of classical propellants. Work
has focused on ILs that decompose when in contact with S-405 catalyst as observed
with molecular propellants such as hydrazine. These ILs are thermally stable, nonvolatile,
possess low toxicity, and are predicted to possess similar performance with
respect to current hypergolic propellants. In the proof-of-concept study, the ILs were
repeatedly ignited on contact with moderately preheated catalyst (150ºC) and
energetically decomposed with no external ignition source. Acknowledgments, We
thank the US Army Research Office STTR Grant W911NF-08-C-0080 and Air Force
Office of Scientific Research Grant F49620-03-1-0357 for support.
COIL-4:12

Decomposition Products in Thermally Stressed Ionic Liquids
Philipp Keil (1) , philipp.keil@cbi.uni-erlangen.de, Egerlandstr. 3, Erlangen, Germany ;
Axel König (1) . (1) Chair of Separation Science and Technology, University of Erlangen-
Nuremberg, Germany
During long-term operation in industrial applications, ILs are subject to aging processes.
Therewith, process impacting or toxic and volatile decomposition products can be
formed. Thermal decomposition of ILs is often studied by TGA or DSC with emphasis
on the determination of upper limits of thermal stability. [1] MS analysis of the exhausting
gas provides additionally information on the formed volatiles. [2] But it is anticipated that
also non-volatile decomposition products can be formed, e.g. cations with scrambled
alkyl-chains or the ongoing discussed trace impurities coloring many ILs. [3]
Identification and quantification of these dissolved components is difficult either due to
the versatile characteristics or the structural similarity compared to the initial IL.
Additionally, the content of these substances is often at low ppm levels. The
contribution presents the results of our research on long-term thermally stressed ILs.
Some are residues originating from our former experiments on melt crystallization of
ionic liquids and were repeatedly melted. Other samples were stressed systematically
for weeks at moderate temperatures T < 125 °C. Samples stored without and with the
presence of stainless steel acting as catalyst for the degradation are compared with
reference material which was refrigerated. Different decomposition products in the
samples are identified by ion chromatography and hydrophilic interaction liquid
chromatography with multi-detection (conductivity-UV/Vis-PDA–MS 3 ). Molecular
structures of these substances are determined by coupled triple quadrupole MS. The
results are discussed with emphasis on de-alkylation, the formation of cations with
scrambled alkyl chains, the differences between various counter anions and the
influence of Chromium-Nickel steel. [1] P. J. Scammells, J.L. Scott, R. D. Singer; Aust.
J. Chem., 58 (2005) p. 155-169 [2] Y.J. Hao, J. Peng, et al.; Thermochim Acta 501,1-2
(2010) p. 78-83 [3] M. J. Earle, C. M. Gordon, et al.; Anal. Chem.; 79(2) (2006) p. 758-
764
COIL-4:13
Thermal Stability of Mono-, Gemini-, and Trigemini Imidazolium Ionic Liquids.
Andrzej Skrzypczak (1) , andrzej.skrzypczak@put.poznan.pl, pl. M.Sklodowskiej-Curie 2,
Poznan Wielkopolska 60-965, Poland ; Filip Walkiewicz (2) . (1) Department of Chemical
Technology, Poznan University of Technology, Poznan Wielkopolska 60-965, Poland
(2) Department of Chemical Technology, Poznan University of Technology, Poznan
Wielkopolska 60-965, Poland
The great interest of ionic liquids composed bulky ions, is their negligible vapour
pressure, low meting point, good thermal stability which make them liquid over a large
temperature range. They are also non-flammable and easy to recycle compounds.
Room temperature ionic liquids are considered now as potential substitutes to many

traditional organic solvents in reaction and separation systems. This work was initiated
to investigate the relationship between structure and decomposition temperature of
tested ILs. We tested mono imidazolium ILs with alkyl and alkoxymethyl substituent and
also their synthesised gemini analogues with alkyl and α,ω-di(methoxy)alkyl spacer .
Last but not least trigemini imidazolium analogous were synthesised and examined.
Great care was taken to ensure that both the water and halide contents of examined
compounds were minimal.
The decomposition temperature was measured with a Mettler-Toledo DSC and TG/DSC
thermal gravimetric analyzer under a nitrogen atmosphere from 300 up to 800
K.Thermal stability of our compounds was examined in dynamic regime with different
heating rates and in isothermal regime. The kinetics for the thermal decomposition was
also measured. According to obtained results the mechanism of thermal degradation is
proposed. Acknowledgement: This investigation received financial support from the
Polish Ministry of Science and Higher Education NN 209437639.
COIL-4:14
On the Nature of Ionic Liquid-Based Mixtures: a Study of Anion-Cation
Interactions by XPS
Ignacio Jose Villar-Garcia (1)(2) , ignacio.villar-garcia@nottingham.ac.uk, Arat Kilo
Campus, Addis Ababa Addis Ababa PO BOX 1176, Ethiopia ; Peter Licence (1) ; Kevin
Robert John Lovelock (1) ; Alasdair William Taylor (1) ; Robert G Jones (1) ; Emily Francis
Smith (1) ; Bitu Birru Hurisso (1) . (1) School of Chemistry, The University of Nottingham,
Nottingham Nottinghamshire NG7 2RD, United Kingdom (2) Chemistry Department,
Faculty of Chemical and Physical Sciences, College of Natural Sciences, Addis Ababa
University, Nottingham Nottinghamshire NG7 2RD, United Kingdom
X-ray photoelectron spectroscopy (XPS) is becoming established as an analytical
technique for the study of ionic liquid-based samples. 1 However, the acquisition of
accurate information, i.e. binding energies, has encountered difficulties in the past.
Here, we present a general method for charge correcting that ensures the reliable

acquisition of binding energies from ionic liquid systems, allowing comparisons between
samples. 2 Accurately determined binding energies have been used to investigate
cation-anion interactions in non-functionalized ionic liquids. 3 Recently, we extended the
study of anion-cation interactions to functionalized ionic liquids and ionic liquid-based
mixtures. As a result we propose a linear correlation between the hydrogen bond
acceptor properties of the anion and the binding energy of cationic based N 1s XP
spectra for fourteen 1-octyl-3-methylimidazolium-based ionic liquids. Ionic liquid-based
mixtures are a fascinating field of study as the properties of these systems can be finely
tuned by manipulation of the ratios of their constituent ions. Understanding the way ions
mix and interact within the liquid media will provide a greater understanding and control
over the resulting properties of the final ionic liquid-based mixtures and will facilitate
their widespread application. We have used XPS, in conjunction with DSC, to
investigate anion-cation interactions for a range of mixtures of ionic liquids. Differences
in binding energies from pure ionic liquids to mixtures are observed and will be
interpreted in terms of a structural model for ionic liquid-based mixtures. 1. Chem.
Rev., 2010, 110, 5158. 2. Phys. Chem. Chem. Phys., 2011, 13, 2797. 3. Chem.-Eur. J.,
2010, 16, 9018.
COIL-4:15
Ionic Liquids – Solvents for the Size Controlled Synthesis and Stabilization of
Nanomaterials
Thomas J. S. Schubert (1) , schubert@iolitec.de, Salzstrasse 184, Heilbronn Baden-
Wuerttemberg 74076, Germany ; Tom F. Beyersdorff (2) ; Frank Stiemke (1) . (1) IoLiTec
GmbH, Heilbronn Baden-Wuerttemberg 74076, Germany (2) IoLiTec Inc., Tuscaloosa
Alabama 35401, United States
In recent years ionic liquids became interesting solvents for synthesis not only of
organic molecules but also inorganic materials such as metal and metaloxide
nanoparticles [1],[2] . One reason for this development is that ionic liquids can dissolve a
wide variety of metal precursors due to their intrinsic polarization. In addition their
surface properties can influence the growth and shape of the synthesized nanomaterials
and their high thermal stability allows syntheses at temperatures up to 250°C including
a good energy uptake as a consequence of microwave irradiation[3]. It was also shown
that pre-organization of ionic liquids enable the synthesis of three dimensional
nanocrystalline networks[4]. Furthermore the tenside like properties of ILs make them
ideal materials for the dispersion and stabilization of nanoparticles. In this presentation
we will present a new method for the size controlled synthesis of metal nanoparticles
and the influence of the anion on the size of the synthesized materials. With this
technology the synthesis of small metal nanoparticles (1-10nm) and the formation of
stable dispersions of these materials is possible[5] ,[6] . In addition we will show that
nanoparticle-powders can easily be deagglomerated and dispersed in various solvents
by the addition of ionic liquids as dispersants to give stable, easy and safe-to-handle
dispersions. Finally, results of the performed stability test via (PCCS, Nanophox ® ) will
be presented. [1] G. Bühler, C. Feldmann, Angew. Chem. 2006, 118, 4982. [2] M. H. G.

Prechtl, J. D. Scholten, J. Dupont, Molecules 2010, 15, 3441. [3] M. Antonietti, D.
Kuang, B. Smarsly, Y. Zhou, Angew. Chem. 2004, 116, 5096. [4] T. W. Wang, H. Kaper,
M. Antonietti, B. Smarsly, Langmuir 2007, 23, 1489. [5] J. Krämer, E. Redel, R.
Thomann, C. Janiak, GIT 2008, 400. [6] C. Janiak, E. Redel, T. F. Beyersdorff, M.
Klingele, T. J. S. Schubert, DE 2007 038 879.0-43, German Patent.
COIL-4:16
Application of Novel Ionic Liquids to the Extraction of Uranium(VI) from Nitric
Acid Medium and a Study on the Chemical Form of the Uranyl Complexes
Extracted
Thomas J Bell (1) , bell.t.aa@m.titech.ac.jp, 2-12-1-N1-34 O-okayama, Meguro-ku,
Tokyo Tokyo-to 152-8550, Japan ; Yasuhisa Ikeda (1) . (1) Department of Nuclear
Reactors, Tokyo Institute of Technology, Tokyo Tokyo-to 152-8550, Japan
The current commercial process for recovering actinides, such as U and Pu, from spent
nuclear fuel consists of dissolving the spent fuels in an aqueous nitric acid solution
followed by selective extraction using a 30% solution of tri-n-butyl phosphate (TBP) in
kerosene. Hydrophobic ammonium based ionic liquids (HAILs) are expected to have the
potential to act as superior solvents to kerosene because they show high stability to
radiolysis, can help reduce the risk of criticality occurring and are non-volatile and nonflammable.
They are also prepared and purified more simply than many other types of
ionic liquids. Following the preparation of some novel HAILs of the form [R2NR'R”][Tf2N]
[Tf2N = (CF3SO2)2N - ] (see Figure 1) via the metathesis reaction, the extraction behavior
of uranyl species from the aqueous nitric acid solution to the ionic liquid phase was
examined to determine the optimum extraction conditions. The concentrations of uranyl
species in the aqueous phase were analyzed by Inductively Coupled Plasma (ICP) and
the distribution ratios (D) calculated. Based on the results obtained a number show
considerable promise as potential substitutes for kerosene. Examination of the
extracted uranyl complexes indicates that the chemical form in the ionic liquid phase
varies depending on the ionic liquid used and in some cases is different to those
extracted into dodecane (as a proxy for kerosene). The outcome of work to characterize
these complexes will be reported. Figure 1:
COIL-4:17
Novel Aqueous Biphasic Systems Composed of Ionic Liquids and Polyethylene
Glycols: Phase Diagrams and Extraction Ability
Mara G. Freire (1)(2) , maragfreire@ua.pt, Av. República, Ap. 127, Oeiras n.a. 2780-901,
Portugal ; Jorge F. B. Pereira (2) ; María Francisco (3) ; Héctor Rodríguez (3) ; Luís P. N.
Rebelo (1) ; Robin D. Rogers (4) ; João A. P. Coutinho (2) . (1) ITQB2, New University of

Lisbon, Oeiras 2780-901, Portugal (2) Chemistry Department, CICECO, University of
Aveiro, Oeiras 2780-901, Portugal (3) Department of Chemical Engineering, University
of Santiago de Compostela, Santiago de Compostela E-15782, Spain (4) The University
of Alabama, Department of Chemistry and Center for Green Manufacturing, Tuscaloosa
Alabama AL 35487, United States
Aqueous biphasic systems (ABS) consist on two immiscible aqueous-rich phases based
on polymer/polymer, polymer/salt or salt/salt combinations. Due to their aqueous
environment, ABS are actually recognized as biocompatible media for cells, cells
organelles, and biologically active substances. Typical polymer-based ABS have been
largely explored; yet, in the past few years, ionic liquids (ILs) have been suggested as
feasible alternatives to polymeric-rich phases. 1 One of the main advantages of IL-based
ABS relays on the possibility of tailoring their phases' polarities and affinities by an
adequate manipulation of their ions arrangement. As a result, systems composed by
ILs, water and inorganic salts, have been mainly studied for the extraction of distinct
biomolecules. Recently, 2 salting-in/-out effects of ILs in polyethylene glycol (PEG)
aqueous media have been reported. Hence, it can be anticipated that a proper selection
of common polymers with adequate ILs will allow the formation of IL-PEG-based ABS.
Therefore, in this work, novel phase diagrams regarding PEGs of diverse molecular
weights, combined with several imidazolium- and choline-based ILs, were investigated
and will be presented. The systems herein considered cover a broad range of
structurally different ILs and polymers, so that specific interactions and phase formation
ability could be manipulated. From a biotechnological perspective, these systems, in
which the two co-existing phases are aqueous, have a great potential. The partition
coefficients of several biomolecules (ranging from alkaloids to antibiotics) were further
investigated. The results obtained indicate that improved and selective extraction was
achieved, and thus, these systems can be envisaged as a novel approach in
biotechnological separation processes. References [1] Gutowski, K. E.; Broker, G.
A.; Willauer, H. D.; Huddleston, J. G.; Swatloski, R. P.; Holbrey, J. D.; Rogers, R. D., J.
Am. Chem. Soc. 125 (2003) 6632. [2] Canongia Lopes, J. N.; Rebelo, L. P. N., Chim.
Oggi-Chem. Today 25 (2007) 37.
COIL-4:18
Synthesis and Characterization of Lithium Ion Conductors based on Liquid
Zwitterions
Masahiro Yoshizawa-Fujita (1) , masahi-f@sophia.ac.jp, 7-1 Kioi-cho, Chiyoda-ku Tokyo
102-8554, Japan ; Tetsuya Tamura (1) ; Yuko Takeoka (1) ; Masahiro Rikukawa (1) . (1)
Department of Materials & Life Sciences, Sophia University, 7-1 Kioi-cho, Chiyoda-ku
Tokyo 102-8554, Japan
We have synthesized ionic liquids that make their own component ions to immobilize
under a potential gradient. One candidate is the zwitterion structure in which both cation
and anion units attach to the parent molecules. However, most zwitterions have melting
points above 100 o C because of the decrease in the motional freedom of each ion and

molecular interactions. In order to depress the melting point, we synthesized zwitterions
containing oxyethylene (OE) units or long alkyl chain as shown in Fig.1. The effects of
OE units or long alkyl chain on the physical and electrochemical properties were
investigated. The zwitterion containing two OE units (OE2imps) was a viscous liquid
having a glass transition temperature (Tg) at only -35 o C. The zwitterion containing
heptyl group (C7imps) was also a viscous liquid having a Tg at -9 o C. The zwitterions
were mixed with an equimolar amount of lithium bis(trifluoromethylsulfonyl)amide
(LiN(Tf)2) in order to investigate their ionic conductivity. The ionic conductivity of
OE2imps/LiN(Tf)2 mixture was 3.8 x 10 -4 S cm -1 at 80 o C, whereas the ionic conductivity
of C7imps/LiN(Tf)2 mixture was 7.2 x 10 -7 S cm -1 at 80 o C. Ether groups were effective
not only in lowering the crystallinity of zwitterions but also in improving the ionic
conductivity.
COIL-4:19
Depolymerization of Cellulose in a Binary Ionic Liquid System
Matthew P Foley (1) , foley@usna.edu, 572M Holloway Road, Stop 9B, Annapolis MD
21402, United States ; Luke M Haverhals (1) ; David K D Klein (1) ; Paul C Trulove (1) ; Hugh
C De Long (2) ; W Matthew Reichert (3) ; William B McIlvaine (1) . (1) Department of
Chemistry, United States Naval Academy, Annapolis MD 21402, United States (2)
Directorate of Mathematics, Information and Life Sciences, Air Force Office of Scientific
Research, Arlington VA 22203, United States (3) Department of Chemistry, University of
South Alabama, Mobile Alabama 36688, United States
Cellulose is the most abundant bioproduced molecule on the planet and has near
limitless potential as a feedstock for a variety of biofuels. The dissolution,
depolymerization, and dehydration of cellulose are critical steps in the generation of
liquid fuels from cellulose. Our research demonstrates the conversion of cellulose to
desirable products in a single pot utilizing a binary ionic liquid system (BILS). In a BILS,
one ionic liquid (IL) serves a solvent to dissolve cellulose (e.g., 1-butyl-3methylimidazolium
chloride) and the other IL acts as an acid catalyst (e.g., 1-methyl-3-
(4-sulfobutyl)imidazolium trifluoromethanesulfonate) that depolymerizes cellulose by
hydrolyzing the 1,4 glycosidic bonds that link sugar units. The utilization of IL basedcatalysts
may be advantageous because, unlike traditional inorganic acids that have
essentially a fixed activity, IL catalysts may be tailored to control the depolymerization

and the ultimate products of this process. Data are presented that detail BILS
promoted conversion of cellulose to cellobiose, glucose, 5-hydroxymethylfurfural, and
additional products via hydrolytic and follow-on dehydration reaction pathways. Data
suggest that initial stochastic hydrolysis of the cellulose polymer leads to formation of
shorter chains and eventually cellobiose and glucose. Dehydration of glucose leads to
5-hydroxymethylfurfural in high yields.
COIL-4:20
Ionic Liquids in Biopolymer Processing: Converting Chitin Into Feedstock
Chemicals
William M Reichert (1) , reichert@jaguar1.usouthal.edu, 6040 USA Dr South, Room 229,
Mobile AL 36688, United States ; Charles V. Gaston (1) ; Sara C. Lassitter (1) . (1)
Department of Chemistry, University of South Alabama, Mobile AL 36608, United States
With the shift from petroleum to renewable energy sources, a new renewable source of
feedstock chemicals is also needed. A potential source of renewable feedstock
chemicals are biopolymers. One biopolymer of interest is chitin, a polysaccharide
constructed of N-acetylglucosamine, which can be found in various sources from the
exoskeletons of crustaceans and insects to fungi. Chitin can be broken down into its
monomer units using enzymes and acids but there are many drawbacks to these
processes, mainly the inefficient heterogeneous hydrolysis and lack of control of final
products. One obstacle for the hydrolysis of chitin is its insolubility in traditional solvents
without degradation or derivitization. Ionic liquids have been shown to dissolve chitin
without any degradation thus opening new reaction pathways, but there are still
drawbacks to using traditional breakdown methods. Along with their unique dissolution
properties, ionic liquids can incorporate various functionalities into the ionic liquid, such
as acid catalytic functionality. Once dissolved in an ionic liquid, an ionic liquid acid
catalyst can be used to hydrolyze the chitin into N-acetylglucosamine and other
degradation products, which could be used to produce biocompatible polymers or be
further modified. This presentation will discuss the synthesis and characterization of
ionic liquid acid catalysts for the degradation of chitin.
COIL-4:21
Towards Model Systems for Solid Catalysts with Ionic Liquid Layers (SCILL):
Site-Specific Interactions of [BMIM][Tf2N] with Pt and Pd Nanoparticles
Marek Sobota (1) , marek.sobota@chemie.uni-erlangen.de, Egerlandstraße 3, Erlangen
91058, Germany ; Mathias Laurin (1) ; Markus Happel (1) ; Max Amende (1) ; Natalia Paape (2) ;
Martin Schmid (1) ; J. Michael Gottfried (1) ; Florian Maier (1) ; Hans-Peter Steinrück (1) ; Peter
Wasserscheid (2) ; Jörg Libuda (1) . (1) Lehrstuhl für Physikalische Chemie II, Friedrich-
Alexander Universität Erlangen-Nürnberg, Erlangen 91058, Germany (2) Lehrstuhl für
Chemische Reaktionstechnik, Friedrich-Alexander Universität Erlangen-Nürnberg,
Erlangen 91058, Germany

Towards an understanding of IL thin-film based heterogeneous catalysts at the
microscopic level, we have prepared single-crystal-based model systems under
ultrahigh vacuum (UHV) conditions. Ultrathin films of ultrapure 1-butyl-3methylimidazolium
bis(trifluoromethylsulfonyl)imide ([BMIM][Tf2N]) were grown on an
ordered Al2O3/NiAl(110) film precovered with Pd or Pt nanoparticles (model SCILL
catalyst). These systems are investigated by time-resolved infrared reflection absorption
spectroscopy (TR-IRAS). One important result derived from these experiments is
schematically shown in Figure 1. It could be demonstrated that the IL strongly interacts
with the supported nanoparticles and partially replaces even strongly bound ligands
such as preadsorbed CO. This ligand effect is specific to the site and material: For Pt
nanoparticles CO is preferentially replaced from (111) facets and remains adsorbed at
the edges of the particle. For Pd nanoparticles, on the other hand, the adsorption sites
at the particle edges are first depopulated, before desorption occurs from the particle
facets. Furthermore, we find evidence for a ligand-effect of the coadsorbed IL, modifying
the Pt-CO bond via electronic interactions. Our findings strongly support the idea that
for SCILL systems the IL can directly modify active metal centers via specific ligand-
type interactions.[1] Fig. 1:
Schematic representation of the population of CO on Pt and Pd nanoparticles under an
ionic liquid layer (see text for details). [1] Sobota et al., Langmuir, 2010, 26, 7199;
Phys. Chem. Chem. Phys., 2010, 12, 10610; submitted to Advanced Materials
COIL-4:22
Ecodesign of Environmental Benign Ionic Lubricants: Assessment of Ecotoxicity
and Biodegradability
Stephanie Steudte (1) , steudte@chem.univ.gda.pl, ul. Sobieskiego 18, Gdańsk 80-952,
Poland ; Piotr Stepnowski (1) ; Amaya Igartua (2) ; Stefan Stolte (3) . (1) Department of
Enviromental Analytics, University of Gdańsk, Gdańsk 80-952, Poland (2) Tekniker
Foundation, Eibar 20600, Spain (3) Department for sustainable chemistry, University of

Bremen, Center for Environmental Research and Sustainable Technology (UFT),
Bremen 28359, Germany
The philosophy of green or sustainable chemistry is the development of high efficient
technical processes and applications using chemicals with a reduced or eliminated
hazard potential for man and the environment. Therefore the development of chemicals
with optimised technical properties should run in parallel with the minimisation of
(eco)toxicological hazard potentials. Due to their high structural variety- including the
possibility to tune properties like density or viscosity- ionic liquids are an excellent model
substance class for these studies. The physico-chemical properties like high thermal
stability or low vapour pressure of the substances have raised the interest to use ionic
liquids as lubricants in resent years. Beside the optimization for application also the
environmental impact should be considered. Therefore studies on toxicity and
biodegradability have been performed for selected ionic liquids. The compounds, mainly
ammonium based cations, were chosen according to structure-activity-relationships and
their potential applicability as lubricants. Ecotoxicity was tested with several model
organisms varying from isolated enzymes, mammalian cells, marine bacteria and algae
to higher organisms like crustacean. Biodegradation experiments according to different
guidelines were performed as well and data obtained by evaluation of sum parameters
or primary degradation were compared. The present study shows that the design of
environmental benign ionic lubricants is- with limitations- feasible.
COIL-4:23
Controlling the Extent of Proton Transfer in Protic Ionic Liquids: A Combined Ab
Initio and Experimental Study
Ekaterina I Izgorodina (1) , katy.pas@monash.edu, Wellington Rd, Clayton, Melbourne
VIC 3800, Australia ; Douglas R MacFarlane (1) ; Anna Gebhardt (2) ; Martina
Lichtnecker (2) . (1) School of Chemistry, Monash University, Clayton, Melbourne VIC
3800, Australia (2) Chemistry, Ludwig Maximilians University of Munich, Munich 80539,
Germany
Protic ionic liquids (PILs) obtained by proton transfer from a BrØnsted acid to a
BrØnsted base have found a wide range of applications from energy generating devices
such as fuel cells to pharmaceutical industry. A difference between pKa aq values of the
acid and the base represents a thermodynamic criterion for determining the extent of
proton transfer, i.e. degree of ionization in the resulting protic ionic liquid. Angell et al.
established that ∆pKa aq should be > 10 to ensure full ionization. 1 Recently we found 2
that the ability of primary and secondary amines to form additional hydrogen bonding
could promote proton transfer for acid-base mixtures with ∆pKa aq < 10. To investigate
this phenomenon further we performed a systematic study on a number of mixtures of
primary, secondary and tertiary amines with a series of carboxylic acids of increasing
acidity: acetic acid, difluoroacetic acid and trifluoroacetic acid. In order to identify the
extent of proton transfer in these mixtures, a thorough analysis of their IR spectra,
transport properties and ionicity (Walden plot) was performed. A high-level correlated

level of ab initio theory was used to calculate enthalpies of the proton transfer reactions.
Theoretical calculations incorporating two acid and two base molecules resulted in the
formation of cyclic tetrameric species, in which the hydrogens on the nitrogen atom in
primary and secondary amines became involved in additional hydrogen bonding with
the carboxylic group of the acid. Calculated vibrational frequencies of the cyclic species
were in excellent agreement with the experimental spectra. Additionally, the effect of
temperature on ionisation in PILs was studied by means of temperature-dependent IR
spectroscopy. References (1) Yoshizawa, M.; Xu, W.; Angell, C. A. J. Am. Chem.
Soc. 2003, 125, 15411-15419. (2) Stoimenovski, J.; Izgorodina, E. I.; MacFarlane, D.
R. Phys. Chem. Chem. Phys. 2010, 12, 10341-10347.
COIL-4:24
Ionic Liquids for Combined Extraction-MALDI-MS and Extraction-LC-MS
Analytical Tools
Rico E Del Sesto (1) , ricod@lanl.gov, PO Box 1663, MS J514, Los Alamos NM 87545,
United States ; Katherine S Lovejoy (1) ; Geraldine M Purdy (1) ; Srinivas Iyer (2) ; Timothy C
Sanchez (2) ; Cynthia A Corley (3) ; John S Wilkes (3) ; Andrew T Koppisch (2) . (1) Materials
Chemistry, Los Alamos National Laboratory, Los Alamos NM 87545, United States (2)
Biosciences Division, Los Alamos National Laboratory, Los Alamos NM 87545, United
States (3) Department of Chemistry, United States Air Force Academy, USAF Academy
CO 80840, United States
Due to the amphiphilic nature and controlled miscibility with water, ionic liquids can be
used to efficiently extract analytes from aqueous systems. Additionally, the multiple
types of intermolecular interactions of ILs with other species make them suitable to
denaturation of fibrous and textile materials. Extraction of organic and inorganic
compounds from water is readily achieved by using water immiscible ionic liquids. We
have also recently developed an ionic liquid-based system for denaturation of dyed
keratin-based wool fibers, which in the process extracts the associated dyestuffs into
the ionic liquid. The extraction solutions can then be used directly as matrix-analyte
compositions for direct MALDI-MS analysis of the dyes, or used in LC-MS for separation
and identification of the components. The non-volatility of the ILs as well as the
incorporated dyes presents an ideal system to use for MALDI-MS. The extraction
processes are useful for many separations methods, and the combined extractionanalysis
tool is ideally set up for forensics applications.
COIL-4:25
Chameleonic Behavior of Ionic Liquids and Its Impact on the Solubility
Parameters Estimation
Marta L. S. Batista (1) , batista.m@ua.pt, Campus Universitário de Santiago, Aveiro
3810-193, Portugal ; João A. P. Coutinho (1) . (1) Department of Chemistry, University of
Aveiro, CICECO, Aveiro 3810-193, Portugal

Ionic Liquids (ILs) are a new generation of solvents with unique physical and chemical
properties which find use in a wide range of applications. The estimated number of
potential ionic liquids is so large that the characterization of every single ionic liquid
became an impossible task. In this work, it was studied the possibility to develop a
solubility parameter scale, with the purpose of predicting the performance of ILs and
hence, to design and choose the best IL for a specific task. In the estimation of solubility
parameters, data of activity coefficients at infinite dilution, that are plentiful in the
literature, was used. The results allowed the identification of a curious behavior of the
ionic liquids that seem to present more than one solubility parameter, acting as polar
molecule in some situations and as non-polar molecule in others. This behavior was
confirmed using solubility data of [BMIM][PF6] in solvent mixtures. The infinite dilution
activity coefficient based solubility parameters are compared with solubility parameters
based on other properties, namely viscosities and enthalpies of vaporization and the
relation between the various sets of solubility parameters is discussed. The results here
obtained suggested that given the complexity of ionic liquid molecules a unidimensional
solubility parameter scale to characterize these fluids is not feasible.
COIL-4:26
Precised View on Carbon Dioxide Absorption in Ionic Liquids
Roland St. Kalb (1) , roland.kalb@proionic.com; Peter Janiczek (1) . (1) Research &
Development, proionic GmbH, Grambach 8074, Austria
In order to increase the efficiency of gas scrubbing units, a series of investigations were
performed in Ionic Liquids (ILs), which show apparent advantages. Reams of
combinations of anions and cations were analysed for their carbon dioxide (CO2)
absorption capacity and some proposed absorption mechanism were published. In this
work, imidazolium- and quaternary ammonium carboxylates were undergone an x-ray
crystal structure analysis. Without any freedom of interpretation, the chemical
absorption of carbon dioxide in the investigated imidazolium-based carboxylates is
performed via the cation. Similarly, we can state, that the mechanism for examined
quaternary ammonium carboxylates works by astonishing strong interaction with the
anion. Furthermore, influencing parameters for absorption are specified. With this
knowledge, mechanisms for desorption are furthermore presented.
COIL-4:27
Carbon Dioxide Capture with Ionic Liquid Absorbents
Joan F. Brennecke (1) , jfb@nd.edu, Department of Chemical and Biomolecular
Engineering, Notre Dame Indiana 46556, United States ; Samuel Seo (1) ; Brett
Goodrich (1) ; Burcu Gurkan (1) ; Yong Huang (1) . (1) Department of Chemical and
Biomolecular Engineering, University of Notre Dame, Notre Dame Indiana 46556,
United States

Ionic liquids present intriguing possibilities for removal of carbon dioxide from a wide
variety of different gas mixtures, including post-combustion flue gas, pre-combustion
gases, air, and raw natural gas streams. Even by physical absorption, many ILs provide
sufficient selectivity over N2, O2, CH4 and other gases. However, when CO2 partial
pressures are low, the incorporation of functional groups to chemically react with the
CO2 can dramatically increase capacity, while maintaining or even enhancing
selectivity. We will demonstrate four major advances in the development of ILs for CO2
capture applications. First, we will show how the reaction stoichiometry can be doubled
over conventional aqueous amine solutions to reach one mole of CO2 per mole of IL by
incorporating the amine on the anion. Second, we will show how we have been able to
completely eliminate any viscosity increase upon complexation of the IL with CO2, by
using aprotic heterocyclic anions (AHA ILs) that eliminate the pervasive hydrogen
bonding and salt bridge formation that is the origin of the viscosity increase. Third, we
will show that the reaction rates for CO2 with AHA ILs are actually faster than
conventional aqueous amine systems. Finally, we will show how the energy necessary
for CO2 capture and regeneration can be further reduced by using ILs that phase
change upon reaction with CO2.
COIL-4:28
Playing Around with Ionic Liquids and Aqueous Two Phase Systems
João AP Coutinho (1) , jcoutinho@ua.pt, University of Aveiro, Aveiro Aveiro, Portugal .
(1) CICECO, Department of Chemistry, University of Aveiro, Aveiro Aveiro 3810-193,
Portugal
Ionic liquid based aqueous two phase systems (ATPS) have emerged in the last few
years as promising media for the purification of biomolecules. Comparing with the
classical polymer based ATPS the ILs provide a much broader range of phase polarities
and lower phase viscosities allowing for a faster mass transfer and easier fluid handling.
In our research group we have been studying the impact on ATPS formation ability of
the ionic liquid cation and anion type. Both basic and acid inorganic salts, sugars and
aminoacids have been used as ATPS inducing compounds and the ability of these
systems to purify a range of biomolecules has been investigated. Other approaches as
using the ILs to modulate the polarity/extraction ability of the polymer phases or to
replace the salt in polymer based ATPS were also addressed. Results of five years of
research, including a good deal of recent results, on the interactions between salts and
ionic liquids in aqueous solution, their effect upon the formation of ATPS, and the
potential of these systems for biomolecules purification will be revisited, with the
partition of caffeine taken as example. The use of ATPS for analytical purposes, and
recovery of ILs from aqueous solutions will also be addressed.
COIL-4:29
Structure, Properties and Applications of Ionic Liquids

Suojiang Zhang (1) , sjzhang@home.ipe.ac.cn, #1 Beiertiao, Zhongguancun, Haidian
District, Beijing, China., Beijing Beijing, China ; Xiaomin Liu (1) . (1) Institute of Process
Engineering (IPE), Chinese Academy of Sciences, Beijing 100190, China
Ionic liquids (ILs) have shown unique physico-chemical properties differing from
aqueous ionic solutions and high temperature molten salts. Based on the systematic
investigation, hydrogen bond network structure and its three-dimensional expansibility in
ionic liquids were revealed. The influence of hydrogen bonds on the clusters of ionic
liquids was investigated. The multi-scale controlling mechanism of hydrogen bonds on
the reaction and separation performance in ionic liquids was obtained. A
comprehensive physichemical property database of ionic liquids was established. The
force fields were developed and the molecular dynamic simulations were performed for
a number of task-specific ionic liquids. Based on the classification of ionic liquids and
the scientific determination of ionic segments, a periodic variation rule of physical
properties versus the structures and molecular weights of ionic liquids was proposed for
the first time, which provides a new approach to designing and screening suitable ionic
liquids used as catalysts and/or separation media. In view of different environmental
pollution sources, such as CO2, VOCs, PET, etc, series of functional ILs have been
developed and new pollution control technology has been established. ILs are
promising solvents for CO2 capture. We have developed a series of task-specific ILs,
which show good absorption capacity, and the energy consumption could reduce 44%,
compared with conventional aqueous amines method. The degradation technology of
PET polyester by using ILs as solvents/catalysts can reduce solvent loss and
environmental pollution. ILs are ideal electrolyte for the research and application of
electrochemistry owing to their excellent properties. The development of ILs can replace
traditional organic electrolyte and realize the low-temperature electrolysis and refining of
aluminun, magnesium and their alloys, reduce energy consumption and pollutant
release. We are devoted to developing ILs electrolytes, aiming to solve the safety
problem of electrolytes with enhancing battery capacity and extending its using
temperature range.
COIL-4:30
Research and Development of Energetic Ionic Liquids
Tom Hawkins (1) , tommy.hawkins@edwards.af.mil, 10 East Saturn Boulevard, Edwards
AFB CA 93524-7680, United States ; Stefan Schneider (1) ; Adam Brand (1) ; Milton
McKay (1) ; Michael Tinnirello (1) . (1) Space and Missile Propulsion Division, Air Force
Research Laboratory, Edwards AFB CA 93524-7680, United States
Current research programs are aiming to develop ionic liquids (ILs) as energetic
materials for various applications. Such applications for ILs include both propulsion and
explosives. Within the propulsion arena, a focus is to replace hydrazine (a highly toxic
compound) as a fuel. The approach to replacing hydrazine is the synthesis and
development of ILs with substantially less vapor toxicity and superior energy density.
Hypergolic bipropellants are defined as fuel and oxidizer combinations that, upon

contact, chemically react and release enough heat to spontaneously ignite, eliminating
the need for an additional ignition source. The feasibility that an IL can undergo
hypergolic ignition with a common oxidizer like nitric acid was demonstrated for the first
time in our laboratory a few years ago. 1,2 Hazardous characteristics, undesirable
physical and chemical properties of such ILs must be identified before further
development by a potential user. IL-based fuels and their properties will be discussed
(including limited safety and sensitivity, and thermophysical properties). In the
development of advanced explosives, an effort is underway to produce material
replacements for 2,4,6-trinitrotoluene (TNT). Energetic ILs have been synthesized and
characterized as explosive ingredients. The physical and chemical property
characterizations and initial performance evaluations of these molecules indicates ionic
liquids are a promising material approach to high performance explosives. 1. S.
Schneider, T. Hawkins, M. Rosander, G. Vaghjiani, S. Chambreau and G. Drake,
Energy Fuels, 2008, 22, 2871-2872. 2. S.D. Chambreau, S. Schneider, M. Rosander,
T. Hawkins, C.J. Gallegos, M.F. Pastewait and G.L. Vaghjiani, J. Phys. Chem. A, 2008,
112, 7816-7824.
COIL-4:31
Phase Behaviors of Ionic Liquids ---Unique Macroscopic Phenomena Caused by
Microscopic Structural Changes and Cooperative Slow Dynamics---
Keiko Nishikawa (1) , k.nishikawa@faculty.chiba-u.jp, 1-33, Yayoi-cho, Chiba Chiba 263-
8522, Japan . (1) Department of Nanomaterial Science, Chiba University, Chiba Chiba
263-8522, Japan
We studied phase behaviors of various imidazolium-based ionic liquids using a
laboratory-made differential scanning calorimeter (DSC) with nano-Watt stability and
sensitivity, backed up Raman scattering measurements. In addition to common
behaviors for many ionic liquids such as pre-melting over a wide temperature range and
excessive super-cooling, we observed unique thermal phenomena: reversible phase
transitions of domains in the pre-melting region [1], rhythmic crystallization and melting
[1, 2], intermittent crystallization [1, 3], complex phase behaviors [4, 5], and extremely
slow phase transitions and structural relaxations. It is considered that they occur
because an imidazolium-based cations is capable of taking plural stable conformations
and the conformational changes occur linking with phase changes. We also measured
longitudinal and transverse relaxation times (T1 and T2) for 1 H, 13 C-T1 and 13 C spectra
for some imidazolium cations as a function of temperature [6]. Their values and spectra
reveal a close relationship between their unique phase behaviours and the dynamics of
carbons constituting the cations. The temperature dependences of T1 values for
segments of the cations differ greatly, resulting in a variation in the characteristic
thermal behaviours of the salts. Values of 1 H-T1 and 13 C-T1 suggest that some carbons
continue to move even in the crystalline or solid states. Using 13 C-T1 data, we also
estimated the temperature dependences of the correlation times for the segmental
motions of carbons in the liquid states. [1] K. Nishikawa et al. Bull. Chem. Soc. Jpn. 82,
806 (2009). [2] K. Nishikawa et al. Chem. Phys. Lett., 458, 88 (2008). [3] K. Nishikawa

et al. Chem. Phys. Lett., 463, 369 (2008). [4] T. Endo et al. J. Phys. Chem. B 114, 407
(2010). [5] T. Endo et al. J. Phys. Chem. B 114, 9201 (2010). [6] M. Imanari et al. Phys.
Chem. Chem. Phys. 12, 2959 (2010).
COIL-4:32
Ionic Liquid Approaches to Novel Pharmaceuticals
Douglas R MacFarlane (1) , d.macfarlane@sci.monash.edu.au, Wellington Rd, Clayton
Victoria 3800, Australia . (1) School of Chemistry, Monash University, Clayton Victoria
3800, Australia
A large fraction of the pharmaceuticals on the market are organic salts. Normally the
salt involves the active ion and a simple counter-ion such as sodium or bromide.
Substitution of this “ballast” ion by a more complex ion chosen to lower the melting point
of the compound can potentially turn the salt into an IL having pharmaceutical activity.
Such Pharmaceutical Ionic Liquids are now recognised as offering a useful strategy for
modifying the properties of existing actives.(1) As an example of these variations in
properties, the membrane permeability of the active can be manipulated by choice of
the cation. Recent developments have focussed on protic ionic liquid variations of
these pharmaceutically active salts – addressing in this case the complex issue of
proton transfer in the IL medium.(2) Where proton transfer is distinctly absent, hydrogen
bonded complexes can nonetheless form, yielding a liquid equivalent of the co-crystal
phases that are well known in pharmaceutical chemistry.(3) In parallel developments.
ILs are being developed as media for delivery of protein therapeutics, representing a
unique medium for the preservation of the protein structure and activity during
delivery.(4) Recent progress in these areas will be discussed in this talk, including
some of the underlying thermodynamic issues that their behaviour raises. 1.
Stoimenovski J, MacFarlane DR, Bica K, & Rogers RD (2010) Crystalline vs. Ionic
Liquid Salt Forms of Active Pharmaceutical Ingredients: A Position Paper. Pharm. Res.
27(4):521-526. 2. Stoimenovski J, et al (2010) Ionicity and proton transfer in protic ionic
liquids. PCCP 12(35):10341-10347. 3. Bica K, Shamshina J, Hough WL, MacFarlane
DR, & Rogers RD (2011) Liquid forms of pharmaceutical co-crystals: exploring the
boundaries of salt formation. Chem. Commun. 47(8):2267-2269. 4. Foureau DM, et al.
(2010) Development of a New Formulation to Enable Sustained IL-2 Release In Vivo.
Journal of Immunotherapy 33(8):896-896.
COIL-4:33
Separations Using Room Temperature Ionic Liquid Membranes
Richard D Noble (1) , nobler@colorado.edu, UCB 424, Boulder CO 80309-0424, United
States ; Douglas L Gin (1) . (1) Department of Chemical & Biological Engineering,
University of Colorado, Boulder CO 80309-0424, United States

Polymeric versions of ILs have been synthesized and used as membranes for gas
separations. In addition to a physical solvent, RTILs might also be incorporated into
RTIL polymers or in supported ionic liquid membranes (SILMs) as the selective
component. The addition of 20% RTIL into an RTIL polymer increases the permeability
ten fold (100 vs. 10 barrer) while maintaining selectivity. Gelled versions exhibit large
permeabilities (~ 1000 barrers) as well as CO2/N2 selectivities (~ 30) that outperform
many polymer membranes in that application. This presentation provides an overview
of our recent efforts and research directions in the design and synthesis of several new
types of functionalized, imidazolium-based RTILs, poly(RTIL)s, and RTIL-based
composite materials for use in the area of targeted gas separations. Specifically, this
presentation will focus on our design rationales behind several new functional RTIL
materials for (1) the separation or capture of CO2 from N2 and CH4; and (2) the
separation of chemical warfare agent (CWA) simulants and toxic industrial compounds
(TICs) from water vapor or for their specific capture. The first application area is
important for industrial energy production and environmental concerns. The second
application area is important for individual protection in military operations and civilian
emergency first-responder situations. Consequently, it would be extremely desirable to
design new selective membrane systems that provide better selective transport or
capture in these two vapor separation areas. We believe this may be accomplished with
imidazolium-based RTILs because of their unique properties and their chemical and
morphological tunability.
COIL-4:34
Hierarchically Structured Electronic Conducting Polymerized Ionic Liquids
Millicent A. Firestone (1) , firestone@anl.gov, 9700 South Cass Avenue, Argonne IL
60439, United States ; Scott Brombosz (1) ; Sungwon Lee (1) . (1) Materials Science,
Argonne National Laboratory, Argonne IL 60439, United States
Proteins facilitate many key cellular processes, including signal recognition, ion
transport, and energy transduction. The ability to harness this evolutionarily-optimized
functionality could lead to the development of protein-based systems useful for
advancing alternative energy storage and conversion. The future of protein-based
materials (and ultimately devices), however, requires the development of materials that
will stabilize, order and control the activity of the proteins. Furthermore, the full
realization of the potential of protein-based functional materials in the fabrication of
devices requires architectures that ensure assembly of the proteins into high density,
ordered arrays for signal amplification and addressability, components for interfacing
with traditional materials or device platforms, and a means to achieve adequate
mechanical strength and chemical resistance without detriment to the biological
components. Toward this end, our research has emphasized the design, synthesis and
characterization of hierarchical, self-assembled, soft nanostructured architectures that
fulfill these criteria. In this talk our efforts to prepare polymerized ionic liquids (poly(ILs))
that incorporate components that facilitate the interfacing and coupling of protein output
(light-generated electron flow) to traditional device architectures will be presented.

Specifically, these polymers have been modified in two ways so as to promote electrical
communication between the encapsulated proteins and an external circuit. In the first
approach, a hybrid material organizes Au nanoparticles in columns within a hexagonally
perforated lamellar structured poly(IL) to serve as a conduction pathway or conduit. In
the second approach, a thiophene moiety is incorporated into the ionic liquid monomer,
yielding an electrically-conductive polymer.
COIL-4:35
New Ionic Liquid-Based Gel Polymer Electrolytes for Li-ion Batteries
Dane Sotta (1) , dane.sotta@ifpen.fr, Rond-Point de l[apos]Echangeur de Solaize,
Solaize Rhône BP3 69360, France ; Julien Bernard (1) ; Valérie Sauvant-Moynot (1) ; Michel
Armand (2) . (1) IFP Energies Nouvelles, Solaize BP3 69360, France (2) Laboratoire de
Réactivité et Chimie des Solides (UMR CNRS 6007), Amiens 80039, France
Liquid and solid electrolytes incorporating ionic liquids show low volatility, high ionic
conductivities and wide electrochemical stability window. Lithium-ion batteries could
benefit from these new electrolytes to answer both safety and performance issues for
use in transportation applications. Ternary gel polymer electrolytes are prepared by in
situ crosslinking of a epoxide-amine resin containing poly(ethylene oxide) segments in
an ionic liquid – lithium salt binary solution (1-butyl-3-methylimidazolium
bis(trifluoromethanesulfonyl)imide - lithium bis(trifluoromethanesulfonyl)imide). Selfstanding,
transparent, optically homogeneous films are obtained after curing.
Physicochemical properties and ionic conductivity of the gels are discussed according
to the nature of the monomers and the proportions of incorporated ionic liquid. Gel
electrolytes exhibit high ionic conductivities, close to those of the corresponding binary
mixtures of ionic liquid and lithium salt. With conductivities higher than 10 -3 S.cm -1 at
20°C for ionic liquid concentration above 75 wt.%, these gels are well suited to be used
as battery electrolytes. Transport mechanisms discussion will be complemented by
NMR measurements that provide 7 Li and 19 F relaxation times in the gel. The
electrochemical stability window allows the use of LiFePO4 and Li4Ti5O12 as positive and
negative electrodes, respectively. Galvanostatic cycling of these electrodes is
performed in half-cells with gel electrolyte directly cured on the electrode. An

encouraging capacity of about 100 mAh/g of active material is reported for several
cycles of charge/discharge.
COIL-4:36
Conductivity and Dielectric Behavior of Imidazolium-Based Polymers: Structure-
Property Relationships
U Hyeok Choi (1) , uzc101@psu.edu, 316 Steidle Bldg., University Park PA 16802,
United States ; Anuj Mittal (2) ; Minjae Lee (2) ; Yuesheng Ye (3) ; Yossef A. Elabd (3) ; Harry W.
Gibson (2) ; James Runt (1) ; Ralph H. Colby (1) . (1) Department of Materials Science and
Engineering, Penn State University, University Park PA 16802, United States (2)
Department of Chemistry, Virginia Polytechnic Institute and State University, Blacksburg
VA 24061, United States (3) Department of Chemical & Biological Engineering, Drexel
University, Philadelphia PA 19104, United States
Recently there has been growing interest in the polymeric forms of ionic liquids (ILs)
and their potential as a new class of polymers that combine the novel properties of ILs
with the enhanced stability and improved mechanical durability resulting from
polymerization. Since the tunability of the chemical composition of ILs, achieved by
pairing various organic cations with numerous anions, allows for fine control of their
physicochemical properties, it is of great interest to understand the general physical
picture behind the effect of various cation side-chain lengths and different anionic
counterions in polymerized ionic liquids (PILs). Here, we synthesize and characterize
ionic polymers with imidazolium cations covalently attached to the polymer chain with a
variety of alky and alky ether termini and various IL counterins; tetrafluoroborate (BF4),
hexafluorophosphate (PF6) and bis(trifluoromethanesulfonyl)imide (TFSI). The
conductivity as a function of temperature, measured utilizing dielectric relaxation
spectroscopy, is shown in Figure 1. Conductivities and dielectric properties of a range of
monomers and polymers containing IL moieties are compared, leading to insight
regarding optimal design of imidazolium polymers for facile ion transport.

Figure 1. Temperature
dependence of ionic conductivities of polymerized ionic liquids with (a) shortest sidechain
1 , (b) intermediate side-chain 2 and (c) longest side-chain 3 . References 1. K.
Nakamura et al, Macromolecules 2010, 43, 6092. 2. H. Chen et al, Macromolecules
2009, 42, 4809 3. L. Minjae et al, Chem. Mater. 2010, 22, 5814.
COIL-4:37
Developing Robust Ionic Liquid-Based Microextraction Methods for
Pharmaceutical Analysis
Jared L Anderson (1) , jared.anderson@utoledo.edu, 2801 W. Bancroft Street, MS 602,
Toledo OH 43606, United States ; Qichao Zhao (1) ; Tien Ho (1) . (1) Department of
Chemistry, The University of Toledo, Toledo OH 43606, United States
Ionic liquids (IL) possess a multitude of properties that make them very useful solvents
in analytical microextractions. The fact that ILs can be structurally tuned to exhibit vast
versatility in separation science makes them particularly attractive in the analysis of
pharmaceutically-relevant molecules. This talk will focus on (1) the use of ILs in the
extraction of genotoxic impurities (GTIs) from active pharmaceutical ingredients (API)
and (2) the development of a sensitive and selective microextraction technique for
efficient enantiomeric excess determination when ILs are used as the chiral solvent in
asymmetric synthesis. GTIs are a category of compounds that are highly regulated in
the pharmaceutical industry due to their DNA mutagenic effects. New guidelines
imposed by the Food and Drug Administration have lowered the permissible amounts of
these compounds in APIs and has generated the need for new analytical methods to
quantitate and remove these compounds prior to formulation. ILs can be structurally
tuned to selectively extract GTIs from complicated APIs using solid-phase
microextraction (SPME). In addition, results highlighting the use of SPME in the
monitoring of chiral reaction products during asymmetric synthesis in which chiral ILs
are used as the reaction solvent will be presented. The SPME approach using chiral

gas chromatography is highly selective and rapid while also providing the opportunity to
examine reaction kinetics as well as a screening tool for new chiral IL solvents.
COIL-4:38
Alternative Flue Gas Cleaning: Selective Gas Absorption by Ionic Liquids and by
Supported Ionic Liquid Phase (SILP) Absorbers
Rasmus Fehrmann (1) , rf@kemi.dtu.dk, Building 206, Kgs. Lyngby Denmark 2800,
Denmark ; Saravanamurugan Shunmugavel (1) ; Søren Kegnæs (1) ; Johannes Due-
Hansen (1) ; Jacob Abildstrøm (1) ; Anders Riisager (1) . (1) Department of Chemistry,
Technical University of Denmark, Kgs. Lyngby 2800, Denmark
Emission of acidic gases such as NOx, SOx and COx, which are produced by
combustion of fossil fuels during, e.g. energy production in power plants, is a major
concern in relation to atmospheric pollution and climate changes by the so-called greenhouse
effect. Accordingly, these gases have to be effectively removed from flue gases.
Presently this is mainly achieved by relatively energy intensive and resource demanding
technologies via selective catalytic reduction (SCR) of NOX with ammonia, by gypsum
formation after SO2 wet-scrubbing while organic amines are being used as absorbents
in CO2 scrubbers. This leads to concern about, e.g. intensive energy requirements for
desorption, corrosion of steel pipes and pumps, CO2 absorption capacity and thermal
decomposition of the amine. In this work, we demonstrate how ionic liquids (IL) can be
tuned by design to perform as selective, high-capacity absorbents of environmentally
problematic flue gases like, e.g. SO2 , NO and CO2 . Reversible absorption
performance has been tested for several different ILs at different temperatures and flue
gas compositions. Furthermore, different porous, high surface area carriers have been
applied as supports for the ionic liquids to obtain Supported Ionic Liquid-Phase (SILP)
absorber materials. The results show that CO2, NO and SO2 can be reversible and
selective absorbed using different ILs and that SILP absorbers are promising materials
for industrial flue gas cleaning. Absorption / desorption dynamics can be tuned by
temperature, pressure, gas concentrations and the properties of the porous carrier.
COIL-4:39
Separations of Aliphatic and Aromatic Hydrocarbons: Putting Different
Hydrophobic Anions into a Commercial Perspective
Markus A Wagner (1) , markus.wagner@merckgroup.com, Frankfurter Str. 250,
Darmstadt Hessen 64293, Germany ; Marc Uerdingen (1) . (1) PM-ABE, Merck KGaA,
Darmstadt 64293, Germany
In our presentation we will compare the performance of several hydrophobic ionic
liquids with three different anions in three different separation processes. First, we will
briefly outline the differences of ionic liquids based on the following anions:
tetracyanoborate (“TCB”), bis(trifluoromethylsulfonyl)imide (“NTf”) and

Tris(pentafluoroethyl)trifluorophosphate (“FAP”). We will compare data on hydrolytic
stability and thermal stability outlining the differences between ionic liquids comprised of
these different anions. Secondly we will demonstrate how they can be used in two
different separation challenges: (a) separation of alkanes from aromatics and (b)
separation of biobutanol from fermentation broths. Efficient Dearomatization processes
are a key challenge for the (Petro-)chemical industry. Conventional processes comprise
liquid extractions, extractive distillations and azeotropic distillations. Although different
types of entrainers can be used there is still a need to find improved products with
respect to selectivity, capacity and downstream processing. Based on activity
coefficients at infinite dilution data, it can be shown that a large number of ionic liquids
have superior selectivity and capacity properties. We will present results from
cooperation partners with a focus on [1-(3-hydropropyl)pyridinium] [FAP] and [HMIM]
[TCB]. The second part of our presentation will deal with the extraction of butanol from
biomass fermentation broths. Using advanced ionic liquids such as [1-Decyl-3methylimidazolium]
TCB] the current benchmark, oleyl alcohol (OA) could be
outperformed by a number of measures.
COIL-4:40
Opportunities and Challenges of Ionic Liquids in Liquid-Liquid Extraction
Processes in the Petrochemical Industry
Héctor Rodríguez (1) , hector.rodriguez@usc.es, School of Engineering, Rúa Lope
Gómez de Marzoa, s/n, Santiago de Compostela A Coruña E-15782, Spain ; María
Francisco (1) ; Martyn J Earle (2) ; Kenneth R Seddon (2) ; Ana Soto (1) ; Alberto Arce (1) . (1)
Department of Chemical Engineering, University of Santiago de Compostela, Santiago
de Compostela E-15782, Spain (2) QUILL Research Centre, The Queen[apos]s
University of Belfast, Belfast BT9 5AG, United Kingdom

The use of ionic liquids as solvents in liquid-liquid extraction processes has been one of
the most widely proposed applications for these characteristic salts over the last
decade. The suitability of a liquid-liquid extraction process is critically conditioned by the
choice of solvent. Ionic liquids, as neoteric solvents with an appealing set of properties,
may offer new possibilities in the development of liquid-liquid extraction processes. Two
cases of particular interest belong to the field of the petrochemical industry: the
separation of aromatic and aliphatic hydrocarbons, and the desulfurisation of fuels. For
these two applications, a series of studies has been carried out to explore different ionic
liquids as extraction solvents. Emphasis has been put on the thermodynamic analysis of
model systems comprising one ionic liquid and two components to be separated. Liquidliquid
equilibria for these ternary systems have been determined, and key parameters
for assessing the suitability of the proposed solvents have been calculated. An analysis
of the results permits the identification of strengths of ionic liquids for the above
mentioned applications, and at the same time raises some challenges, which will be
discussed.
COIL-4:41
Ionic Liquid Thermal Phase Behavior: Linking Together Ion Structure, Crystal
Packing and Disorder
Wesley A. Henderson (1) , whender@ncsu.edu, 911 Partners Way, Raleigh NC 27695,
United States . (1) Chemical & Biomolecular Engineering, North Carolina State
University, Raleigh NC 27695, United States
The single distinguishing feature of ionic liquids which differentiates them from the
plethora of other known salts is their low melting point. The melting point of a salt is
often assumed to be a fairly straightforward physical property – both conceptually, as
well as its measurement. Deconvoluting the full thermal phase behavior of real salts,
however, can often lead to fascinating discoveries. The melting point of a salt, as well
as other features such as solid-solid phase transitions and the glass transition, are
dictated by both crystal packing and disordering mechanisms available to the ions.
Electrostatic forces ensure that a given ion will be surrounded by counterions. The
manner in which this occurs is governed by molecular interactions such as hydrogen
bonding, steric effects, electron lone-pair repulsions, etc. If the ions are relatively small
and pseudospherical, then they will form a close-packed arrangement. Frequently, such
packing leads to high melting salts. Longer alkyl groups on cations tends to hinder
efficient packing of the ions. As the alkyl chain length increases, the portion of the cation
which is uncharged increases. At low temperature, most salts will form an ordered
crystal structure. As the temperature increases, various modes are available to
accommodate the increasing thermal energy of the system. In some cases, large
amounts of disordering may occur without impacting the crystal packing. Instead, crystal
structural changes occur to provide the additional space needed for these motions.
Melting of the salt occurs when such disordering disrupts the ordered arrangement of
the ions. Frequently very subtle differences in ion structure lead to dramatic changes in
melting point and other properties. These features have been explored in great detail to

gain insight into how these intriguing salts may be manipulated to obtain a given set of
desired properties.
COIL-4:42
NMR Studies on the Rotational and Translational Motions of Ionic Liquids
Composed of 1-Ethyl-3-Methylimidazolium Cation and
Bis(trifluoromethanesulfonyl)amide and Bis(fluorosulfonyl)amide Anions and
Their Binary Systems Including Lithium Salts
Kikuko Hayamizu (1) , hayamizu.k@aist.go.jp, Higashi 1-1-1, Tsukuba Center 5,
Tsukuba Ibaragi 305-8565, Japan ; Seiji Tsuzuki (1) ; Shiro Seki (2) ; Yasuhiro
Umebayashi (3) . (1) Tsukuba Center 5, National Institute of Advanced Industrial Science
and Technology, Tsukuba Ibaragi 305-8565, Japan (2) Central Research Institute of
Electric Power Industry, Komae Tokyo 201-8511, Japan (3) Department of Chemistry,
Faculty of Science,, Kyushu University, Fukuoka Fukuoka 812-8581, Japan
1-Ethyl-3-methyl-imizalium (EMIm) is a popular and important cation and produces
stable ILs with various anions. In this study two amide-type anions,
bis(trifluoromethanesulfonyl)amide (TFSA) and bis(fluorosulfonyl)amide (FSA) were
investigated by multinuclear NMR spectroscopy. In addition to EMIm-TFSA and EMIm-
FSA, lithium salt doped binary samples were prepared (EMIm-TFSA-Li and EMIm-FSA-
Li). The spin-lattice relaxation times (T1) were measured by 1 H, 19 F and 7 Li NMR
spectroscopy and correlation times of 1 H NMR, τc(EMIm) for librational molecular
motions of EMIm and those of 7 Li NMR, τc(Li) for a lithium jump were evaluated in the
temperature range between 253 and 353 K. We found that bulk viscosity (η) and cation
diffusion coefficient DEMIm have good relationships with the τc(EMIm). Similarly linear
relations of the η and DEMIm versus τc(Li) were obtained, respectively. One-jump
averaged distances of Li were calculated from τc(Li) and DLi. The experimental values of
the diffusion coefficients, ionic conductivity, viscosity and density were analysed by the
classical SE, NE and SED equations for the neat and binary ILs to clarify
physicochemical and mobile properties of individual ions.
COIL-4:43
Ion-Ion Interactions and Diffusion Properties of Lithium-Doped Pyrrolidinium
Based Ionic Liquids: PYR14 BETI and PYR14 IM14
Andrea Mele (1) , andrea.mele@polimi.it, Via L. Mancinelli, 7, Milano Italy 20131, Italy ;
Franca Castiglione (1) ; Enzio Ragg (2) ; Giovanni B Appetecchi (3) ; Maria Montanino (3) ;
Stefano Passerini (4) . (1) Dipartimento di Chimica, Materiali e Ingegneria Chimica “G.
Natta”, Politecnico di Milano, Milano, Italy (2) Dipartimento di Scienze Molecolari
Agroalimentari, Università di Milano, Milano, Italy (3) TER Dept., ENEA, Italian Agency
for the New Technology, Energy, and the Environment, Roma, Italy (4) Institute of
Physical Chemistry, University of Muenster, Münster, Germany

Room-temperature ionic liquids (RTILs) gained great interest in recent years as a new
class of electrolyte materials for lithium batteries, solar and fuel cells due to their
peculiar properties. Novel IL based on N-methyl-N-butyl pyrrolidinium (PYR14) cation
with two fluorinated anions: (trifluoromethanesulfonyl)-(nonafluorobutanesulfonyl)imide
(IM14) and bis(pentafluoroethanesulfonyl) imide (BETI) doped with LiX salt (X= BETI or
IM14) at (0.9:0.1) molar ratio were prepared. The two compounds were characterized
using NMR spectroscopy and theoretical calculations. Two-dimensional 1 H and 19 F
pulsed field gradient spin-echo (PGSE) NMR was used to measure independently the
self-diffusion coefficients of the individual ions [1] . 2D heteronuclear HOESY [ 1 H- 19 F]
and [ 1 H- 7 Li] experiments gave us information on cation-cation and cation-anion
interactions in the bulk materials. Combining all the NMR results it was possible to spot
on the local organization and diffusion/conductivity mechanism for the Li-doped
samples. Interesting differences in the transport properties were observed by changing
the anion with a fixed cationic species. DFT calculations were also performed on the
[Li(BETI)2] - and [Li(IM14)2] - complexes to determine the solvation of the lithium ion [2] in
the doped IL. The absolute minimum energy structures for both systems correspond to
a bidentate coordination of the Li + with two oxygen atoms for each involved anion.
[1] F. Castiglione, E. Ragg,
A. Mele, G. B. Appetecchi, M. Montanino, S. Passerini, J. Phys. Chem. Lett. 2011, 2,
153. [2] J. C. Lessegues, J. Grondin, C. Aupetit, P. Johansson, J. Phys. Chem. A 2009,
113, 305.
COIL-4:44
Evaluating the Dispersive and Electrostatic Components of the Cohesive Energy
of Ionic Liquids Using Molecular Dynamics Simulations and Molar Refraction
Data
Jose Nuno Canongia Lopes (1)(2) , jnlopes@ist.utl.pt, Av Rovisco Pais, Lisboa Portugal
1049 001, Portugal ; Karina Shimizu (1) ; Joao M. M. Araujo (2) ; Anabela J. L. Costa (2) ;
Isabel M. Marrucho (2) ; Luis Paulo N. Rebelo (2) . (1) Centro de Quimica Estrutural,
Instituto Superior Tecnico, Lisboa 1049 001, Portugal (2) Instituto de Tecnologia
Quimica e Biologica / UNL, Lisboa 1049 001, Portugal

Recently, the density and the cohesive molar internal energy calculated by molecular
dynamics simulations were correlated with previously reported experimental density and
molar refraction data for seventeen different ionic liquids.[1] The link between the
dispersive component of the total cohesive energy of the fluid and the corresponding
molar refraction was established in an unequivocal way. The results have shown that
the two components of the total cohesive energy (dispersive and electrostatic) exhibit
strikingly different trends and ratios along different families of ionic liquids, a notion that
may help explain their diverse behavior toward different molecular solutes and solvents.
The contributions from the dispersive and electrostatic interactions to the total energy
markedly depend on the nature of the ions. Very large ions such as
tetraalkylphosphonium cations originate disproportionate dispersive contributions.
Strongly basic anions like acetate yield large electrostatic contributions when combined
with cations that can provide acidic hydrogen atoms (e.g., imidazolium-based cations).
These different dispersive/electrostatic energy ratios are directly related to the
polar/nonpolar character of ionic liquids [2] and can explain their diverse behavior
toward different solutes or solvents.[3] Towards a better understanding of this behavior,
molecular dynamics simulations were carried out to calculate the density and the
cohesive molar internal energy of nine ionic liquids. The ionic liquids have a common
cation (cholinium) combined with anions belonging to the carboxylate series, with
varying length of the alkyl side chain, from a number of carbon atoms n = 2 to 9. [1] K.
Shimizu et al. J. Phys. Chem. B 2010, 114, 5831. [2] J. Canongia Lopes et al. J. Phys.
Chem. B 2006, 110, 3330. [3] J. Canongia Lopes et al. J. Phys. Chem. B 2006, 110,
16816.
COIL-4:45
Structure of PEO in Ethylammonium Nitrate and Adsorbed at the Silica Interface
Rob Atkin (1) , rob.atkin@newcastle.edu.au, Chemistry Building, University of Newcastle,
Newcastle NSW 2308, Australia ; Oliver Werzer (1) ; Gregory G Warr (2) . (1) Discipline of
Chemistry, University of Newcastle, Newcastle NSW 2308, Australia (2) School of
Chemistry, University of Sydney, Sydney NSW 2006, Australia
The structure of poly(ethylene oxide) (PEO) dissolved in bulk ethylammonium nitrate
(EAN) has been determined using small angle neutron scattering as a function of
concentration. These measurements reveal that the radius of gyration of PEO in EAN is
smaller than in water, suggesting that EAN is a poorer solvent. The morphology of PEO
adsorbed at the silica – ethylammonium nitrate interface has been investigated using
colloid probe AFM force curve measurements. Steric repulsive forces were measured,
confirming that PEO is able to compete with the ethylamine cation and adsorb to the
silica surface. The range of the repulsive interaction increases with polymer molecular
weight (e.g. from 1.4 nm for 0.01 wt% 10 kDa PEO to 40 nm for 0.01 wt% 300 kDa
PEO) and concentration (e.g. from 16 nm at 0.001 wt% to 78 nm at 0.4 wt% for 300 kDa
PEO). Fits to the force curve data could not be obtained using standard models for a
polymer brush, but excellent fits were obtained using the mushroom model, suggesting

the adsorbed polymer films are compressed and relatively poorly solvated, consisted
with the SANS data.
COIL-4:46
Micro-Patterning and Actuation of Phosphonium-Based Photo-Responsive
Ionogels for Micro-Fluidic Applications
Fernando Benito-Lopez (1) , fernando.lopez@dcu.ie, Dublin City University, Glasnevin,
Dublin Dublin 9, Ireland ; Candice Blin (2) ; Robert Byrne (1) ; Dermot Diamond (1) ; Peer
Fischer (2) . (1) National Centre for Sensor Research, School of Chemical Sciences,
CLARITY Centre for Sensor Web Technology, Dublin 9, Ireland (2) Institute for Physical
Measurement Techniques (IPM), Fraunhofer, Freiburg 79110, Germany
The concept of “Micro-total-analysis-Systems” or “Lab-on-chip” has emerged over the
past 20-years but, despite of the fact their incredible potential to revolutionise analytical
science few products have reached the market so far[1]. Moreover, important issues like
durability, disposability and cost of manufacture slow down the process of the
integration of micro-fluidics into commercially relevant analytical products[2]. We believe
that the next breakthroughs on micro-fluidic technology will come with the development
of unconventional strategies in fundamental material science where 'switchable' or
'stimuli-responsive' materials, that can be remotely switched between forms with
radically different properties, will substitute conventional fluid handling processes in
analytical instrumentation[3]. We present the synthesis, surface patterning and
characterisation of micro-valve structures and channel constrictors that underpin further
movement towards the realization of next generation micro-fluidic components. The
micro-structures are fabricated using novel materials (ionogels) based on phosphonium
ionic liquids (ILs), and photo-responsive polymer gels with spiropyran moieties.
Actuation can be achieved within seconds and easily controlled without the need for any
physical contact between the stimulus source (light) and the resulting action, Figure-1.
Furthermore, the actuation time can be tuned by simply changing the IL-anion, for
instance replacing [NTf2] - by [dca] - without changing the micro-fluidic device.
Figure-1: Microscope images
of glass surface patterned phosphonium NTf2 (left) and dca (right) ionogels before and
after white light illumination. Scanning-Electron-Microscopy (SEM) image of NTf2

ionogel (centre). [1]G.M.Whitesides,LabChip,10,(2010),2317.
[2]R.Murray,Anal.Chem.,82,5,(2010),1569. [3] R.Byrne,etal.,Materials
Today,13,(2010),16.
COIL-4:47
Self-Assembly of Block Copolymers in Ionic Liquids
Paschalis Alexandridis (1) , palexand@buffalo.edu, 304 Furnas Hall, Buffalo NY 14260-
4200, United States ; Aikaterini Tsoutsoura (1) . (1) Department of Chemical and
Biological Engineering, University at Buffalo - The State University of New York, Buffalo
NY 14260-4200, United States
In the context of developing self-assembly as a useful approach to the synthesis and
manufacturing of complex systems and materials, our group has a long-standing
interest on the utilization of selective solvents for the modulation of the organization of
amphiphilic molecules such as block copolymers and surfactants. Room-temperature
ionic liquids (ILs) have emerged as solvents with unique properties, including low vapor
pressure and high thermal stability. We are exploring the self-assembly of amphiphilic
block copolymers in ionic liquids, as affected by the ionic liquid chemical composition
and intermolecular interactions, and as reflected in the stability, structure, and
characteristic length-scales of ordered (lyotropic liquid crystalline) phases formed by the
amphiphile. We discuss here the structuring of poly(ethylene oxide)-poly(propylene
oxide)-poly(ethylene oxide) (Pluronic) block copolymers in the ionic liquids
ethylammonium nitrate (EAN), 1-butyl-3-methylimidazolium tetrafluoroborate
(bmimBF4), and 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF6), and
their mixtures with water.
COIL-4:48
Protic Ionic Liquids: Applications to Non-Humidified Fuel Cells
Masayoshi Watanabe (1) , mwatanab@ynu.ac.jp, 79-5 Tokiwadai, Hodogaya-ku,
Yokohama Kanagawa 240-8501, Japan . (1) Department of Chemistry & Biotechnology,
Yokohama National University, Yokohama 240-8501, Japan
The development of novel proton-conducting materials with little or no dependence on
humidity at temperatures above 100 °C remains an important challenge to the
realization of practical fuel cells. We have shown that certain protic ionic liquids (PILs)
and base-rich melts support active H2 oxidation and O2 reduction under entirely nonhumid
conditions at temperatures higher than 100 °C, which opens up the possibility of
their use as intermediate temperature fuel cell electrolytes. Furthermore, the ionic liquid
electrolytes can be processed into electrolyte membranes by their hybridization with
polymers, which would offer the practical utility in fuel cells. In this study, the
characterization of a PIL, diethylmethylammonium trifluoromethanesulfonate
([dema][TfO]), as a proton conductor for a fuel cell and the fabrication of a membrane-

type fuel cell system using [dema][TfO] under non-humidified conditions at intermediate
temperatures are presented. In terms of physicochemical and electrochemical
properties, [dema][TfO] exhibits high activity for fuel cell electrode reactions, and the
open circuit voltage (OCV) of a liquid fuel cell is determined to be 1.03 V at 150 °C.
Sulfonated polyimides in the diethylmethylammonium form exhibit excellent
compatibility with [dema][TfO]. The composite membranes exhibit good thermal stability,
high ionic conductivity, and mechanical strength and gas permeation comparable to
those of hydrated Nafion. H2/O2 fuel cells prepared using the composite membranes
can successfully operate at temperatures from 30 °C to 140 °C under non-humidified
conditions, and a current density of 250 mA cm −2 is achieved at 120 °C.
COIL-4:49
Task-Specific Ionic Liquids for Energy-Related Applications
Sheng Dai (1)(2) , dais@ornl.gov, 1 Bethel Valley Road, Oak Ridge TN 37831, United
States . (1) Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge TN
37831, United States (2) Department of Chemistry, University of Tennessee, Oak Ridge
TN 37831, United States
Conventional synthesis of electrode materials and electrolytes in energy storage
devices relies heavily on molecular solvents. Alternatively, the synthesis of functional
electrode and electrolyte materials using, or in the presence of, ionic liquids represents
a burgeoning direction in materials chemistry. Ionic liquids are a family of nonconventional
molten salts that can act as both templates and precursors to functional
materials, as well as solvents. They offer many advantages, such as negligible vapor
pressures, high ion conductivities, wide liquidus ranges, good thermal stability, tunable
solubility of both organic and inorganic molecules, and much synthetic flexibility. The
unique solvation environment of these ionic liquids provides unique media for controlling
ion transport and synthesizing electrode materials. Challenges and opportunities in this
research area will be discussed. Acknowledgments: This work was conducted at the
Oak Ridge National Laboratory and supported by the Division of Chemical Sciences,
Geosciences, and Biosciences, Office of Basic Energy Sciences, U.S. Department of
Energy, under contract No. DE-AC05-00OR22725 with UT-Battelle, LLC.
COIL-4:50
Ionic Liquid Production in "Green" Solvents
Aaron M. Scurto (1)(2) , ascurto@ku.edu, 1530 W. 15th St., 4132 Learned Hall, Lawrence
KS 66045, United States ; Sylvia O. Nwosu (1) ; Jay C. Schleicher (3) . (1) Department of
Chemical & Petroleum Engineering, University of Kansas, Lawrence KS 66045, United
States (2) Department of Chemistry, University of Kansas, Lawrence KS 66045, United
States (3) GE, Inc., Houston TX 77027, United States

New applications for ionic liquids in reactions, extractions, engineering fluids, material
synthesis, etc. are being developed at a rapid pace. However, to provide for current and
future large-scale implementation, ionic liquids themselves must be synthesized in a
“green”/sustainable manner and at low cost. However, most currently reported
syntheses are based upon small batch production, and do not have the needed
chemistry/kinetic, heat and mass transport, and thermodynamic phase equilibrium data
for any large-scale development. This presentation will illustrate how molecular level
understanding of the various aspects of the synthesis of ionic liquids in conventional
solvents and environmentally-benign compressed CO2 can lead to greener production
strategies. The effect of alkylating agent and solvent effects on reaction kinetics will be
presented for the synthesis of model imidazolium and pyridinium ionic liquids. Phase
equilibrium thermodynamics, heat and mass transport properties will also be discussed.
Various levels of life-cycle analysis can be used to help determine more optimal
possibilities to help achieve the potential of ionic liquids for future sustainable
processes.
COIL-4:51
Ionic Liquid Monomer Forming Stable SEI on Graphite in PYR14TFSI-LiTFSI
Electrolyte
Elie Paillard (1) , elie.paillard@uni-muenster.de, Corrensstrasse 28/30, Münster NRW
48149, Germany ; Melanie Bedu (2) ; Martin Winter (1) ; Stefano Passerini (1) . (1)
Department of Physical Chemistry, Westfalische Wilhelm Universität Münster, Münster
49149, Germany (2) Site SNPE, Chemin de la Loge, Solvionic S. A., Toulouse 31078,
France
Ionic liquids (ILs) such as N-methyl-N-butyl-pyrrolidinium
bis(trifluoromethanesulfonyl)imide (PYR14TFSI) present negligible vapor pressure, no
flammability, and both high thermal and electrochemical stability. Thus, their use as
electrolytes for Li-ion batteries is investigated. If at first the intercalation of the cation of
the IL in graphite was seen as an interesting property for a new battery concept, in
practice it results in the exfoliation/destruction of the electrode. Most reports, where a
mixture of lithium salt and IL allow reversible Li + insertion into graphite, involve the
expensive bis(fluorosulfonyl)imide anion (FSI - ). Thus, additives such as vinylene
carbonate (VC) have been proposed. Here, we report for the first time the use of 1ethyl-3-vinylimidazolium
bis(trifluoromethanesulfonyl)imide EVIMTFSI as a 5 %wt
additive for SEI formation on graphite in an electrolyte that does not possess intrinsic
SEI forming ability: 0.9 PYR14TFSI-0.1 LiTFSI. Figure 1 shows some voltage profiles
obtained cycling a graphite electrode, using this electrolyte. We observe that the
reduction of the vinyl function occurs above the insertion potential of pyrrolidinium into
graphite (which would occur around 0.8V vs Li + /Li), in the first cycle. It results in a first
plateau and a large irreversible capacity. Nevertheless, reversible capacity starts close
to the theoretical one on the first charge and reaches a stable 460 mA.h.g -1 with
efficiencies higher than 99% after the initial formation cycles as illustrated by cycle 60.

[Figure1] Figure 1. Voltage profiles for a Graphite/5%wtEVIMTFSI-
95%wt(0.9PY14TFSI-0.1LiTFSI)/Li cell
COIL-4:52
NHC Catalytic Activity of Imidazolium-Based ILs
László Nyulászi (1)(2) , nyulaszi@mail.bme.hu, Szt. Gellért tér 4., Budapest H-1111,
Hungary ; Oldamur Hollóczki (1)(2) ; Zsolt Kelemen (1) ; Balázs Németh (1) ; Tamás
Veszprémi (1)(2) ; József Nagy (3) ; Dirk Gerhard (4) ; László Szarvas (4) ; Klemens Massone (4) .
(1) Department of Inorganic and Analytical Chemistry, Budapest University of
Technology and Economics, Budapest H-1111, Hungary (2) Materials Structure and
Modeling Research Group of the Hungarian Academy of Sciences, Budapest University
of Technology and Economics, Budapest H-1111, Hungary (3) Department of Organic
Chemistry and Technology, Budapest University of Technology and Economics,
Budapest H-1111, Hungary (4) BASF AG, Ludwigshafen D-67056, Germany
Dialkylimidazolium salts are an important family of ionic liquids, due to their stability.
While their potential to form catalytically active N-heterocyclic carbenes by
deprotonation has been recognized for a while, this has only been achieved by strong
bases, or by electrolytic reduction. Recently, we have shown by DFT calculations that
the basicity of the counteranion can compete for the acidic proton of the imidazolium
cation even in case of acetate anion. Accordingly, by evaporation of EMIM-acetate at
high temperature and low pressure, we have presented photoelectron spectroscopic
and mass spectrometric evidence demonstrating the presence of the carbene-acetic
acid complex and the free carbene (and acetic acid) in the gaseous phase. Since in the
liquid phase the interaction between the oppositely charged particles stabilizes the ionic
species with respect to the isolated ion pair, the ionic form dominates in the liquid, and
the presence of the carbene remains hidden for spectroscopic investigations.
Nevertheless, for a chemical reaction or for catalytic activity the small concentration
might be sufficient. Accordingly, we could
demonstrate that EMIM-acetate can successfully catalyze benzoin condensation with
good yields if degassed prior to the reaction. In the presence of air further oxidation
reactions – catalysed again by the NHC content of EMIM-acetate - took place. Thus the
combination of the properties of ILs with NHCs is possible. Furthermore the use of
imidazolium-acetates facilitates a simple handling of the NHC source.
COIL-4:53
Did Ionic Liquids Support Origin of Life?
Hiroyuki Ohno (1) , ohnoh@cc.tuat.ac.jp, 2-24 Nakacho, Koganei, Tokyo 184-8588,
Japan ; Kyoko Fujita (1) . (1) Department of Biotechnology, Tokyo University of Agriculture
and Technology, Koganei, Tokyo 184-8588, Japan

Some recent results we obtained strongly inspired us that there should be a great
contribution of ionic liquids to the origin of life in the ancient Earth. At the early stage of
the birth of life, there should have been many component molecules produced by
chance. For the higher functionalization, molecules should construct higher ordered
structure so-called “domain”. The domain can be provided either assembled molecules
or polymers. Considering the major components of life are these assembled molecules
and polymers, polymerization is essentially important to step-up the functionalities of
early stage of these molecules. There are some possibilities that the ionic liquids had
played important roles to prepare condensed phase for polymerizartion. Amino acids
were ionic liquidized with suitable counter ions to enable condensed state of the amino
acids. Nucleic acid bases were also ionic liquidized. These biologically important
molecules were condensed to shift the equilibrium to form macromolecules. In the small
volume of aqueous salt solution, water should be evaporated and there should be
unique environment of ionic liquids composed of biomolecular ions. Also, hydrated
choline dihydrogen phosphate was revealed as a potential solvent for many different
proteins. This is based on the unique biocompatibility of this hydrated salt. The unit
structure of this salt can be seen in the phospholipid molecules for cell membranes[1].
Phosphorylcholine unit is known as a hydrophilic part of major phospholipids. This
structure has been revealed to show excellent biocompatibility. Surface of the cell
membrane might be the vestige of choline dihydrogen phosphate for the protection of
biomolecules and biopolymers. Considering these results, here we propose an exciting
hypothesis that the ionic liquids had supported the origin of life by supplying unique
environment in the ancient Earth. [1] H. Ohno, K. Fukumoto, and J. Kagimoto, 231 st
ACS Meeting Proceedings (I&EC 219) (2006) Atlanta
COIL-4:54
Molecular Structure and Dynamics of Azolium-Azolate Ionic Liquids
Natalia V Pogodina (1) , natalia.pogodina@fmf.uni-freiburg.de, Stefan-Meier Strasse 21,
Freiburg D-79104, Germany ; Ezzeldin Metwalli (2) ; Peter Müller-Buschbaum (2) ; Günter
Dlubek (3) ; Julia Shamshina (4) ; Robin D Rogers (4) ; Christian Friedrich (1) . (1) Material
Research Center (FMF), The University of Freiburg, Freiburg D-79104, Germany (2)
Department of Physics, The Technical University of Munich, Munich D-85747, Germany
(3) The Institute of Innovative Technologies (ITA), Köthen/Halle, Lieskau D-06120,
Germany (4) Center for Green Manufacturing and Department of Chemistry, The
University of Alabama, Tuscaloosa AL 35487, United States
Ionic liquids (IL) are a new class of complex fluids with unique and fascinating physical
properties. Therefore investigation of dynamics and structure of IL is vital for the
fundamental understanding of their physical nature as well as for the successful
engineering design in applications. We investigate physical properties and dynamics of
ILs with different molecular structures (with emphasis on azolium-azolates) in a broad
temperature range (from room temperatures up to glass transition), utilizing differential
scanning calorimetry (DCS), positron annihilation lifetime spectroscopy (PALS),
rheology and small- and wide-angle X-ray scattering (SAXS/WAXS) [1,2]. The important

physical parameters of ILs, such as glass transition (Tg ) and Vogel temperatures,
fragility, volume expansion coefficient and fractional free volume at Tg are determined
and allowed to classify studied ILs as fragile glass-formers. ILs ions interact and form
clusters, the size of which is increasing at lower temperatures. Rheological studies
showed structural heterogeneities, revealed in the deviations from quadratic frequency
dependence of elastic modulus in the terminale zone, peculiar Van-Gurp plots,
thixotropic behavior and broad relaxation time distribution with cooperative ion
dynamics. X-ray scattering peaks provided information about the relative
orientation/distance between ions as well as the structural organization at nanometer
scale. Controlling interactions between IL ions and clusters is the key to IL efficient
performance and novel applications. [1] Yang Yu, G. Dlubek, R. Krause-Rehberg, W
Beichel, S. Bulut, N.V.Pogodina, I. Krossing, and Ch. Friedrich, „The free volume in an
imidazolium triflimide ionic liquid from positron lifetime: amorphous, crystalline and liquid
states“ , J. Chem. Phys. B (2010), v.133, p.124502 [2] N. V. Pogodina, M. Nowak, J.
Läuger, Ch. O. Klein, M. Wilhelm, Ch. Friedrich „Molecular Dynamics of Ionic Liquids as
Probed by Rheology“, J. Rheol. (2011), v.55, p.241
COIL-4:55
Computational Dielectric Spectra of Polarizable Ionic Liquids
Christian Schröder (1) , christian@mdy.univie.ac.at, Waehringerstrasse 17, Vienna
Vienna 1090, Austria . (1) Institute for Comp. Biol. Chemistry, University of Vienna,
Vienna 1090, Austria
Classical molecular dynamics simulations on ILs are based on fixed partial atomic
charges which cannot respond to a local environment. In our polarizable simulations the
induced dipole moments are orientated by the local electric field enhancing singleparticle
dynamics of ILs without changing the structure significantly [1].
Although polarization forces
model the response to the local environment, their influence has a much longer range

affecting the collective dynamics of ILs which can be best seen in spectra of the
generalized dielectric constant ∑*(ν). Furthermore, ∑*(ν) comprises information on
polarity, viscosity, conductivity and the refractive index and may serve to validate our
underlying force field. However, the computational ∑*(ν) can be decomposed in various
contributions not directly accessible by the experiment [2]: The induced collective dipole
moments behave like the rovibrational collective dipole moments [1] and contribute to
the dielectric permittivity. The influence on the dielectric conductivity [3,4] characterizing
the collective translational phenomena beyond the static conductivity is of indirect
nature. A computationally cheap byway to polarization forces is the use of downscaled
permanent partial charges to mimic an effective polarization. This strategy,
however, is only partially successful for the generalized dielectric constant ∑*(ν). [1] C.
Schröder, O. Steinhauser, J.Chem.Phys. 133,154511(2010) [2] C. Schröder, J. Hunger,
A. Stoppa, R. Buchner, O. Steinhauser, J.Chem.Phys. 129,184501(2008) [3] C.
Schröder, O. Steinhauser, J. Chem.Phys. 131,114504(2009) [4] C. Schröder, O.
Steinhauser, J.Chem.Phys. 132,244109(2010)
COIL-4:56
Thermosolvatochromism in Pure and Mixed Ionic Liquids
Anil Kumar (1) , a.kumar@ncl.res.in, Pashan Road, Pune Maharashtra 411008, India .
(1) Division of Physical Chemistry, National Chemical Laboratory, Pune Maharashtra
411008, India
Polarity issues of ionic liquids will be discussed in terms of thermosolvatochromism
response. Various parameters such as polarity index π*, ET parameter, Hydrogen bond
donor and acceptor capabilities, α and ß, respectively of pure ionic liquids at different
temperatures will be presented. Interesting results on the deviations in polarity
parameters from idea behavior in the case of the ionic liquid solutions will be quantified
in terms of preferential solvation models.
COIL-4:57
New Type of Synergetic Catalysis for the Efficient CO2 Chemical Fixation to
Produce Cyclic Carbonates
Jian Sun (1) , jsun@home.ipe.ac.cn, NO.1 Berertiao, Zhongguancun, Haidian district,
Beijing Beijing, China ; Weiguo Cheng (1) ; Jinquan Wang (1) ; Suojiang Zhang (1) . (1)
Institute of Process Engineering,Chinese Academy of Sciences, Beijing Beijing 100190,
China
Both greenhouse effect and resource utilization of CO2 have attracted much attention in
the past decades. One of the most attractive synthetic protocols utilizing CO2 is the
cycloaddition of CO2 to epoxide affording cyclic carbonates (Green Chem., 2010, 12,
1514). Numerous catalysts have been developed for this transformation. Among which,
the combinations of ionic liquids (ILs) with Lewis acid have resulted in many highly

effective processes due to the synergetic catalysis of Lewis acid and IL. Recently,
since phenol acted as a Brønsted acid to accelerate the ring-opening of epoxide
through hydrogen bonding was reported in 2003 (J. Org. Chem., 2003, 68, 6705), two
types of catalysts were developed: hydrogen bonding strengthened functionalized ILs
and similar IL complex systems, and a new type of synergetic catalysis related to
hydrogen bonding was widely proposed correspondingly. The first category includes
CH/Urea (Green Chem., 2007, 9, 169), PANI-HI (Chem. Eur. J., 2007, 13, 6992), HBetI
(J. Mol. Catal. A, 2008, 284, 52), [(CH2CH2OH)mim]Br (Tetrahedron Lett., 2008, 49,
3588), [HDBU]Cl (Adv. Synth. Catal., 2010, 352, 2233), [bmim][Ala] (Lett. in Org.
Chem., 2010, 7, 73), [(CH2)nCOOH)2im]Br (ChemSusChem, 2011, DOI:
10.1002/cssc.201000305), etc. These ILs showed higher activity than traditional ILs due
to the synergetic catalysis of -OH (-H, or -COOH) group and anion of IL. The second
category contains SiO2-PrPBu3I (Chem. Commun., 2006, 1664), KI/β-CD (Green
Chem., 2008, 10, 1337), PPh3BuI/H2O (Tetrahedron Lett., 2009, 50, 423), Cellulose/KI
(Chem. Commun., 2011, 47, 2131), and so on. In these catalytic systems, the hydrogen
boding donors can be solvent, support, and natural products. The above type of
synergetic catalysis will provide a new idea for novel catalyst development especially for
functional ILs.
COIL-4:58
Efficient Production of HMF from Fructose in Ionic Liquids/Solvents Biphasic
System by Employing Supercritical CO2
Suojiang Zhang (1) , sjzhang@home.ipe.ac.cn, Beiertiao 1, Zhongguancun, Haidian
District, Beijing 100190, China, Beijing Beijing 100190, China ; Chunyan Shi (1) ; Jiayu
Xin (1) ; Xingmei Lu (1) . (1) Institute of Process Engineering, Chinese Academy of
Sciences, Beijing Beijing, China
Biomass is a promising alternative for the sustainable supply of valuable intermediates
and liquid fuels, which is abundant, renewable and widely available in nature. Recently,
converting biomass to valuable chemicals and fuels has received extensive attentions.
Among them, HMF produced from carbohydrates has been paid special attentions
because it can be easily obtained from abundant and cheap resources such as sugars,
starch and even cellulosic materials and converted to value-added materials like
medicines, resin plastics, diesel oil additives and biofuels etc. Despite the numerous
value-added approaches for its conversions, HMF is still not produced at large scale
due to its high production and purification costs. Ionic Liquids (ILs) have been found to
be efficient solvents and catalytic systems for the production of HMF. To attain efficient
production of HMF, a biphasic reaction system was designed. It was found that organic
substance/ILs systems are completely miscible in all proportions at atmospheric
pressure. While high pressure CO2 is introduced in organic substance/ILs system,
phase separations can be realized, selective dehydration of fructose is carried out in the
ILs-rich phase and the produced HMF in the ILs-rich phase is continuously extracted
into the organic/CO2 phase. Importantly, the addition of supercritical CO2 to the organic
phase improves the partitioning of HMF into the extracting phase, and leads to

increased HMF yields at lower reaction temperature. Furthermore, this process
eliminates the energy consuming separation steps because ILs were not found in the
HMF containing organic/CO2 phase. Thus, the high purity HMF can be obtained just by
evaporation of low boiling point organic substance. Lastly, the proportion between upper
(organic-rich) and lower (ILs-rich) phases can be adjusted by controlling the pressure,
thus, the distribution of HMF in two phases can be easily controlled.
COIL-4:59
Thermodynamic Properties of Ionic Liquids-Acetonitrile mixtures: Application to
Supercapacitors
Johan Jacquemin (1) , johan.jacquemin@univ-tours.fr, Parc Grandmont, Tours Centre
37200; Thamra Abdallah (1) ; Benedicte Claude-Montigny (1) ; Daniel Lemordant (1) . (1)
Department of Chemistry, University François Rabelais of Tours, Tours 37200, France
Acetonitrile (ACN) has been widely used as solvent in supercapacitors [1] as it presents
many advantages such as a low viscosity, a good conductivity and a high permittivity.
However, owing to its high vapor tension and chemical properties, it is highly flammable
and toxic. Then it is desirable to reduce as much as possible its vapor pressure. As
indicated by the Raoult's law, the addition of an ionic compound, such as ionic liquid
(IL), is able to reduce drastically the vapor pressure of pure ACN, especially when the
solution is non ideal and exhibits a negative deviation to the linearity. The aim of this
investigation is to determine some thermodynamic properties of IL-ACN mixtures.
Excess molar volumes are calculated from density measurements and are fitted to a
Redlish-Kister polynomial equation. In addition, the enthalpies of mixing are determined
by calorimetric measurements. All data are used to determine the evolution of the
solution structure when the composition is varied. References [1] M. Arulepp, L.
Permann, J. Leis, A. Perkson, K. Kumma, A. Jänes, E. Lust, Influence of the solvent
properties on the characteristics of a double layer capacitor, J. Power Sources,
133, 320-328 (2004). [2] P.Wasserscheid, T. Welton (Eds.), Ionic liquids in synthesis,
Wiley-VCH (2002).
COIL-4:60
Linking Structure to the Transport Properties of Ionic Liquid PY15TFSI-LiTFSI
Mixtures
Qian Zhou (1) , qzhou2@ncsu.edu, 911 Partners Way, Campus Box 7905, Raleigh NC
27695, United States ; Wesley A Henderson (1) . (1) Department of Chemical &
Biomolecular Engineering, North Carolina State University, Raleigh NC 27695, United
States
Next-generation batteries for EVs and PHEVs require new electrolytes with high thermal
and electrochemical stability to enable the use of high-voltage electrodes, as well as
ensure long device life and safety at elevated operating temperature and under abuse

conditions. There has been a rapidly expanding interest in using ionic liquids (ILs) as
alternative electrolyte materials for Li-ion battery electrolytes. Such electrolytes,
however, tend to be more viscous and have a lower ionic conductivity than current
state-of-the-art electrolytes. To glean an improved understanding of how ion transports
occurs in IL-based electrolytes, the structural and transport properties of binary
PY15TFSI-LiTFSI mixtures have been examined in detail (Figs. 1 and 2).
Figure 1. Raman spectra of
(1-x) PY15TFSI-(X) LiTFSI mixtures at -150°C, -20°C and -80°C.

Figure 2. Ion packing in the
crystal structure of the (1-x) PY15TFSI-(x) LiTFSI (x = 0.67) (two views shown–rotated
90°) (Li - purple, O - red, S - yellow, N- blue, F - green).
COIL-4:61
Electrocatalysis of AuPd Alloy Nanoparticles Prepared by Simultaneous Sputter
Deposition in Ionic Liquids toward Ethanol Oxidation
Ken-ichi Okazaki (1)(2) , ken-zaki@apchem.nagoya-u.ac.jp, Furo-cho, Chikusa-ku,
Nagoya Aichi 464-8603, Japan ; Masanori Hirano (1) ; Shushi Suzuki (1) ; Susumu
Kuwabata (3)(2) ; Tsukasa Torimoto (1)(2) . (1) Graduate School of Engineering, Nagoya
University, Nagoya Aichi 464-8603, Japan (2) CREST, Japan Science and Technology
Agency, Nagoya Aichi 464-8603, Japan (3) Graduate School of Engineering, Osaka
University, Suita Osaka 565-0871, Japan
Metal nanoparticles (NPs) have attracted considerable interest in the fields of catalysis,
because their size-dependent physicochemical properties are quite different from those
of bulk materials. Furthermore, an alloy exhibits unique catalytic properties distinct from
those of monometallic materials. Therefore, to control the composition and the size of
alloy NPs was one of the key technologies in the fields. As for the electrocatalysis of
fuel cells, it was reported that Pd-based alloy shows high activity for electro-oxidation of
ethanol in alkaline media. Since Pd is a more abundant and less expensive element

than Pt, it is expected that Pd-based alloy NPs are alternative electrocatalysts for
replacing Pt. Recently, we have successfully prepared AuAg alloy NPs in ionic liquids
(ILs) by simultaneous sputter deposition without additional stabilizing agents. Here, we
report the preparation of AuPd alloy nanoparticles by this technique and investigate
their electrocatalytic activity for the ethanol oxidation. The simultaneous sputter
deposition of Au and Pd onto IL (bmim-TFSA) was carried out under an argon pressure
of 20 Pa at room temperature. XRD analyses revealed that the obtained NPs were
AuPd alloy, whose chemical composition was controllable by varying the source ratio of
Pd and Au foils in the targets. The average diameter of the AuPd NPs was determined
from TEM observations to be ca. 2 nm. The obtained AuPd alloy NPs (Au/Pd = 1/1)
were immobilized on HOPG surface, by casting NPs-contained bmim-TFSA on HOPG,
followed by heating at 423 K. The HOPG surface was fully covered with AuPd NPs. The
thus-obtained electrode exhibited 5 times higher current of anodic peak, assigned to
ethanol oxidation, than those of Au or Pd NPs-immobilized electrodes. The onset
potential of anodic current of AuPd alloy NPs electrode was 0.41 V vs. RHE, which was
ca. 50 mV more positive than that of bulk Pt electrode.
COIL-4:62
Transport Properties in Protic Ionic Liquids PILs
Mériem Anouti (1) , meriem.anouti@univ-tours.fr, Parc de grandmont, Tours 37200,
France ; Johan Jacquemin (1) ; Hervé Galiano (2) ; Patrice Porion (3) ; Daniel Lemordant (1) .
(1) Chemistry, Tours University, Tours 37200, France (2) Synthesis and polymeres
transformation, CEA, Tours 37260, France (3) Chemistry CNRS, CNRS - Orléans
University, Orléans 45071, France
Protic ionic liquids (PILs) are a subset of ILs formed by the combination of a Brønsted
acid with a Brønsted base. When a PIL is synthesized by mixing a strong acid with a
strong base, the proton is fixed very tightly to the base. a pulsed-field gradient spin-echo
(PGSE) nuclear magnetic resonance (NMR) method can be applied in order to
determine the self-diffusion coefficients of the individual ionic species over a wide
temperature range. Pyrrolidinium based PILs namely, hydrogen sulfate, [Pyrr][HSO4],
and pyrrolidinium trifluoroacetate [Pyrr][CF3COO] as model of proton conductor PILs,
are characterized with regard to viscosities, diffusivity, and conductivities, at various
temperatures. The self-diffusion coefficients (D) of the cation and anion species in both
studied PILs were independently determined in the same temperature range by
observing 1 H and 19 F nuclei with the pulsed-field gradient spin-echo NMR technique.
With regard to the mechanism of self-diffusion, based on the values of the coefficients,
a relatively large difference was observed between the two ionic liquids (Ils).
Independently of the temperature, the D values indicated that the diffusion of both ions
was similar, signifying that they were tightly bound together as ion pairs. Mobile protons
attached to nitrogen atoms exhibited D values five times higher than those of the
pyrrolidinium cation or hydrogenosulfate anion in [Pyrr][HSO4], and twofold those in the
case of pyrrolidinium trifluoroactetae [Pyrr][CF3CO2]. The temperature-independent
cation transference number and the effective hydrodynamic radius were deduced from

transport properties and Stokes–Einstein equation. Such parameters play an important
role in charge and mass transports in ILs not only from an engineering viewpoint but
also to obtain more fundamental knowledge. proton conduction follows a combination of
Grotthuss- and vehicle-type mechanisms, which confirms that Brønsted acid-base ionic
liquid systems are good candidates as proton conductors.
COIL-4:63
Preparation of Lipid-Inspired Ionic Liquids via Thiol-Ene Reaction and Study of
the Sulfur Position in a C18 Alkyl appendage on their Melting Points.
Arsalan Mirjafari (1) , mirjafari@usouthal.edu, 307 N University Blvd., Mobile Alabama
36688, United States ; Richard A O[apos]Brien (1) ; Kaila M Mattson (1) ; Samuel M.
Murray (2) ; Kevin N West (2) ; James H Davis, Jr. (1)(2) . (1) Department of Chemistry,
University of South Alabama, Mobile Alabama 36688, United States (2) Department of
Chemical and Biomolecular Engineering, University of South Alabama, Mobile Alabama
36688, United States
Previous research in our group investigated the effect of side-chain unsaturation
utilizing imidazolium-based ionic liquids (ILs) with relation to the fluid-mosaic model and
its dramatic effect on melting points. Influenced by the potential of click chemistry, we
explored the thiol-ene reaction with different ene-functionalized ILs by reacting them
photochemically with alkylthiols, yielding lipid-like C18-based ILs, with a thioether
linkage, in a single step. In addition, we utilized differential scanning calorimetry to study
the impact to the IL melting points, based on the sulfur position in the thioether linkage.
Several different ILs were employed as ene substrates for the study. Imidazolium-based
cations with either N-allyl, N-heptenyl, N-octenyl, N-decenyl or N-undecenyl chains were
chosen to assess the effect, if any, of having the sulfur moiety at various chain lengths
from the center of the cationic charge. In addition, two different anions were studied to
discern any control over the course of the thiol-ene reaction. All of the imidazoliumbased
ILs contained a C18 alkyl appendage, similar to that of a natural fatty acid, with a
thioether linkage at various positions within the alkyl chain. The synthetic methodology
will be discussed, as well as the impact of these structural modifications upon IL melting
points and computational insights into their basis.
COIL-4:64
Design of Organoboron Ion-Gels as Lithium Ion Transport Matrix

Noriyoshi Matsumi (1) , matsumi@jaist.ac.jp, 1-1 Asahidai, Nomi, Ishikawa 923-1292,
Japan, Nomi Ishikawa 923-1292, Japan . (1) School of Materials Science, Japan
Advanced Institute of Science and Technology, Nomi Ishikawa 923-1292, Japan
Design of organoboron electrolytes is attractive approach to prepare highly conductive
matrix with high lithium transference number. So far, a variety of solid polymer
electrolytes including boron atom in their main chain were prepared using hydroboranes
as key precursor [1]. This method was also successfully extended to the preparation of
organoboron ionic liquids[2]. In the present paper, we report design of organoboron
ion-gels and their ion conductive properties in detail. First, novel organoboron ion-gels
including lithium borate structure were facilely prepared by condensation of cellulose
with boric acids in ionic liquid in the presence of LiOH aq [3]. The ionic conductivity of
ion-gels including 7 wt% of EMImCl was comparable to that of ionic liquid. Non protic
ion-gels were also prepared by dehydrocoupling reaction of cellulose with hydroboranes
in ionic liquids, which showed ionic conductivity of exceeding 10 -4 Scm -1 . Organoboron
ion-gels of high thermal stability were also prepared by in-situ polymerization method. A
radical polymerization of ionic liquid monomer and borosilicate matrix formation by solgel
processing were carried out simultaneously to give homogeneous hybrid electrolyte.
The hybrid electrolytes obtained showed maximum ionic conductivity of 2.6 x 10 -3 Scm -1
at 50 o C. These transparent and homogeneous hybrid materials were found to be stable
up to 400 o C< from thermogravimetric analysis. References 1. N. Matsumi, K. Sugai,
H. Ohno, Macromolecules 2002, 35, 5731.; N. Matsumi, K. Sugai, H. Ohno,
Macromolecules 2003, 36, 2321. 2. N. Matsumi, M. Miyake, H. Ohno, Chem. Commun.
2004, 2852.; N. Matsumi, K. Sugai, M. Miyake, H. Ohno, Macromolecules 2006, 39,
6924. 3. N. Matsumi, Y. Nakamura, K. Aoi, T. Watanabe, T. Mizumo, H. Ohno, Polym.
J. 2009, 41, 437. Acknowledgement We are grateful to financial support for the
present study by New Energy and Industrial Technology Development Organization
(NEDO) of Japan.
COIL-4:65
Ionic Liquids for In Situ and Downstream Product Recovery of Fine Chemicals
and Biofuels from Fermentation Systems
Aaron M. Scurto (1)(2) , ascurto@ku.edu, 1530 W. 15th St., 4132 Learned Hall, Lawrence
KS 66045, United States ; Satya Aravind Gangu (1) . (1) Department of Chemical and
Petroleum Engineering, University of Kansas, Lawrence KS 66045, United States (2)
Bioengineering Program, University of Kansas, Lawrence KS 66045, United States
Fermentation (whole-cell biocatalysis) is used to produce a large variety of chemicals
and fuels, often from a variety of biomass sources. Efficient and low-energy separations
are the key to sustainable processes. While batch fermentation followed by separation
is the most common method, in situ separations with immiscible solvents may allow
even higher throughput and efficiency due to lower product inhibition of the
microorganisms. Two of the most important properties for biphasic systems are: 1)
advantageous solute partitioning into the solvent phase and 2) low toxicity of the solvent

to the microorganism. However, few types of organic solvents are flexible enough to be
good extractants for the product, biocompatible to the microorganism, have low energy
requirements and have a low human and environmental impact. Biphasic biocatalysis
with ionic liquids may overcome some of these issues. In the present work, a
methodology will be presented towards optimized in situ fermentation extraction utilizing
ionic liquids. The liquid-liquid equilibrium (partitioning) of solutes such as butanol,
ethanol, acetone and (+)-cis-(1R,2S)-1,2-napthalene dihydrodiol (NDHD) between water
and a model ionic liquid, 1-hexyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)amide
([HMIm][Tf2N]) have been measured. The results indicate that high partition coefficients
and large selectivities over water can be achieved. These data have been used to
simulate a system where an ionic liquid is used for initial extraction of butanol followed
by distillation. Compared with the industrially optimized distillation method, the IL-based
approach requires lower heat duties. Molecular toxicity was measured and expressed
as EC50 values by observing growth curves with various concentrations of the IL to the
IL saturation point. The effect of the cation and anion has been investigated for
imidazolium ionic liquids (1-alkyl-3-methylimidazolium [RMIm]), quaternary ammonium,
and phosphonium ionic liquids. Initial studies into the mechanism of toxicity of ILs to
microorganisms will be presented.
COIL-4:66
Effect of Cation Symmetry on the Thermal Denaturation of Proteins by
Imidazolium Ionic Liquids
Edward L. Quitevis (1) , edward.quitevis@ttu.edu, Box 41061, Lubbock TX 79409,
United States ; Julie A. Krapfel (1) ; Stephen C. Bacon (2) ; Naveed Nooruddin (1) . (1)
Department of Chemistry & Biochemistry, Texas Tech University, Lubbock TX 79409,
United States (2) Department of Mechanical Engineering, Prairie View A&M University,
Prairie View TX 77446, United States
The effect of 1-propyl-3-methylimidazolium bromide ([C3C1im]Br) and 1,3 -
diethylimidazolium bromide ([C2C2im]Br) on the thermal denaturation of ribonuclease A
(RNase A) has been studied by the use of differential scanning calorimetry. These ionic
liquids (ILs) differ only in the symmetry of the alkyl substitution on the imidazolium ring
of the cation. Previous studies have shown bromide salts shift the denaturation
temperature Tm to lower temperatures. Our results indicate that both of the above
bromide salts shift Tm to lower temperatures, but the shift is less for the symmetric
[C2C2im] + cation than for the asymmetric [C3C1im] + cation: At pH 5.5, Tm = 61.7 ± 0.1 o C
in IL-free solution; Tm = 49.5 ± 0.1 o C in 1.5 M [C2C2im]Br solution; and Tm = 47.9 ± 0.2
o C in 1.5 M [C3C1im]Br solution.
COIL-4:67
Structural and Rheological Characterization of Pluronic Wormlike Micelles in
Ionic Liquids

Carlos R Lopez-Barron (1) , lopez@udel.edu, 150 Academy St, Newark DE 19716,
United States ; Norman J Wagner (1) . (1) Department of Chemical Engineering,
University of Delaware, Newark DE 19716, United States
Self-assembly of amphiphilic molecules in ionic liquids has been topic of extensive
study during the last decade. We have begun a systematic study to understand the
aggregation of surfactants and block copolymers in protic ionic liquids. One of the most
interesting morphologies we have found is wormlike micelles (WLM). These are formed
when Pluronic L121 (EO5PO70EO5) is dissolved in ethylammonium nitrate (EAN). Using
a combination of experimental methods including rheology, cross-polarized light
microscopy, small angle neutron scattering and conductivity measurements, we
characterized the phase diagram of L121/EAN. SANS measurements reveal that this
system self-assemble into a mass fractal network of cylindrical micelles. This highly
interconnected structure is responsible of the high viscoelasticity with very long
relaxation times as measured by shear rheology. Phase separation, marked by a sharp
decrease in the viscosity and solution cloudiness at T>40 °C, generates a morphology
made of micro-domains with lamellar morphology dispersed in dilute liquid. The cloud
point is also marked by a sharp change in the solution conductivity.
COIL-4:68
Accelerated Enzymatic Hydrolysis by Microwave-Assisted Pretreatment of
Biomass in Ionic Liquids
Sung Ho Ha (1) , shha@hnu.kr, 461-6 Jeonmin-dong, Yuseong-gu, Daejeon 305-811,
Republic of Korea ; Yoon-Mo Koo (2) . (1) Department of Chemical Engineering and
Nano-Bio Technology, Hannam University, Daejeon 305-811, Republic of Korea (2)
Department of Biological Engineering, Inha University, Incheon 402-751, Republic of
Korea
Room temperature ionic liquids (ILs) have recently been very popular as green solvents
due to their unique physicochemical properties of negligible vapor pressure, nonflammability,
excellent thermal stability and a strong ability to dissolve a wide range of
organic and inorganic compounds. They also have great potential as reaction media or
co-solvent for enzymatic bioconversion including biodiesel production. Cheap glucose
from cellulose opens a wide window of opportunities for the production of bioenergy and
plartform chemicals. Nevertheless, the recalcitrance of cellulose poses a key problem
for chemcial and biological processes in biorefinery schemes. Dissolving cellulose in
ionic liquids, however, helps to overcome the hurdles of the low reactivity of the
cellulose fibers resulting in the enhancement of enzymatic saccharification and
fermentation. In this presentation, the application of ILs in biomass pretreatment will be
mainly addressed. ILs have been used as alternative solvent for cellulose
pretreatment. Pretreatment of biomass is key factors for enhance enzymatic
saccharification and fermentation of biomass for biofuel and bio-based chemical
industry. The ILs-pretreated celluloses become less crystalline and in somewhat
condition have lower degree of polymerization (DP) than that of the nature. Microwave

heating could cause a significant decrease in DP of cellulose dissolved in ILs which led
to a great improvement on cellulase-catalyzed cellulose hydrolysis.
COIL-4:69
Physicochemical Properties of Maize Cob Cellulose Powders Reconstituted from
Ionic Liquid Solution
Héctor Rodríguez (1)(2) , hector.rodriguez@usc.es, School of Engineering, Rúa Lope
Gómez de Marzoa, s/n, Santiago de Compostela A Coruña E-15782, Spain ;
Chukwuemeka P Azubuike (3)(1) ; Augustine O Okhamafe (4) ; Robin D Rogers (1)(5) . (1)
QUILL, School of Chemistry and Chemical Engineering, The Queen[apos]s University of
Belfast, Belfast BT9 5AG, United Kingdom (2) Department of Chemical Engineering,
University of Santiago de Compostela, Belfast BT9 5AG, United Kingdom (3)
Department of Pharmaceutics and Pharmaceutical Technology, Faculty of Pharmacy,
University of Lagos, Lagos, Nigeria (4) Department of Pharmaceutics and
Pharmaceutical Technology, Faculty of Pharmacy, University of Benin, Benin-City,
Nigeria (5) Department of Chemistry and Center for Green Manufacturing, The
University of Alabama, Belfast BT9 5AG, United Kingdom
Annually renewable agricultural residues represent an abundant, inexpensive, and
readily available source of cellulose. The main problem which has prevented the wide
use of cellulose as a renewable source of chemicals is that it is insoluble in common
solvents. A renewed interest on techniques for cellulose processing and modification
has arisen as a result of the discovery of specific ionic liquids as solvent systems for
cellulose activation/solubilization. In this work, native α-cellulose was extracted from an
agricultural residue (maize cobs) using a non-dissolving method based on inorganic
substances, and then a modification of its physicochemical properties was induced by
dissolving it in the ionic liquid 1-butyl-3-methylimidazolium chloride ([C4mim]Cl), followed
by regeneration via addition of water or acetone. A thorough characterization was
carried out for the samples obtained, including X-ray diffraction and infrared
spectroscopy studies, and thermal and physical properties determination. Spectroscopic
results confirmed the expected conversion of the crystalline cellulose I structure of
native α-cellulose to cellulose II after dissolution and precipitation in [C4mim]Cl.
Thermogravimetrical analysis and differential scanning calorimetry data showed quite
similar thermal behavior for all cellulose samples, although with somewhat lower
stability for the regenerated celluloses, as expected. The comparison of
physicochemical properties of the regenerated celluloses and the native cellulose
mainly suggests that the regenerated ones may have better flow properties. No
substantial differences were observed among regenerated celluloses produced by
addition of the different antisolvents at different conditions. From the results of the
characterization developed, it can be concluded that the cellulose II powders derived
from maize cob and generated by dissolution and reconstitution from [C4mim]Cl can
imply a better processability, e.g., for their use as excipients in the pharmaceutical
industry.

COIL-4:70
Interactions of Choline-Based Ionic Liquids with Lipid Vesicles: Effects on the
Gel-To-Liquid Crystalline Phase Transition
Gloria D Elliott (1) , gdelliot@uncc.edu, 9201 University City Blvd., Charlotte NC 28223-
0001, United States ; Katherine D Weaver (1) ; Matthew Van Vorst (1) ; Ranganathan
Vijayaraghavan (2) ; Douglas R MacFarlane (2) . (1) Department of Mechanical Engineering,
University of North Carolina at Charlotte, Charlotte NC 28223-0001, United States (2)
Department of Chemistry, Monash University, Clayton Victoria, Australia
Choline-based ionic liquids have been investigated as potential stabilizers in therapeutic
protein formulations but, because of their relative novelty, questions remain as to their
true biocompatibility upon delivery into the body. In the current work model membranes
have been used as analogs to human cells, to explore the nature of ionic liquid toxicity
and to identify possible adverse effects on membrane structures. Differential scanning
calorimetry was used to investigate the effects of choline based ionic liquids and control
compounds upon the sol-gel transition of unilamellar vesicles prepared from 1,2dipalmitoyl-3-sn-phosphatidylcholine.
The midpoint of the transition,Tm, the change in
enthalpy, ∆H, and the width of the transition peak at half-height, ∆T½, were used to
classify the nature of the interaction with the membrane. Choline chloride and choline
dihydrogen-phosphate showed no significant effect on Tm, or ∆H but did lower ∆T½
indicating an increase in cooperativity of the gel-to-liquid crystalline phase transition,
consistent with a non-penetrating/non-interacting compound. Choline bis(2,2,4trimethylpentyl)
phosphinate significantly decreased Tm but only slightly affected ∆H and
∆T½, an effect observed with surface active compounds. Choline tartarate and choline
levulinate caused slight decreases in Tm and ∆H but showed significant increases in
∆T½ indicating a decrease in the cooperativity of the gel-to-liquid crystalline phase
transition. This is frequently seen with membrane-penetrating compounds. The degree
of depression in the Tm values was compared to calculated LogPow coefficients and a
clear trend was not apparent except that the compound which most significantly
depressed Tm, choline bis(2,2,4-trimethylpentyl) phosphinate, did have the highest
LogPow value and indicated a high degree of lipophilic character. This observation also
coincides with the known toxicity of this compound. It is clear from these studies that the
anion can significantly affect interactions with lipid-based model membranes.
COIL-4:71
Probing Transport in Ionic Liquids and Ionomer Membranes Using Multi-Modal
NMR
Zhiyang Zhang (1) , zhiyangz@vt.edu, 119 Davidson Hall, Blacksburg VA 24060, United
States ; Jianbo Hou (1) ; Louis A Madsen (1) . (1) Department of Chemistry, Virginia Tech,
Blacksburg VA 24060, United States

Transport behaviors in ionic liquids (ILs) play a crucial role in the performance of ILbased
electrolyte applications. We are evaluating how the myriad cationic and anionic
species (single ions and aggregates) present in ILs contribute to transport. Pulsed-fieldgradient
NMR (PFG-NMR) is a non-destructive and powerful method to investigate selfdiffusion,
allowing measurement of distinct species by using spectral separation
(chemical specificity). Due to the ~ 10 ms timescale of PFG-NMR, we observe the
weighted average diffusion coefficient over charged and neutral species. PFG-NMR
with an added electric field pulse (electrophoretic NMR) can additionally measure the
electrophoretic mobilities of only charged species. We are investigating transport
properties of cations and anions of ILs, as well as ILs inside ionomer-based “artificial
muscle” actuators using PFG-NMR and electrophoretic NMR. In order to understand ion
aggregation, we are measuring transport properties of cations and anions in mixtures of
1-ethyl-3-methyl-imidazolium tetrafluoroborate (C2mim-BF4) and water. In dilute
solution, the measured mobilities and the mobilities estimated from diffusion coefficients
(via Nernst-Einstein) are similar, indicating free motion of single ions. As ionic solutions
become more concentrated, clearly ions do not travel independently. Furthermore, we
are working on electrophoretic NMR experiments to measure mobilities of ILs inside
mechanical actuators, with implications for describing anomalous actuation behaviors
that likely arise from ion aggregation. Finally, we will discuss how the combination of
PFG-NMR and electrophoretic NMR can give quantitative information on the individual
contributions of different charged species to the ionic conductivity of ILs.
COIL-4:72
Effects of Dialkylphosphate Ionic Liquids on Cloned and Metagenomic Enzymes
Marie F. Thomas (1) , mthomas@bnl.gov, PO Box 5000, Upton New York 11973, United
States ; Luenluen Li (2) ; John Dunn (2) ; James F. Wishart (1) ; Niels van der Lelie (2) . (1)
Department of Chemistry, Brookhaven National Laboratory, Upton New York 11973,
United States (2) Department of Biology, Brookhaven National Laboratory, Upton New
York 11973, United States
Dialkylphosphate ionic liquids are increasingly being studied for the pretreatment of
biomass. It is well known that residual ionic liquid left in processed samples can have
detrimental effects on cellulases used for enzymatic hydrolysis. However based on the
existing literature, dialkylphosphate ionic liquids appear to be less denaturing to these
enzymes. In this study, the stability of a β-glucosidase cloned from the straw mushroom
Volvariella volvacea and four metagenomic enzymes were examined in 1,3dimethylimidazolium
dimethylphosphate [mmim][dmp], 1-ethyl-3-methylimidazolium
dimethylphosphate [emim][dmp], and 1-ethyl-3-methylimidazolium diethylphosphate
[emim][dep]. For comparison, the enzymes were also examined in 1-ethyl-3methylimidazolium
acetate [emim][OAc], which is commonly used for the pretreatment
of lignocellulosic materials. The enzymes were most active in the dimethylphosphate
ionic liquids. The effects of ionic liquid structure on enzyme activity will be discussed.
This work was supported by a Laboratory-Directed Research and Development grant
from Brookhaven National Laboratory, under contract #DE-AC02-98CH10886 with the

U. S. Department of Energy Office of Basic Energy Sciences and the BioEnergy
Science Center. The BioEnergy Science Center is a U.S. Department of Energy
Bioenergy Research Center supported by the Office of Biological and Environmental
Research in the DOE Office of Science.
COIL-4:73
Ionic Liquids Comprised of Biologically Active Amines
John R Canada (1) , jrcanada@crimson.ua.edu, 250 Hackberry Lane, Tuscaloosa AL
35487; Parker D McCrary (1) ; Preston A Beasley (1) ; Asako Narita (1) ; Robin D Rogers (1) .
(1) Department of Chemistry and Center for Green Manufacturing, The University of
Alabama, Tuscaloosa AL 36487, United States
Biologically active amines are found to have acute oral toxicities of above 2000 mg/kg in
rats. We have made ionic liquids based upon these edible amines with common active
pharmaceutical ingredients (APIs). The amines are used to control the physical and
chemical properties of the target APIs while not adding toxicity. We are currently
investigating the physical, chemical, and biological properties of these new salts, as well
as conducting solubility tests. This presentation will discuss our current progress and
future challenges.
COIL-4:74
Anomalous Diffusion of Ionic Liquids Inside Ionic Polymers
Jianbo Hou (1) , jianbo@vt.edu, Davidson Hall 107, Department of Chemistry,
Blacksburg Virginia Tech 24061, United States ; Louis A Madsen (1) . (1) Department of
Chemistry, Virginia Tech, Blacksburg Virginia 24061, United States
Ionic liquids (ILs) are promising candidates in applications ranging from fuel cells to
lithium-ion batteries to soft mechanical actuators. When combining ILs with ionic
polymers, topological features such as domain structure and connectivity within the
polymer network will impact ion transport. These features strongly determine the
performance of IL+polymer-based materials and devices. We will present novel
phenomena regarding ion diffusion of ILs inside ionic polymers using pulsed-fieldgradient
(PFG) NMR. The chemical specificity of NMR allows separate measurement of
cation ( 1 H) and anion ( 19 F) diffusion. Our measured ion diffusion coefficients (Dcation and
Danion) exhibit strong dependence on both gradient pulse duration (δ) and diffusion time
(∆)(see figure), indicating the presence of local barriers sensed by diffusing ions. In
agreement with experimentals, further theoretical analysis and computational results
explain the finite gradient pulse effect and time-dependent diffusion behaviors. We
estimate that the relevant domain length scale that characterizes the ionic polymer is ~
300 nm using an empirical model of diffusion in a porous network. This study has
relevance for fundamental understanding of IL-polymer interactions, ionic polymer
morphology, improvement of IL diffusion studies, andthe design of IL-polymer

composite actuators. Anion
diffusion coefficients (filled circles) inside ionic polymers at 65 o C as a function of
gradient pulse duration (δ, 1.5 -3 ms) and diffusion time (∆). Fits using the Padé
transport model (dotted lines) yield the characteristic length scale (Ls). Note the δdependent
underestimation of Ls.
COIL-4:75
Applying the COSMO Model for the Design of New Ionic Liquids for Carbohydrate
Dissolution
Rasmus Fehrmann (1) , rf@kemi.dtu.dk, Building 206, Kgs. Lyngby 2800, Denmark ;
Andreas Kunov-Kruse (1) ; Anders Riisager (1) . (1) Department of Chemistry, Technical
University of Denmark, Kgs. Lyngby, Denmark
Ionic Liquids (ILs) are promising reaction media for the catalytic processing of
biochemicals in, as ionic liquids are excellent solvents for a wide variety of
carbohydrates that are hard to process in conventional solvents . Despite a lot of
promising ILs for especially cellulose has appeared the last few years, the approach has
mostly been by trial-and-error. Here we investigate how simple theoretical chemistry
can be used to engineer novel types of Brønsted acidic ILs for cellulose and
carbohydrate processing. Profiles of more than 100 promising anions have been
investigated, using Density Functional Theory (DFT) and the COnducter-like Screening
MOdel (COSMO) using cellobiose as a model for cellulose. The group of simple linear
dicarboxylate anions showed very promising properties for dissolving cellulose sugars.
On basis of the theoretical results the three ionic liquids containing the
butylmethylimidazolium ([BMIM] + ) cation and Hydrogen Succinicate , Hydrogen
Gluterate and Hydrogen Adipinate anions, respectively, were synthesized. The solubility
of glucose, cellobiose and cellulose was tested at 100 ○ C by adding the carbohydrate in
small amounts until saturation was reached. The COSMO modelling showed that ILs
based on the group of mono deprotonated carboxylic acids where promising as
carbohydrate solvents . The group was investigated as a function of carbon chain
length. The modelling showed that the hydrogen bond accepting (HBA) properties of the

anion is increasing with the chain length which led to increased bonding with the
carbohydrates. In addition, also the hydrophobic properties are increasing with chain
length. Despite that the COSMO model is considered simple compared to quantum
chemical methods, there was a very good correlation between theory and the
experiments which showed that all three ionic liquids could dissolve very high amounts
of glucose and cellobiose. The solubility maximum for the Hydrogen Gluterate anion
predicted by the model was also confirmed.
COIL-4:76
Thermophysical Characterization of Novel Lipid-Inspired Ionic Liquids.
Arsalan Mirjafari (1) , mirjafari@usouthal.edu, 307 N University Blvd., Mobile Alabama
36688, United States ; Samuel M. Murray (2) ; Richard A O[apos]Brien (1) ; Kevin N West (2) ;
James H Davis, Jr. (2)(1) . (1) Department of Chemistry, University of South Alabama,
Mobile Alabama 36688, United States (2) Department of Chemical and Biomolecular
Engineering, University of South Alabama, Mobile Alabama 36688, United States
Recently, our groups demonstrated that long chain n-alkyl-N-methylimidazolium-based
ionic liquids can be designed to remain room temperature liquids by incorporating cisunsaturation
into the alkyl chain. Typically, such ionic liquids with n-alkyl chains of 10
carbons or longer are room temperature solids. This increase in melting point relative to
analogous ILs with shorter n-alkyl chains is due to the longer n-alkyl chains aligning to
form a continuous non-polar domain where enhanced dispersion force interactions lead
to higher melting points. In lipid-inspired ionic liquids, the “kinked” structure caused by
the unsaturation disrupts packing efficiency resulting in significantly lower melting
points. Additionally, the melting point trends of these species mimics those of the
natural lipids containing analogous fatty acid chains. The observed melting point
decrease for ionic liquids with long unsaturated alkyl chains is significant and results in
many of the species having melting points well below room temperature. Initial studies
indicated that non-polar molecules have a significant solubility in these solvents and has
prompted further investigation into their properties. We have continued to study these
as well as a new generation of structurally diverse and oxidatively stable lipid-inspired
ionic liquids, characterizing their physical properties through melting point, viscosity and
solubility measurements. Many of these ionic liquids have unusually high solubilities for
non-polar compounds and offer the possibility of designing processes which take
advantage of this solubility for reactions and separations. In this work, we present data
describing the thermophysical properties of the next generation of lipid-inspired ionic
liquids as pure components and in mixtures.
COIL-4:77
Use of Ionic Liquid-Based Aqueous Biphasic Systems for Lipase Separation
Isabel M. Marrucho (1) , imarrucho@itqb.unl.pt, Universidade Nova de Lisboa, 127,
Oeiras Oeiras 2780-901, Portugal ; Francisco Deive (2) ; Ana Rodriguez (3) ; Diana Ruivo (1) ;

Luis P.N. Rebelo (1) . (1) Instituto de Tecnologia Química e Biológica, ITQB 2, Oeiras
2780-901, Portugal (2) Department of Chemical Engineering, Universidade de Santiago
de Compostela, Santiago de Compostela 15782, Spain (3) Department of Chemical
Engineering, Universidade de Vigo, Vigo 36310, Spain
Triacylglycerol hydrolases or lipases are an ubiquitous class of enzymes which show
potential due to the fact that they are stable and active in organic solvents, they don't
require cofactors, and they exhibit a high degree of enantio- and regioselectivity.
Lipase-catalyzed processes have received great attention since they are one of the
most interesting biocatalyst for industrial use, in sectors ranging from the petrochemical,
pharmaceutical, food and paper to waste management industries [1,2]. During the last
decade ionic liquids (ILs) have emerged as alternative solvents for biocatalysis. As a
result of collaboration between academics and industry and due to the variety of their
distinctive, specific features, these ILs have found applications in broader fields [3]. In
this sense, ILs provide a powerful means for enzymes, in which they can catalyze
reactions impossible in commonly used organic solvents. In the case of lipases, stability
and biocalysis are the unique areas of research that have been tackled, and the
development of IL-based aqueous extraction systems is yet to be explored. In this
work, a process to extract lipolytic enzymes based on aqueous biphasic systems (ABS)
using ILs and an inorganic salt (K2CO3) is proposed. The activity of a model
Thermomyces lanuginosus lipase (TlL) in some of the most common hydrophilic ILs,
based on the 1-alkyl-3-methylimidazolium cation, combined with chloride, alkylsulphate,
alkylsulphonate and acetate anion is researched. Several conditions influencing lipase
activity and ABS formation were investigated. Parameters such as temperature, pH,
deactivation kinetics and water content were evaluated in order to propose a viable
extraction process. References: [1] A. Houde, A. Kademi, D. Leblanc, Appl. Biochem.
Biotech.2006, 118, 155-170 [2] F. J. Deive, E. Carvalho, L. Pastrana, M. L. Rua, M. A.
Longo, M. A. Sanroman, Bioresource Technol.2009, 100, 3630-3637 [3] N. V.
Plechkova, K. R. Seddon, Chem. Soc. Rev.2008, 37, 123-150
COIL-4:78
Microscopic State of Ionic Liquid Ion Pairs at Low Concentrations in Water as
Studied from Molecular Dynamics Simulations
Jindal K. Shah (1)(2) , jshah@nd.edu, 150 Fitzpatrick Hall, Notre Dame IN 46556, United
States ; Patrick Yee (2) ; Edward J. Maginn (2) . (1) Center for Research Computing,
University of Notre Dame, Notre Dame IN 46556, United States (2) Department of
Chemical and Biomolecular Engineering, University of Notre Dame, Notre Dame IN
46556, United States
Inorganic salts are known to undergo dissociation in water due to large free energy gain
upon hydration of the individual ions. In the case of ionic liquids, however, the question
of association/dissociation of ions when dissolved in water remains to date largely
unexplored. In this study, we apply techniques of molecular simulations to investigate
the microscopic state of the ionic liquid ion pair under extremely low aqueous

concentration (~0.0003 mole fraction). To this end, we calculate the potential of mean
force (PMF) and hence the work required to bring the ions together as a function of the
separation distance. We carry out molecular dynamics calculations on three ionic liquids
of varying hydrophobicity: 1-ethyl-3-methylimidazolium chloride [C2mim]Cl, [C2mim]
ethylsulfate [C2H5SO4] and 1-n-butyl-3-methylimidazolium
bis(trifluoromethylsulfonyl)imide [C4mim][NTf2]. The PMFs of the three ionic liquids are
characterized by two free energy minima corresponding to contact pair and solvent
separated pair, while the long-range behavior is different. The most hydrophobic ionic
liquid [C4mim][NTf2] exhibits the deepest free energy minima and suggest that the most
favorable thermodynamic state of ion pairs is either association through direct ion-ion
interaction or that with a single layer of water separating the ions. In addition to similar
characteristics, the PMF of the ionic liquid [C2mim][C2H5SO4] also shows features
indicative of dissociation. In the case of the ionic liquid [C2mim]Cl, the PMF clearly
suggests that the most preferred thermodynamic state is that in which ions are
completely dissociated. We explain the results in terms of hydrophobicity of these ionic
liquids. Further insight into the solvation of the ions is provided by the organization of
water molecules around the ions.
COIL-4:79
Aggregation of a Redox Amphiphilic Ionic Liquid in Ionic Liquid and in Aqueous
Solution
Juliette Sirieix Plenet (1) , juliette.sirieix_plenet@upmc.fr, PECSA case 51, 4 place
jussieu, Paris Paris 75252 cedex 05, France ; Laurent Gaillon (1) ; Cecile Rizzi (1) . (1)
Departement of chemistry, Laboratoire de Physicochimie des Electrolytes, Colloïdes et
Sciences Analytiques, Université Pierre et Marie Curie – Paris 6, UMR7195 CNRS-
ESPCI-UPMC, Paris 75252 cedex 05, France
Ionic liquids (ILs) offer competitive substitutes to classical organic solvent in synthesis,
separation processes or electrochemistry. They may be considered as polar solvents
when exhibiting water-like properties. It was notably observed that, in IL media,
surfactants could self-organize to form aggregates. However surfactant aggregation
study, through well-known classical methods, is limited in ILs because of low surface
tension, high conductivity or high ionic strength of these media. As a matter of facts,
only few papers could be found in literature devoted to this subject. In order to
modulate the solubilization and transport properties of amphiphilic ionic liquids (AILs),
and control their aggregation, we synthesized a functionalized AIL exhibiting a redox
moiety: the Fc(CH2)11MeImBr [1]. The redox moiety allowed to modify the charge

according to the AIL redox state. We studied these
two AILs and more particularly their self aggregation in aqueous solution and in two ILs
media (hydrophilic BMImBF4 and hydrophobic BMImNTf2). In water, we characterized
the aggregation of both reduced and oxidized AILs by tension surface measurements.
Using the redox AIL as an electrochemical probe, it was shown that electrochemistry
was a tool of choice to characterize the aggregation [1]. In IL media, the aggregation of
these redox AILs could be observed by taking advantage of their electrochemical
properties and these results had to be confirmed from usual techniques. [1] B. Chamiot
et al. Langmuir, 25, 2009, 1311.
COIL-4:80
Ammonium Ionic Liquids in Wood Preservation
Jadwiga Zabielska-Matejuk (1) , J_Matejuk@itd.poznan.pl, ul. Winiarska1, Poznan
Wielkopolska 60-654, Poland ; Weronika Przybylska (1) . (1) Department of Wood
Protection, Wood Technology Institute, Poznan Wielkopolska 60-654, Poland
The ecological aspects play an increasing role in the search for and application of new
wood preservatives. Ionic liquids exhibit a broad spectrum of microbiological activity.
The possibility of modification of structure of ionic liquids facilitates design of
compounds with specific properties such as for example good penetration onto wood
and effective wood protection against decay, blue stain and mould fungi. These
compounds are environmentally friendly because their biodegradability by soil
microorganisms exceeds 60%. The aim of this study was to determine fungistatic and
fungicidal action against wood degrading fungi of ionic liquids containing a nitrate(V) or
nitrate(III) ions as well as environmentally-friendly cation of natural origin obtained from
plant (natural coconut oil) or animal fats. Investigation were also carried out on salts
containing a didecyldimethylammonium, benzalkonium cations and functional: organic
herbicide, aminotriazole as well as coloured anions. We examined the impact of ionic
liquids on wood, especially the adsorption processes of ionic liquids on the surface of
Scots pine and beech wood. Kinetic and equilibrium adsorption of these salts were
evaluated. The investigated ionic liquids with ammonium cations and herbicide,
aminotriazole, nitrates anions demonstrated the strongest action against the mould
fungi. The fungicidal value of these salts for Coniophora puteana ranged from 3.1 kg/m 3
to 6.3 kg/m 3 . The most active against blue stain fungi were nitrates(V) with cation
obtained from natural coconut oil. The Scots pine wood ( Pinus sylvestris L.) saturated
in a 2-minute bath of 2% solution cocotrimethylammonium nitrate(V) was resistant to the
attack by the test blue stain fungi. The coloured ionic liquids were effective in stabilizing

of wood colour and delay in processes of wood photodegradation caused by exposure
to UV radiation. Acknowledgements This investigation received financial support from
project POIG.01.03.01-30-074/08 co-financed by the European Regional Development
Found within the Innovative Economy Operational Program 2007-2013.
COIL-4:81
Phosphonium-Based Ionic Liquids to Improve the Separation of Ethanol-Water
Mixtures
Catarina M. S. S. Neves (1) , catarinasn@ua.pt, Campus Universitário de Santiago,
Aveiro Aveiro 3810-193, Portugal ; José F. O. Granjo (2) ; Mara G. Freire (1) ; Al
Robertson (3) ; Nuno M. C. Oliveira (2) ; João A. P. Coutinho (1) . (1) Departamento de
Química, CICECO, Universidade de Aveiro, Aveiro 3810-193, Portugal (2) CIEPQPF,
Departamento de Engenharia Química, Universidade de Coimbra, Coimbra 3030-790,
Portugal (3) Cytec Canada Inc., Niagara Falls Ontario, Canada
Bioalcohols are produced from biomass by fermentation, and distillation is commonly
used to separate the alcohol from the aqueous phase. This is, however, a high energy
consumption process, and alternative approaches to perform this separation are being
pursued. In this work, the use of phosphonium-based ionic liquids (ILs) for the extraction
of ethanol from fermentation broths is investigated. Ternary phase diagrams, necessary
for the design and to implement an alternative liquid-liquid extraction process for the
alcohol recovery, were determined for tetradecyltrihexylphosphonium-based ILs
combined with the anions bis(trifluoromethylsulfonyl)imide, dicyanamide, bromide,
chloride, bis(2,4,4-trimethylpentyl)phosphinate, decanoate, and methanesulfonate. The
modelling of the equilibrium data was performed using the COSMO-RS and NRTL
models, the first aiming at screening other ionic liquids not experimentally studied, and
the latter aiming at designing a separation process. Due to the satisfactory results
obtained with COSMO-RS, a scan of different ILs not experimentally available was
carried out. The predictions suggested that tricyanomethane- and tetracyanoboratebased
ILs could also be used for improved extractions. The gathered data indicate that
phosphonium-based ionic liquids are the best extractive solvents yet reported to
perform water-ethanol separations. The economic and environmental advantages of the
approach here proposed will be presented and discussed.
COIL-4:82
Photopatternable Phosphonium/Imidazolium Ionogels for Electrochromic
Applications
Andrew Kavanagh (1) , andrew.kavanagh@dcu.ie, Dublin City University, Dublin Ireland,
Ireland ; Kevin J Fraser (1) ; Robert Copperwhite (2) ; Mohamed Oubaha (2) ; Colette
McDonagh (2) ; Dermot Diamond (1) ; Robert Byrne (1) . (1) National Centre for Sensor
Research, School of Chemical Sciences, Dublin City University, CLARITY, The Centre

for Sensor Web Technologies, Dublin Ireland, Ireland (2) National Centre for Sensor
Research, Dublin City University, Optical Sensors Laboratory, Dublin Ireland, Ireland
One of our research interests is the use of Ionic Liquids (IL's) as sensing and actuating
materials within polymeric supports, so called Ionogels 1-3 . We now aim to highlight our
recent research into the use of IL's in solid state electrochromic device fabrications. The
polymeric support for this work comes in the form of the hybrid organic-inorganic sol-gel
material; which when photpolymerized with phosphonium and imidazolium based IL's
forms the basis of directly Photopatternable Ionogels. Photopatterning was performed
using 2-photon polymerisation, a technique which allowed the formation of threedimensional
woodpile structures with sub-micron resolution. The ionogels also exhibit
a measured ionic conductivity which facilitates their use as a solid state electrolyte when
doped with an electrochromic Viologen dye. Characterisation by electrochemical
impedance and Raman spectroscopy shows the ionogels also exhibited the reversible
one electron transfer optical equilibria classical of viologen based devices. Subsequent
characterisation of these equilibria was performed via spectroelectrochemistry in which
reduction via an applied potential generates the blue monoradical cation within the
ionogel. We believe these materials have great potential in applications such as
photonic devices and flexible conducting substrates.
: (a) and (b) SEM images of
three-dimensional woodpile structures from SZ4-20wt% [P6,6,6,14][DCA], (c) and (d)
photopatterning of SZ4-20wt% [P6,6,6,14][DCA] (1) Kavanagh,A. et al; Analyst,2011, 136,
348-353. (2) Yang,S. Y.; Byrne R. et al;Chemical Communications,2010, 46, 7972-
7974. (3) Benito-Lopez,F.; Byrne, R. et al; Lab on a Chip, 2010, 10, 195-201.
COIL-4:83
Actinides and Ionic Liquids: Unique Environments for f-Element Chemistry
Steven P. Kelley (1) , spkelley@crimson.ua.edu, Box 870336, Tuscaloosa AL 35487-
0036, United States ; Erica L. Stoner (1) ; T. Gannon Parker (1) ; Robin D. Rogers (1) . (1)
Department of Chemistry and Center for Green Manufacturing, The University of
Alabama, Tuscaloosa Alabama 35487-0036, United States

Although ionic liquids (ILs) comprise a tremendous family of compounds, there are
several properties that are general among ILs yet uncommon in molecular liquids. The
most well-known property is the low vapor pressure shown by most ILs. This has
resulted in ILs being investigated as safer and more environmentally friendly
alternatives to volatile organic compounds. However, ILs also possess other properties
such as unusual solvating power, short range order, and a tendency to resist
crystallization on cooling which can result in both novel findings and unforeseen
challenges when ILs are newly applied to a field. One such field from which ILs have
received much attention is the processing of spent nuclear fuel. In much of this work
hydrophobic ILs have been used as nonaqueous phases in extractions, but there has
been less research into the fundamental chemistry of actinides in ILs. Because the
environment in an IL consists solely of ions, ILs are particularly interesting for metal
chemistry. The metal ion can interact with counterions without the interference of
solvents. However it can be a challenge to access this chemistry because metal salts
are often insoluble in ILs. Furthermore traditional evaporation-based crystallization
techniques are not usable with ILs. In order to better understand the chemistry of
actinides in ILs and improve the use of ILs in separations, we have begun to explore the
chemistry of uranyl salts and complexing agents in ILs. We present here our preliminary
results which include the crystal structures of several unique complex slats prepared
from ILs, including salts of the well-known uranyl triacetate anion and a novel uranyl
dicyanamide salt, the first uranyl dicyanamide complex to be crystallized from an IL.
COIL-4:84
Forces, Structure, and Dynamics in Ionic Liquids
Barbara Kirchner (1) ; Stefan Zahn (1)(2) . (1) Wilhelm-Ostwald-Institut, University of
Leipzig, Leipzig 04103, Germany (2) School of Chemistry, Monash University, Leipzig
04103, Germany
A significant influence of dispersion forces on interaction energy and equilibrium
distance is observed for diverse ionic liquids (ILs) highlighting the important role of
dispersion forces in depressing the melting point [1,2]. Thus, dispersion-corrected
density functional approaches are recommended strongly to obtain reliable results [3].
Car-Parrinello molecular dynamics simulations of a protic IL, monomethylammonium
nitrate (MMAN), reveal that the ions rattle in a cage of counter ions similar to aprotic ILs
[4]. In contrast to imidazolium-based ILs, a tetrahedral hydrogen bond coordination of
water is observed in MMAN due to the good incorporation of water into the hydrogen
bond network of the protic IL. Therefore, one might expect a larger dipole moment of
water in the investigated water-IL mixture compared to neat water. However, the
opposite is observed indicating strong electrostatic screening in protic ILs [5].

a: SDF of O atoms at NO3 -
(red), of H atoms at the NH3 group of CH3NH3 + (pink), and of N atom of CH3NH3 + (blue)
in Car-Parrinello simulations of a water-MMAN mixture. The green spheres illustrate the
preferred position of the most acidic proton of imidazolium-based ILs b: Dipole moment
distribution of pure water (red) and of water in MMAN (green) Literature: [1] Angew.
Chem. Int. Ed., 2008, 47, 3639-3641 [2] Phys. Chem. Chem. Phys., 2008, 10, 6921-
6924 [3] J. Phys. Chem. A, 2008, 112, 8430-8435 [4] J. Chem. Phys., 2010, 132,
124506 [5] Phys. Chem. Chem. Phys., submitted
COIL-4:85
Chiral Ionic Liquids: From Recognition to Chiral Separation
Maria Vasiloiu (1) , mvasiloiu@ioc.tuwien.ac.at, Getreidemarkt 9/163, Vienna Vienna
1060, Austria ; Peter Gaertner (1) ; Katharina Bica (1) . (1) Institute of Applied Synthetic
Chemistry, Vienna University of Technology, Vienna 1060, Austria
Chiral ionic liquids (CILs) have been recognized for years as an alternative strategy to
carry out chiral transformations in areas as diverse as separation or catalysis.[1]
However, although the features of chiral ionic liquids might provide a new and attractive
approach to induce chirality, they often fail to induce significant selectivity when used as
sole source of chirality and need to be carefully designed for a specific asymmetric
reaction.[2] With this in mind, we performed a systematic study of the diastereomeric
interactions of a small set of new and known chiral ionic liquids of both protic and

alkylated origin. Based on
the commercially available amino alcohols ephedrine and prolinol we present the design
and synthesis of novel basic and highly coordinating chiral ionic liquids and discuss their
application in chiral recognition and separation. [1] Prechtl, M.; Scholten, J. Current
Org. Chem. 2009, 13, 1259. [2] Bica, K.; Gaertner, P. Eur. J. Org. Chem. 2008, 19,
3235.
COIL-4:86
Molecular Simulation of New Ionic Liquid Lubricants for Metal Surfaces
Ana C. F. Mendonça (1) , ana7catarina@gmail.com, 24 av. des Landais, Aubière
Auvergne 63177, France ; Patrice Malfreyt (1) ; Agílio A. H. Pádua (1) . (1) CNRS -
Université Blaise Pascal Clermont-Ferrand, Laboratoire de Thermodynamique et
Interactions Moléculaires, Aubiere Auvergne 63171, France
The main objective of this work is the description at the molecular level of the structure
and interactions between ionic lubricants and an iron surface using molecular dynamics
simulation. This technique has proven to be an important tool in unrevealing the
microscopic origins of many tribological phenomena such as lubrication, friction and
wear. To tackle this problem, a force field that describes the different molecular
interactions and conformations in the systems was developed. Ion-ion interactions were
parameterized in a specific model for the novel ionic lubricants selected, which present
suitable ecotoxicological and tribological properties. The ionic liquids chosen are based
on alkyl-ammonium cations and alkyl-sulfonate anions. Quantum calculations using a
density functional method suitable for non-covalent interactions were used to define the
ion-metal potential, at different distances and orientations. A classical site-site potential
function was adjusted to the DFT energies and complemented by a polarization term.
The interfacial properties of the ionic liquid at the iron surface were investigated using
molecular simulation, including the spatial and orientational ordering of the ionic liquid,
in order to gain insight into properties relevant for lubrication.

COIL-4:87
Straight Ahead or Bent up? Enthalpies of Vaporization of [CnMIM][NTf2] from Two
New Methods: Quartz Crystal Microbalance and Thermogravimetry
Sergey P. Verevkin (1) , sergey.verevkin@uni-rostock.de, Dr-Lorenz-Weg 1, Rostock
18059, Germany ; Dzmitry H. Zaitsau (1) ; Vladimir N Emel’yanenko (1) ; Ricardas Ralys (1) ;
Christoph Schick (2) ; Andreas Heintz (1) . (1) Department of Physical Chemistry, University
of Rostock, Rostock 18059, Germany (2) Department of Physics, University of Rostock,
Rostock 18057, Germany
Experimental measurements of vapor pressures in the range < 1 Pa is a challenging
task. Ionic liquids (ILs) as a neoteric solvents and environmentally friendly solvents have
extremely low vapor pressures (~ 10 -10 Pa at 298 K). This fact significantly decreases
the number of possible experimental methods suitable for the determination their
enthalpies of vaporization. Development of two new experimental methods Quartz
Crystal Microbalance (QCM) and Thermogravimetry (TGA) have been performed in our
laboratory. The comprehensive investigation of the enthalpy of vaporization for the 1alkyl-3-methyl-imidazolium
bis-(trifluoromethylsulfonyl)-imides was carried out using
Langmuir equation for the vaporization from the open surface. The reliability of
Langmuir method coupled with the quartz microbalance mass uptake determination was
proved by the experiments with the data for [C2mim][NTf2], where reliable results are
available from the traditional Knudsen method. TGA method was extensively tested with
the low-volatile molecular compounds . It was found that the enthalpy of vaporization for
[Cnmim][NTf2] homolgues series additively increases from [C2mim][NTf2] to
[C16mim][NTf2] with the increment value of 3.2 kJ·mol -1 for CH2 group at 380 K. This
value is 0.5 to 1.0 kJ·mol -1 lower than that those found for the molecular compounds: nalkyl
benzenes, n-alkyl nitriles, and n-alkanols.
COIL-4:88
Thermochemistry of Alkylammonium Nitrate Protic Ionic Liquids
Sergey P. Verevkin (1) , sergey.verevkin@uni-rostock.de, Dr-Lorenz-Weg 1, Rostock
18059, Germany ; Vladimir N Emel’yanenko (1) ; Andrei V. Yermalayeu (1) ; Ricardas
Ralys (1) ; Dzmitry H. Zaitsau (1) ; Christoph Schick (1) ; Simona-Maria Stana (2) ; Kenneth R.
Seddon (2) . (1) Department of Physical Chemistry, University of Rostock, Rostock 18059,
Germany (2) The QUILL Research Centre, School of Chemistry and Chemical
Engineering, The Queen[apos]s University of Belfast, Belfast BT9 5AG, United Kingdom
In recent years, there has been an escalating interest in protic ionic liquids and in their
various potential applications for separation processes, and as electrolytes for
photoelectrochemical (solar) cells or fuel cells. Protic ionic liquids are formed through
the transfer of a proton from a Brønsted acid to a Brønsted base. This leads to
differences between protic ionic liquids and aprotic ionic liquids, in that the former have
a proton available for hydrogen bonding and usually possess non-negligible boiling

points below their decomposition temperature. In this work, three protic ionic liquids
[CnNH3][NO3] (n = 4, 6, or 8) were synthesised and carefully purified for thermochemical
measurements. The molar enthalpies of formation were measured by means of
combustion calorimetry. Molar enthalpies of fusion were measured using differential
scanning calorimetry. The vaporisation process of these protic ionic liquids at different
temperatures was studied by thermogravimetry and with a quartz-crystal-microbalance.
Ab initio calculations of the enthalpy of formation in the gaseous phase have been
performed for the ionic species using the G3MP2 and the CBS-QB3 composite
methods. Combination of calorimetric methods with the modern high-level quantumchemical
calculations has produced insight into the energetics of protic ionic liquids, and
the molar enthalpies of vaporisation of the series of ionic liquids are discussed.
Experimental results have been tested for consistency using the group additivity
procedure. It has been established that the enthalpies of formation of these ionic liquids
obey the group additivity rules.
COIL-4:89
New Ampholytic Ionic Liquids as Proton Conductors in Fuel Cells
Marcel Treskow (1) , marcel.treskow@chalmers.se, Condensed Matter Physics,
Gothenburg SE-41296, Sweden ; Jagath Pitawala (1) ; Aleksander Matic (1) ; Patrik
Johansson (1) . (1) Department of Applied Physics, Chalmers University of Technology,
Gothenburg 41296, Sweden
The application of water containing electrolytes for fuel cells limits their use to
temperatures below 100 °C. Water-free proton conductors, such as protic ionic liquids
(PILs) are suitable alternatives to avoid this limitation and were reported the first time in
2003 [1,2]. This first generation of PILs was obtained by protonation of amines with
strong acids, resulting in an equilibrium between ionic and neutral species, the latter
possibly leading to decomposition at higher temperatures. Here we present a new
approach to PILs; by neutralization of basic methyl carbonate ionic liquids with
trifluoromethane-sulfonamide (CF3SO2NH2) (Fig 1). Due to the decarboxylation of the
starting material during the neutralisation process, we obtain an ampholytic ionic liquid
with a high proton conductivity (σ(RT)= 5.0 mScm -1 ) (Fig 3) and a rather low glass
transition temperature (Tg = -70 °C) (Fig 2). The ampholytic character of the CF3SO2NH -
anion makes possible proton release and absorption without any need for change in the
structure. Altogether, this makes this anion and our new class of ionic liquids interesting
as proton conductors for fuel cell applications. We report a full characterisation of our
new ionic liquids, including conductivity, electrochemical properties and thermal stability.
As the molecular level dynamic properties are important we also use 1 H and 19 F-NMR

DOSY experiments to obtain the diffusion constants and transport numbers.
COIL-4:90
New Generation of Energetic Materials based on Novel Asymmetric Multiheterocyclic
Architectures
Preston A Beasley (1) , pabeasley@crimson.ua.edu, 250 Hackberry Lane, Tuscaloosa
Alabama 35487, United States ; Parker D McCrary (1) ; Robin D Rogers (1) . (1) Department
of Chemistry and Center for Green Manufacturing, The University of Alabama,
Tuscaloosa Alabama 35487, United States
This presentation will discuss our exploration of a novel platform for potential energetic
materials based on ionic liquid ions comprised of asymmetric multi-heterocyclic ions.
The strategy we employ uses known chemistry to prepare nitrogen-rich ions to prepare
ionic liquids with higher energetic density, lower viscosity, and lower impact and friction
sensitivity. This presentation will review the syntheses routes taken to create the new
ions and how we have used ionic liquids strategies to then convert them into new salts.
Current challenges, limitations, and future outlooks will also be discussed. This
research was supported by the Air Force Office of Scientific Research (Grant F49550-
10-1-0521)
COIL-4:91
An in situ STM / DTS Study of the Ionic Liquid / Au(111) Interface in Extremely
Pure [Py1,4]FAP and [EMIm]FAP: Potential Dependent Solvation Layers
Natalia Borisenko (1)(2) , natalia.borissenko@tu-clausthal.de, Arnold-Sommerfeld-
Strasse 6, Clausthal-Zellerfeld Niedersachsen 38678, Germany ; Robert Hayes (3) ; Rob
Atkin (3) ; Frank Endres (1)(2) . (1) Institute of Particle Technology, Clausthal University of
Technology, Clausthal-Zellerfeld 38678, Germany (2) EFZN Goslar, Clausthal-Zellerfeld
38678, Germany (3) Centre for Organic Electronics, The University of Newcastle,
Newcastle 2308, Australia

Ionic liquids have attracted a great interest as promising solvents for electrochemistry.
As ionic liquid speciation significantly impacts the interfacial characteristics, they cannot
be regarded as neutral solvents. The electrochemical double layer of ionic liquids is
complicated; as it rather consists of multilayers. Unfortunately, the interface ionic liquid /
electrode has so far not yet been extensively studied and relatively little is known about
the structure and property of the metal / ionic liquid interface. In this study in situ
scanning tunneling microscopy (STM) and in situ distance tunneling spectroscopy
(DTS) measurements have been employed to elucidate the structure of the charged
Au(111) / ionic liquid interface. Data for two extremely pure ionic liquids, namely
1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate ([Py1,4]FAP) and
1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([EMIm]FAP) with
the same anion are presented. The distance dependence of the tunneling current has
been measured as a function of potential. The height of the tunneling barrier between
the STM tip and the gold substrate was estimated from the DTS results. The in situ
STM results reveal that interfacial layers or solvation layers are probed at the Au(111) /
ionic liquid interface. The structure and properties of these layers are dependent on the
liquid and on the applied electrode potential. In the case of [Py1,4]FAP the Au(111)
structure undergoes a reconstruction and in a certain potential regime the famous (22 x
√3) herringbone superstructure is probed, while in [EMIm]FAP of the same quality
Au(111) does not exhibit the herringbone superstructure pattern. Furthermore, the
interface Au(111) / [EMIm]FAP reveals slow processes and there are hints for the
adsorption of the cation. The subsequent investigation of solvation layers of different
ionic liquids under electrochemical conditions as well as on the influence of solutes and
temperature on solvation layers are important for better understanding the influence of
ionic liquids on electrochemical reactions.
COIL-4:92
Ion Exchange or Salt Extraction?
Camiel H C Janssen (1)(2) , camiel.janssen@wetsus.nl, Agora 1, Leeuwarden Friesland
8900 CC, The Netherlands; Sybrand J Metz (2) ; Jaap van Spronsen (1) ; Geert-Jan
Witkamp (1) ; Maaike C Kroon (3) . (1) 3ME, Delft University of Technology, Delft, The
Netherlands (2) Wetsus, Delft, The Netherlands (3) Chemical Engineering, Eindhoven,
University of Technology, Eindhoven, The Netherlands
Ionic liquids (ILs) can be used for several separation processes. Nowadays it becomes
more important to separate or recover metal salts from aqueous phases to prevent a
shortage in the future. ILs, especially in combination with crown ethers, can be used as
extractants for this type of separation. One of the major problems when ILs are used
for this separation process is the occurrence of ion exchange. In that case some cations
of the IL are exchanged for some of the cations of the metal salt. Not only does ion
exchange cause the loss of the IL, but it also generates a new hydrophilic IL. This
hydrophilic IL is in most cases even more toxic to the environment than a traditional
volatile organic solvent. Some ILs give prevalence to the desired salt extraction,
whereas others seem to have ion exchange as prevailing mechanism. A schematic

epresentation of both processes is shown fig 1. In this work, a large number of ILs and
crown ethers have been systematically investigated on their separation mechanism and
efficiency. Several trends in this process emerging from these experiments reveal the
change from ion exchange to salt extraction as prevailing mechanism as a function of
molecular structure of the IL. For example imidazolium NTf2 based ILs with large alkyl
chains have mutual extraction as prevailing mechanism, whereas shorter alkyl chains
give rise to ion exchange. This is of importance for the applicability of the metal salt
extraction process, as a large bleach of toxic hydrophilic IL into the aqueous phases can
severely limit the possibilities of application. The various trends will be discussed at the
conference and further results and data will be presented.
COIL-4:93
Physicochemical Properties of Binary Systems Composed of N-methyl-N-
Pentylpyrrolidinium Bis(trifluoromethanesulfonyl)imide and aprotic Solvents
Wesley A Henderson (1) , whender@ncsu.edu, 911 Partners Way, Campus Box 7905,
Raleigh NC 27695, United States ; Eric T Fox (1) ; Elie Paillard (1) . (1) Department of
Chemical and Biomolecular Engineering, North Carolina State University, Raleigh NC
27695, United States
Ionic liquids (ILs) are promising alternative electrolyte materials for replacement, at least
in part, of the aprotic solvents and/or high melting salts (i.e., Et4NBF4) widely utilized in
lithium batteries and electrochemical capacitors. However, ILs have a number of factors
preventing their widespread adoption, including poor wetting behavior of electrodes and
separators, modest conductivity, and high cost. This work addresses these issues by
characterizing the physicochemical properties of binary solvent-IL mixtures composed
of N-methyl-N-pentylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PY15TFSI) and
aprotic solvents, such as acetonitrile (AN), diethyl carbonate (DEC), dimethyl carbonate
(DMC), ethylene carbonate (EC) and propylene carbonate (PC). Variations in the
density and viscosity are reported and correlated with the ionic conductivity and thermal
phase behavior of these mixtures. Such mixtures embody many beneficial
characteristics such as low flammability and hindered/inhibited crystallization at low

temperature. Fig. 1.
Conductivity (mS/cm) of (x) PC-(1-x) PY15TFSI mixtures (x = mol fraction). [1]
Arbizzani, C.; Beninati, S.; Lazzari, M.; Soavi, F.; Mastragostino, M. J. Power Sources
2007, 174, 648. [2] Lazzari, M.; Soavi, F.; Mastragostino, M. J. Electrochem. Soc.
2009, 156, A661. [3] Galinski, M.; Stepniak, I. J. Appl. Electrochem. 2009, 39, 1949. [4]
Yuyama, K.; Masuda, G.; Yoshida, H.; Sato, T. J. Power Sources 2006, 162, 1401. [5]
Nanjundiah, C.; McDevitt, S. F.; Koch, V. R. J. Electrochem. Soc. 1997, 144, 3392.
COIL-4:94
Oxidation of Cinnamyl Alcohol and Separation of 3-Phenylglycidol in Ionic Liquid
+ Carbon Dioxide Systems
Somayeh Kazemi (1) , s.kazemi@tudelft.nl, Leeghwaterstraat 44, Delft Zuid Holland, The
Netherlands; Maaike Kroon (2) ; Cornelis Peters (1)(3) ; Geert Jan Witkamp (1) ; Isabel
Arends (4) . (1) Department of Process and Energy, Delft University of Technology, Delft,
The Netherlands (2) Department of Chemical Engineering and Chemistry, Eindhoven
University of Technology, Eindhoven, The Netherlands (3) Chemical Engineering
Program, The Petroleum Institute, Delft, The Netherlands (4) Department of
Biotechnology, Delft University of Technology, Delft, The Netherlands
It is expected that future chemical engineering processes will use more environmentally
benign solvents as reaction and separation media. For instance, the application of ionic
liquids (ILs) in combination with supercritical carbon dioxide (scCO2) has been recently
developed for this purpose. When using an IL as a solvent for the reaction, in
combination with scCO2 as co-solvent, the reaction can be performed in a homogenous
phase by selection of a suitable pressure, temperature and CO2 concentration. After the
completion of the reaction, changing the conditions result in a multi-phase system, in

which one of the phases is an IL and at least one of the other phases is the CO2-rich
phase, from which the product is recovered substantially free of IL. In this study, the
catalytic oxidation of cinnamyl alcohol to 3-phenylglycidol in presence of ILs and CO2
has been studied. The reaction has been optimized with respect to the following
parameters: (i) amount of oxidizing agent, (ii) type of catalyst, and (iii) amount of
catalyst. Several ILs with different properties were also employed instead of
conventional volatile organic solvents, to study the effect of type of IL on the model
reaction. Moreover, the difficulties in separating the product 3-phenylglycidol from the IL
+ CO2 system are addressed. The results for the reaction and separation in the IL +
CO2 system, including relevant comparisons, will be presented at the conference.
COIL-4:95
NMR as a Probe of Nanostructured Domains in Ionic Liquids: Does Domain
Segregation Explain Increased Performance of Free Radical Polymerisation
Simon Puttick (1) , pcxsp3@nottingham.ac.uk, B3, University Park, Nottingham
Nottinghamshire NG7 2RD, United Kingdom ; Adrienne L Davis (1) ; Kevin Butler (1) ;
Lynette Lambert (2) ; Jaouad El Harfi (1)(3) ; Derek J Irvine (1)(3) ; Andrew K Whittaker (2) ;
Kristofer J Thurecht (2) ; Peter Licence (1) . (1) School of Chemistry, University of
Nottingham, Nottingham, United Kingdom (2) Australian Institute of Bioengineering and
Nanotechnology, University of Queensland, Brisbane, Australia (3) Process and
Environmental Research Division, Faculty of Engineering, University of Nottingham,
Nottingham, United Kingdom
Rotating frame nuclear Overhauser effect spectroscopy (ROESY) has been used to
probe the chemical environment in dialkyl-imidazolium ionic liquids. 1
A qualitative use of the
distance dependence of the rotating frame Overhauser enhancement (ROE) has shown
that reactants and intermediates have variable affinities for the distinct domains that are
proposed within ionic liquids. A model system based on the free radical polymerisation
of methyl methacrylate (MMA) has been developed to investigate any differing affinities,
and to investigate the hypothesis that segregation of species between domains within
the ionic liquid structure is contributory towards the generation of unexpectedly high
rates of polymerisation and final polymer molecular weights. 2 1. S. Puttick et al in
preparation. 2. K. J. Thurecht et al Macromolecules, 2008, 41, 2814-2820.
www.nottingham.ac.uk/ionicliquids
COIL-4:96

Surface Hydrophobization of Bacterial Cellulose in Ionic Liquids
Liliana C. Tomé (1)(2) , liliana.tome@itqb.unl.pt, Av. República, Apartado 127 2780-157
Oeiras, Portugal ; Mara G. Freire (1)(2) ; Luís Paulo N. Rebelo (2) ; Armando J. D.
Silvestre (1) ; Carlos P. Neto (1) ; Isabel M. Marrucho (1)(2) ; Carmen S. R. Freire (1) . (1)
Chemistry Department, University of Aveiro, CICECO 3810-193 Aveiro, Portugal (2)
Universidade Nova de Lisboa, Instituto de Tecnologia Química e Biológica, ITQB2
3810-193 Aveiro, Portugal
The rapidly growing quest for renewable resources capable of replacing petroleum
based macromolecules, is giving to sources like polysaccharides a major importance.
Cellulose, the major component of plant cell walls, is one of the most studied
polysaccharides. In addition, nanocellulose fibers have also attracted considerable
attention in the last few years, namely, bacterial cellulose, nanofibrillated cellulose and
cellulose whiskers. Bacterial cellulose is an extracellular polysaccharide produced in a
highly pure form as a three-dimensional network of highly crystalline nano- and
microfibrils, which possess unique physical and mechanical properties and have been
extensively explored for the development of new nanocomposites materials. However,
the extremely hydrophilic nature of cellulose fibers causes a very low interfacial
compatibility with less polar polymeric matrices. To overcome this problem the reduction
in the polar character of the surface of cellulose fibers is necessary. Controlled
heterogeneous chemical modifications have proved to be suitable techniques to
overcome this problem. Most of the chemical approaches described for the surface
hydrophobization involve the use of harmful organic solvents like toluene, which
represents an important concern when one considers the scale-up of these processes.
In this context, we have explored the heterogeneous hydrophobization of bacterial
cellulose fibers, and, for comparative purposes, vegetal cellulose fibers, with several
anhydrides and fatty acyl chlorides in ionic liquids (low-melting-point salts with high
stability and easy recyclability). This approach constitutes an important “green” step in
processes associated with the valorization of this renewable resource. The occurrence
of the surface modification was confirmed by elemental analyses, FTIR spectroscopy,
and contact angle measurements. The crystallinity and morphology of the modified
cellulose fibers were evaluated by X-ray diffraction and scanning electron spectroscopy,
respectively, and the thermal stability was evaluated by thermogravimetric analyses.
COIL-4:97
Alkyl-Methyl-Phosphonate Ionic Liquids.
Swetlana Sachnov (1) , swetlana.sachnov@crt.cbi.uni-erlangen.de, Egerlandstr. 3,
Erlangen 91058, Germany ; Peter Steffen Schulz (1) ; Peter Wasserscheid (1) . (1)
Department of Chemical Reaction Engineering, University Erlangen-Nuremberg,
Erlangen 91058, Germany
The optimization of the physico-chemical properties of an ionic liquid is commonly
carried out by structural variations of either its cation or anion. The cation modification is

usually achieved by different alkylating agents in the amine or phosphine
quarternization in the synthesis of the IL cation. [1] In case of the IL anion, structural
flexibility is more difficult to realize. One specific example is the transesterification of
methylsulphate anions using various alcohols. [2] Our contribution reports on a new
class of ionic liquids that provides also a similar structural flexibility in the anion design.
Our starting point is the readily available ionic liquid [EMIM] methyl-methylphosphonate.
We found that [EMIM] methyl-methyl-phosphonate can be reacted with
many different strong alkylating agents RX to give the corresponding alkyl-methylmethyl-phosphonester
(a mild alkylating agent itself) and the corresponding [EMIM]X
ionic liquid. The phosphonester is used on his part as methylating agent for the
quaternization reactions of any amine or phosphine giving access to a wide variety of
ILs of the type [cation] alkyl-methyl posphonate.
The obtained alkyl-methylphosphonate
ILs are completely halide free, stable up to 300 °C and display viscosities
in the range of 200-700 mPa s-1. [1] P. Wasserscheid, T. Welton, Ionic Liquids in
Synthesis, 2nd Ed., Wiley-VCH,Weinheim, 2003. [2] S. Himmler, S. Hörmann, R. van
Hal, P.S. Schulz, P. Wasserscheid, Green Chem., 2006, 8, 887.
COIL-4:98
Thermodynamics of Complex Formation in RTIL
K. Popov (1) , ki-popov@mtu-net.ru, Mosow, Russian Federation ; A. Vendilo (2) ; E.
Esipova (2) ; I. Filimonov (2) ; V. Chistov (2) ; D. Djigailo (3) ; I. Pletnev (3) ; M. Lajunen (4) ; H.
Rönkkömäki (5) . (1) Department of Physical and Colloid Chemistry, Moscow State
University of Food Production, Moscow, Russian Federation (2) Institute of Reagents
and High Purity Substances (IREA), Moscow, Russian Federation (3) Department of
Chemistry, M.V.Lomonosov State University, Moscow, Russian Federation (4)
Department of Chemistry, University of Oulu, Oulu, Finland (5) Finnish Institute of
Occupational Health, Oulu, Finland
The thermodynamic quantities for the formation of [Cs(18C6)] + and [Cs(DB18C6)] + in
RTILs indicate that enthalpy change promotes complex formation in hydrophilic RTIL,
whereas the corresponding change of entropy is negative and provides the
decomposition of [Сs(18C6)] + . However, this not the case of hydrophobic RTILs
[HMIM][N(Tf)2], [BMIM][N(Tf)2], [TOMA][Sal], [THA][DHSS], that reveal a positive
entropy change like acetonitrile. Moreover, the entropy change gives the dominating
contribution to [Cs(18C6)] + stability in [BMIM][N(Tf)2], [TOMA][Sal] and [THA][DHSS].
Only one hydrophobic RTIL ([BMIM][PF6]) demonstrates the same behavior as
hydrophilic RTILs and polar molecular solvents. Thus, the thermodynamic quantities
emonstrate clearly, that the contributions to the overall stability of CsL complex may
differ rather significantly. The reaction enthalpies and entropies, reveal greater diversity,
than log K1 depending on RTIL composition. The complexation of Cs + is the most
exothermic in [BMIM][BF4]. Moreover, the observed ∆H1 value is the highest known for

CsL in both molecular solvents and RTIL. At the same time the corresponding entropy
change for this solvent is also the highest, diminishing the enthalpy contribution to the
log K1. The data obviously indicate, that both cation and anion of RTIL affect the
complex formation stability and thermodynamic functions change. References 1.
A.G.Vendilo, D.I.Djigailo, I.V.Pletnev, I.I.Torocheshnikova “Thermodynamics of Cs +
complexes formation with dibenzo-18-crown-6 in RTILs” Russ. J. Inorg. Chem. 2011, in
press. 2. A.G.Vendilo, V.I.Chistov, V.I.Provalov “Thermodynamics of Cs + compex
formation with dibenzo-21-crown-7 and dibenzo-24-crown-8 in 1-butyl-3methylimidazolium
bis[trifluoromethyl)sulphonyl]imide” Russ. J. Inorg. Chem. 2011, in
press.
COIL-4:99
Physicochemical and Electrochemical Properties of Glyme-Li Salt Equimolar
Complexes as Lithium Ionic Liquids
Naoki Tachikawa (1) , ntachika@ynu.ac.jp, 79-5 Tokiwadai, Hodogaya-ku, Yokohama
Kanagawa 240-8501, Japan ; Kazuki Yoshida (1) ; Takashi Tamura (1) ; Mizuho Tsuchiya (1) ;
Kaoru Dokko (1) ; Masayoshi Watanabe (1) . (1) Department of Chemistry and
Biotechnology, Yokohama National University, Yokohama Kanagawa 240-8501, Japan
The design of room temperature ionic liquids has become one of the most fascinating
domains of current chemistry. Li + -conducting ionic liquids are promising for application
to safe and non-flammable lithium secondary batteries. Most of the studies use ionic
liquids as solvents and lithium salts are dissolved in the ionic liquids. However, lithium
ion transference number of these systems is low because the total ionic concentration is
high compared with lithium ion concentration. In this study, we propose glyme-Li salt
equimolar complexes that have the potential to be used as lithium ionic liquids. The
glyme-Li salt equimolar complexes are comprised of equimolar mixture of a glyme
(CH3O(CH2CH2O)nCH3) and a Li salt. The oxygen atoms of glyme can coordinate with a
lithium ion, forming [Li(glyme)] + complex. The resulting composition with equimolar
mixture of glyme and Li salt consists of [Li(glyme)] complex cation and an anion. Here,
we investigated the physicochemical and electrochemical properties of glyme-Li salt
complexes. Certain glyme-Li salt complexes are liquid at ambient temperature and
show high thermal stability, high lithium ion concentration, high lithium ion transference
number and high oxidative stability. Furthermore, we introduce asymmetric structure
into [Li(glyme)] complex by changing alkyl chain length of the glyme molecular. The
melting point and/or glass transition temperature of glyme-Li salt equimolar mixture can
be reduced by using asymmetric glyme. The self-diffusion coefficients of lithium ion and
the glyme molecule are the same within experimental error. It suggests lithium ion and
glyme molecular diffuse together. In addition, a battery cell using the [Li(glyme)][TFSA]
electrolyte shows the stable charge-discharge operation, indicating that the
[Li(glyme)][TFSA] complex is applicable as a 4 V class lithium battery electrolyte.
COIL-4:100

Highly Adsorbent Activated Carbon for Removing Ionic Liquids from Aqueous
Effluents
Jesus Lemus (1) , jesus.lemus@uam.es, Cantoblanco universidad, Madrid Madrid
28049, Spain ; Jose Palomar (1) ; Miguel Angel Gilarranz (1) ; Juan Jose Rodriguez (1) . (1)
Chemical Engineering, Universidad Autonoma de Madrid, Madrid 28049, Spain
The separation of imidazolium based ionic liquids (ILs) from aqueous solution by
adsorption has been investigated using several commercial activated carbons (ACs), in
order to determine the characteristics that must have an adsorbent for effective removal
of ILs from aqueous stream. Commercial ACs of very different porosity and other
adsorbents of different chemical nature, such as silica or alumina, have been used in
adsorption against a common IL (OmimPF6), with the aim of obtaining a large variety of
adsorbents. Equilibrium experiments were carried out for obtaining the adsorption
isotherms of ILs on adsorbents at different temperatures. The influence of both cation
and anion nature and molecular size was analyzed by studying 26 different ILs. The
incorporation of IL on the AC surface was studied by N2 adsorption-desorption
measurements, mercury porosimetry and elemental analysis. In addition to this, a
COSMO-RS computational approach was developed to estimate molecular and
thermodynamic properties of the solvent-adsorbate-adsorbent system, which allowed us
to analyze the adsorption mechanism from a molecular point of view. We found that
both chemical and physical properties of adsorbents are essential to assess their
capacity to retain ILs in aqueous solution, which should be selected depending on
chemical nature and molecular size of IL. The results of this work indicate that the
adsorption with ACs is an affordable and versatile environmental application to remove
hydrophobic ILs, but also hydrophilic ILs, from water streams, proposing the use of
acetone for adsorbent regeneration. It has also been demonstrated that the adsorption
of refractory can be improved modifying the amount and nature of oxygen groups on the
AC surface, particularly by including hydroxyl groups to promote hydrogen-bonding
interactions with the basic groups of hydrophilic ILs.
COIL-4:101
Structural Organization and Phase Behaviour of 1-Butyl-3-Methylimidazolium
Hexafluorophosphate: An High Pressure Raman Spectroscopy Study
Alessandro Triolo (1) , triolo@ism.cnr.it, via Fosso del Cavaliere, 100, Rome Lazio, Italy
; Olga Russina (2) ; Barbara Fazio (3) ; Christian Schmidt (4) . (1) Istituto Struttura Materia,
Consiglio Nazionale delle Ricerche, Italy (2) Università di Roma, Sapienza, Italy (3)
Istituto Processi Chimico-Fisici, Consiglio Nazionale delle Ricerche, Italy (4) GFZ
German Research Centre for Geosciences, Germany
The complexity of the phase diagram of a representative room temperature ionic liquid
(1-butyl-3-methylimidazolium hexafluorophosphate, [bmim][PF6]) is explored by means
of Raman spectroscopy at high pressure (up to 1,000 MPa) and high temperature (from
room temperature to 100 °C) conditions.

The first experimental
evidence of the existence of a second crystalline phase for this salt at high pressure
conditions is provided. By comparing the low frequency vibrational bands for the liquid
state and the two observed crystalline phases, we confirm the scenario that considers
the crystal polymorphism in this class of materials as a consequence of the rotational
isomerism of the butyl chain. Furthermore the pressure dependence of other vibrational
bands indicates the existence of a structural rearrangement across the pressure of
approximately 50 MPa at ambient temperature.
COIL-4:102
Stabilization of Ruthenium Nanoparticles in Ionic Liquids
Ajda Podgoršek (1) , ajda.podgorsek@univ-bpclermont.fr, 24 avenue des Landais,
Aubière 63171, France ; Alfonso S. Pensado (1) ; Paul S. Campbell (2) ; Gorka Salas (2) ;
Catherine C. Santini (2) ; Agílio A.H. Pádua (1) ; Margarida F. Costa Gomes (1) . (1)
Laboratoire de Thermodynamique et Interactions Moléculaires, Clermont Université,
UMR 6272 CNRS-Université Blaise Pascal, Aubière 63171, France (2) LC2P2, Equipe
Chimie Organométallique de Surface, ESCPE, Université de Lyon, Institut de Chimie de
Lyon, UMR 5265 CNRS-Université de Lyon-ESCPE Lyon, Villeurbanne F-69616
Villeurbanne, France
Ionic liquids (ILs), particularly those based on imidazolium cations, display a high
degree of self-organization. 1 Some ILs are suitable as media for generation and
stabilization of metallic nanoparticles (NPs). 2,3 It was demonstrated that the size and the
shape of NPs are modulated not only by the reaction conditions, but also by the nature
of the ILs, dictating the size of nano-domains. 3 However, the stabilization of NPs is a
complex issue and the question of precisely how ILs stabilize NPs remains under
debate. In this communication we report a study of the interactions between RuNPs
and 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquids,
[C1CnIm][NTf2], n = 2,4,6,8,10. RuNPs were synthesized by the decomposition of

(η 4 -1,5-cyclooctadiene (η 6 -1,3,5-cyclo-octatri-ene)-ruthenium(0). The difference in the
interaction energy between RuNPs in [C1C4Im][NTf2] and RuNPs in [C1CnIm][NTf2] was
measured by isothermal titration calorimetry. Furthermore, the effect of the nature of the
cation and the anion on the stabilization of NPs in ILs was investigated as well as the
influence of additional co-stabilizing agents (i.e. amines). In parallel, a molecular
interaction model was developed to describe the interactions between the ionic liquid
and a NP. The intermolecular energy between fragments of the ions and a cluster of Ru
atoms was calculated using a density functional suitable for non-covalent interaction,
and a classical site-site potential function was adjusted to these results. Polarization of
the metallic atoms was also included. A RuNP solvated in [C1C4Im][NTf2] was simulated
using molecular dynamics in order to obtain energetic and structural information. The
calorimetric and simulation results contribute to an understanding at the molecular level
of the stabilization mechanism of RuNPs in 1-alkyl-3-methylimidazolium
bis(trifluoromethylsulfonyl)imide ionic liquids. 1. J. N. Canongia Lopes et al.,
J.Phys.Chem.B, 2006, 110, 3330-3335. 2. J. Dupont et al., Chem.Soc.Rev, 2010, 39,
1780-1804. 3. T. Gutel et al., J.Mat.Chem., 2007, 17, 3290-3292.
COIL-4:103
Catalytic Conversion of Fructose to Ethyl Levulinate with Brønsted Acid Ionic
Liquids
Anders Riisager (1) , ar@mail.kemi.dtu.dk, Anker Engelundsvej 1, Kgs. Lyngby Lyngby-
Taarbaek Kommune 2800, Denmark ; Saravanamurugan Shunmugavel (1) ; Olivier
Nguyen Van Buu (1) . (1) Department of Chemistry-, Technical University of Denmark,
Kgs. Lyngby Lyngby-Taarbæk Kommune 2800, Denmark
Today most organic chemicals are being produced by catalytic transformations of fossil
resources such as oil, coal and natural gas. Within a few decades, the availability of
these fossil resources is projected to decrease thus making it imperative to use
alternative carbonaceous resources as feedstock. Carbohydrates are abundant and
inexpensive carbonaceous resources available in nature. Since carbohydrates
constitute a renewable and carbon neutral resource, it has become increasingly
important to find feasible ways to convert them into useful chemicals such as 5hydroxymethylfurfural
(HMF), lactic acid, levulinic acid, etc. Levulinic acid has in
particular been recognized as an important bio-derived platform chemical that may
provide a source to produce chemicals and fuels. Levulinic acid is also useful as a
solvent, food flavoring agent, plasticizer, resin intermediate and building block for, e.g.
tetrahydrofuran and succinic acid. To produce levulinic acid, carbohydrates are
traditionally being treated with mineral acid. However, a major drawback in this process
is tedious work-up procedures during downstream separation stages. Functionalised
ionic liquids have emerged as alternative catalysts in many organic reactions due to
their advantages such as, e.g. non-measurable vapour pressure, good thermal stability
and good phase-separation with lipophilic reagents. In the present study, we have
studied the conversion of sucrose, fructose and glucose into ethyl levulinate over
sulfonic acid functionalised ionic liquids in the presence of ethanol as reactant and

solvent. At 140 o C fructose was found to rapidly dehydrate to form HMF which
subsequently reacted with ethanol to form ethyl levulinate with a yield around 70 %
within 5 h.
COIL-4:104
External-Field-Responsive Soft Materials Including Ionic Liquids and Viscoelastic
Nanocomposites
Yukihiro Yoshida (1) , yyoshida@meijo-u.ac.jp, Shiogamaguchi 1-501 Tempaku-ku,
Nagoya 468-8502, Japan ; Kazuya Kai (2) ; Hiroshi Kageyama (2) ; Gunzi Saito (1) . (1)
Research Institute, Meijo University, Nagoya 468-8502, Japan (2) Department of
Energy & Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University,
Kyoto 615-8510, Japan
We synthesized a room-temperature (RT) ionic liquid composed of cobalt bis(dioxolene)
complex dianion with 2,2'-bipyridine having two carboxylate groups at 4-positions. The
magnetic moment exhibits an abrupt upturn at around 30 °C through the glass transition
(–11 °C), and the valence-tautomeric behavior was confirmed by the electronic
absorption spectra. We
also synthesized a viscoelastic nanocomposite composed of negatively-charged MnO2 x–
(x ∼ 0.2) nanosheets, by a RT one-pot processing in aqueous solution. In the clayish
nanocomposite, trimethoxysilyl-containing cations were graft polymerized, and the
resultant cross-linked siloxane network was imprinted on the MnO2 nanosheets to afford
the zwitterionic hairy slabs. Water network formed near the MnO2 slabs allows the
Grotthuss-like proton conduction, which varies greatly depending on both temperature
and humidity. The highest conductivity was observed at 80 °C and 95% RH (1.3 × 10 –4
S cm –1 ). In the congress, we will also present viscoelastic nanocomposites composed of
transition-metal oxide nanosheets other than MnO2.
COIL-4:105
Surface Crystallization of an Ionic Liquid

Doseok Kim (1) , doseok@sogang.ac.kr, #1 Sinsoo-Dong, Seoul Seoul, Republic of
Korea ; Yoonnam Jeon (1) ; Woongmo Sung (1) ; Jaeho Sung (1) ; David Vaknin (2) ; Wei Bu (2) ;
Yukio Ouchi (3) . (1) Department of Physics, Sogang University, Seoul 121-742, Republic
of Korea (2) Department of Physics and Astronomy, Iowa State University, Ames,
United States (3) Department of Chemistry, Nagoya University, Japan
Surface crystallization at the vapor/liquid interface of the ionic liquid (1-butyl-3methylimidazolium
hexafluorophosphate) was observed using synchrotron X-ray
diffraction. Sharp Bragg reflections emerge in grazing-angle X-ray diffraction patterns 40
o C above the bulk melting temperature revealing the presence of long-range ordered
phase at the surface in coexistence with the bulk parent liquid. The unique structure of
the vapor/liquid interface where butyl chains attached to the cations are expelled to the
vapor side facilitate inter-ionic electrostatic interactions that lead to the crystallization.
Our results demonstrate the complexity of ionic-liquids structure with their tendency to
spontaneously phase separate into nano-domains with finite correlations lengths in
coexistence with the liquid phase, that by virtue of interfacial boundary conditions these
nano-domains grow laterally to form quasi-two-dimensional macroscopic crystals.
2-dimensional maps (Qxy, Qz)
of XRD data for surface (a) at 66 o C, (b) 25 o C, and for bulk (c) at 68 o C, and (d) at 21
o C.
COIL-4:106
Chiral Discrimination Controlled by Amino Acid Chiral Ionic Liquids: A
Chiroptical Study
Todd Hopkins (1) , tahopkin@butler.edu, 4600 Sunset Avenue, Indianapolis IN 46208,
United States ; Laurel Heckman (1) ; Dustin Stanton (1) . (1) Department of Chemistry,
Butler University, Indianapolis IN 46208, United States

Controlling chirality and chiral discrimination is extremely important in the
pharmaceutical and agrochemical industries. The structural and chemical diversity of
chiral ionic liquids (CILs) make them very suitable as both solvent and discrimination
agent in a number of chiral processes (catalysis, synthesis, and separations). In this
presentation, the chiral discrimination ability of CILs with chirality derived from amino
acids, including d- and l-alanine methyl ester bis(trifluoromethanesulfonyl)imide (Tf2N - ),
and d- and l-serine methyl ester Tf2N - , will be described. The chiral discrimination is
determined by measuring the circularly polarized luminescence from a racemic mixture
of Eu(dpa)3 3- (where dpa = 2,6-pyridine dicarboxylate dianion) complexes. Chiral
discrimination results will be discussed in terms of the structural elements of the CILs
used.
COIL-4:107
Proteomic Analyses of Ionic Liquid Stress Response in Ascomycota Fungi
Isabel Martins (1) , imartins@itqb.unl.pt, Av. da República, Oeiras - 2780-157, Portugal ;
Paula Alves (1) ; Helga Garcia (1) ; Luis Paulo N. Rebelo (1) ; Cristina Silva Pereira (1)(2) . (1)
Instituto de Tecnologia Química e Biológica - Universidade Nova de Lisboa, ITQB-UNL,
Oeiras 2780-157, Portugal (2) Apartado 12, Instituto de Biologia Experimental e
Tecnológica (IBET), Oeiras 2780-157, Portugal
Ionic liquids are a remarkable group of alternative green solvents, which cannot, a priori,
be considered either benign or toxic. There are numerous studies focussing their toxicity
and eco-toxicity, especially aiming at a better understanding of their chronic and/or
lethal effects.[1] Penicillium strains, despite their apparent high tolerance to grow in their
presence, were shown to dramatically alter their metabolism.[2] Some ionic liquids have
opposite behaviours. The cholinium cation is benign and can be up-taken directly by the
fungal cells and transformed into several metabolites. Imidazolium cation is generally
regarded as toxic and recalcitrant. It increases both the production of reactive-oxygen
species and the intracellular calcium concentration in human cell lines, and inhibits in
vitro the activity of adenosine monophosphate deaminase and of cytochrome P450. In
the present study, we have analysed the myceliar proteome of model Ascomycota
strains after two weeks of exposure to imidazolium and cholinium chlorides. Only 3% of
the fungal myceliar proteome was differentially expressed (~1000 polypeptides
analysed). These proteins are being matched with specific pathways, falling in various
functional categories from metabolism to cellular processes. Some of them have a dual
role, e.g. transaldolase is involved in the metabolism of carbohydrates and in the
biosynthesis of secondary metabolites (viz. up and down regulated in the presence of
imidazolium and cholinium, respectively). These data constitute a solid foundation of the
mechanisms used by fungi to survive in media containing ionic liquids. Corresponding
author: spereira@itqb.unl.pt 1. Petkovic, M., K.R. Seddon, L.P.N. Rebelo, and C. Silva
Pereira. Chemical Society Reviews, 2010. 40 (3), 1383-1403. 2. Petkovic, M., J.
Ferguson, A. Bohn, J. Trindade, I. Martins, M.B. Carvalho, M.C. Leitao, C. Rodrigues,
H. Garcia, R. Ferreira, K.R. Seddon, L.P.N. Rebelo, and C.S. Pereira. Green Chemistry,
2009. 11(6): p. 889-894.

COIL-4:108
Understanding Ionic Liquids Potential in Fungal Biotransformation
Cristina Silva Pereira (1)(2)(3) , spereira@itqb.unl.pt, Av. da República, Oeiras -, Portugal
; Diego Hartmann (1) ; Helga Garcia (1) ; Isabel Martins (1) ; Marija Petkovic (1) ; Rui Ferreira (1) ;
Kenneth Seddon (1)(3) ; Luis Paulo N. Rebelo (1) ; Paula Alves (1) . (1) Instituto de Tecnologia
Química e Biológica - Universidade Nova de Lisboa, ITQB-UNL, Oeiras 2780-157,
Portugal (2) Instituto de Biologia Experimental e Tecnológica (IBET), Oeiras 2780-157,
Portugal (3) The Queen’s University Ionic Liquid Laboratories, QUILL, Queen’s
University of Belfast, Oeiras 2780-157, Portugal
Our group is investigating ionic liquids toxicity towards biotechnologically relevant fungi.
Some Ascomycota species show active growth in media containing extremely high ionic
liquid concentrations - up to two molar in some cases [1-3]. Sub-lethal concentrations of
ionic liquids, even for those apparently benign, have ubiquitously altered the fungal
metabolome [3]. In other words, new potentially interesting low molecular weight
molecules are being bio-synthesized as a consequence of the stress caused by the
ionic liquid. A rather holistic approach focussing on fungal altered morphology,
metabolome, proteome and transcriptome, is being developed by us in order to identify
critical survival mechanisms which enable fungi to tolerate high ionic liquids
concentrations. Our data make it apparent that the ionic-liquids induce major alterations
in gene expression levels, especially in secondary metabolite biosynthetic and
regulatory genes. 20 to 30% of genes already mapped in know metabolic pathways
were differentially expressed during fungal growth in media supplemented with these
chemicals. About 20% of those genes belong to secondary metabolism categories. This
includes major changes in laeA transcript levels (global regulator). They also altered
transcription of genes signalling in critical developmental processes in filamentous fungi.
These include e.g. cot-1 (hyphal elongation) and brlA/abaA/wet (central regulatory
pathway of sporulation). Corresponding author: spereira@itqb.unl.pt 1. Petkovic, M.,
J.L. Ferguson, H.Q.N. Gunaratne, R. Ferreira, M.C. Leitão, K.R. Seddon, L.P.N.
Rebelo, and C. Silva Pereira. Green Chemistry, 2010. 12(4): p. 643-649 2. Petkovic,
M., J. Ferguson, A. Bohn, J. Trindade, I. Martins, M.B. Carvalho, M.C. Leitao, C.
Rodrigues, H. Garcia, R. Ferreira, K.R. Seddon, L.P.N. Rebelo, and C.S. Pereira. Green
Chemistry, 2009. 11(6): p. 889-894. 3. Deive, F.J., A. Rodríguez, A. Varela, C.
Rodrígues, M.C. Leitão, J.A.M.P. Houbraken, A.B. Pereiro, M.A. Longo, M. Ángeles
Sanromán, R.A. Samson, L.P.N. Rebelo, and C. Silva Pereira. Green Chemistry, 2010.
COIL-4:109
Thermal Stability and Evaporation of Supported Ionic Liquid Phases
Florian Heym (1) , florian.heym@uni-bayreuth.de, Universitätsstraße 30, FAN A,
Bayreuth Bayern 95440, Germany ; Johannes Thiessen (1) ; Christoph Kern (1) ; Wolfgang
Korth (1) ; Andreas Jess (1) . (1) Chair of Chemical Engineering, University of Bayreuth,
Bayreuth 95444, Germany

In the published literature the thermal stability of ionic liquids (ILs) is often determined
by thermogravimetrical (TG) measurements. To characterize the thermal stability and
the maximum operation temperature the onset temperature is usually used. This onset
temperature can be misleading during the design of processes without considering the
fact that for some ILs evaporation already starts before thermal instability occurs 1, 2 . In
order to determine the thermal decomposition and evaporation parameters of the pure
ionic liquids [EMIM][NTf2], [BMIM][NTf2], [EMIM][MeSO4] and [EMIM][CF3SO3]
experiments were conducted at ambient pressure by thermogravimetry (TG) using a
new method to distinguish between decomposition and evaporation 3 . Furthermore,
experiments were conducted in high vacuum (HV) with a magnetic suspension balance
(MSB). Here, evaporation as well as the intermediate range between diffusion and
effusion were measured 3 . For an industrial application of the Supported Ionic Liquid
Phase (SILP) technology, the long term thermal stability is an important factor. Also the
knowledge of the evaporation behavior of SILPs is essential for the design of processes
using SILP systems. In order to characterize the mass loss due to evaporation and
decomposition of SILPs the systems of Silica 100 and different porous glases coated
with [EMIM][NTf2] were chosen. The characterization of the SILP material was done by
nitrogen adsorption (BET- and BJH - methods). The evaporation experiments were
conducted under HV using a MSB and a vacuum TG - setup. The modeling of the
resulting mass loss during these experiments was based on the combination of the
effusion theory and the BET – theory. 1 Seeberger, A., Andresen, A. K., Jess, A.,
Phys. Chem. Chem. Phys., 2009, 11, 9375 - 9381. 2 Heym, F., Etzold, B., Kern, C. and
Jess, A. Phys. Chem. Chem. Phys., 2010, 12, 12089-12100 3 Heym, F., Etzold, B.,
Kern, C. and Jess, A. Green Chemistry (under review)
COIL-4:110
Photo-Induced Bimolecular Electron Transfer in Ionic Liquids
MIN LIANG (1) , mul15@psu.edu, 104 Chemistry Building, University Park Pennsylvania
16802, United States ; Anne Kaintz (1) ; Gary Baker (2) ; Mark Maroncelli (1) . (1) The
Pennsylvania State University, Department of Chemistry, University Park PA 16802,
United States (2) The University of Missouri, Department of Chemistry, Columbia MO
65211, United States
Ionic liquids (ILs) are currently being explored as electrolytes in dye-sensitized solar
cells, batteries, and super-capacitors. Understanding electron transfer kinetics in IL
media is relevant in such applications as well as being of fundamental interest. A central
question is how electron transfer kinetics in ILs might differ from those in conventional
solvents. A number of recent studies have suggested that bimolecular electron transfer
kinetics, although slower than in conventional solvents, are much faster than expected
in ionic liquids. We have used fluorescence quenching experiments to measure photoinduced
electron transfer rates in a series of pyrrolidinium ionic liquids between the
electron acceptors coumarin 152 and 9,10-dicynoanthracene and the donor N,Ndimethylaniline.
Quenching rates were determined from both steady-state emission
spectra and time-resolved fluorescence decays measured using time-correlated single

photon counting (25 ps time resolution). In a few cases, fluorescence up-conversion
measurements (250 fs) were also performed to examine the “static” quenching
component. Stern-Volmer analyses of steady-state and time-resolved data indicate that
reaction rates are much larger than expected based on the simple Smoluchowski
equation for bimolecular rate constants. While such predictions are accurate for these
same reactions in conventional solvents, they fail in ionic liquids due primarily to much
slower diffusion in ionic liquids. This slower diffusion leads to significantly nonexponential
fluorescence decays which indicate that time-dependent kinetics play an
important role in these solvents. Use of a complete time-dependent reaction model,
including distance-dependent electron transfer rates predicted by classical Marcus
theory and measured solute diffusion coefficients, provides a satisfying description of
the quenching kinetics observed.
COIL-4:111
Texturing of Glassy Carbon Electrode Surfaces and Particles Production in
Imidazolium-Based Ionic Liquids
Catherine C Santini (1) , santini@cpe.fr, 43 Bd du 11 Novembre 1918, Villeurbanne
France, France ; Thibault Alphazan (1) ; Bastien Doumèche (2) . (1) UMR 5265 C2P2,
CNRS, France (2) ICMBS, Génie Enzymatique, Université Lyon 1, France
Nowadays, the development of Fuel Cells is up-and-coming but financial and technical
issues have led researchers to find new materials in order to make “greener” Fuel Cells.
These are ideally based on graphite electrodes instead of noble metals, renewable
substrates and ionic liquids as electrolytes (non flammable, low vapour pressure).
Moreover, ionic liquids can be considered as solvents as well as reactants
functionalizing the graphite surface.[1,2] Meanwhile, the influence of an ionic liquid (1butyl,3-methylimidazolium
bis(trifluromethylsulfonyl)imide ([C1C4Im][NTf2])) on glassy
carbon electrodes has to be studied under several working potentials as a function of
time and in the presence or the absence of water. In this communication, we will report
the conditions in which the electrodes are modified giving nano-to-micro-sized carbon
objects. These have been characterized by fluorescence, transmission or scanning
electron microscopy (TEM or SEM), while the surface texture of the glassy carbon
electrode has been investigated by atomic force microscopy (AFM), [figure 1]. [1] Lu,
J.-x. Yang, J. Wang, A. Lim, S. Wang and K. P. Loh, ACS Nano 2009, 3, 2367-2375.
[2] Liang C., Huang J-F., Li Z., Luo H., and Dai S., Eur. J. Org. Chem. 2006, 586-589
COIL-4:112
“Amphiphilic” Ionic Liquid: Theoretical Study
Artem Anatolievich Aerov (1) , aerov@polly.phys.msu.ru, Leninskie Gory, Moscow
119991, Russian Federation ; Alexei Removich Khokhlov (1)(2) ; Igor Ivanovich
Potemkin (1)(2) . (1) Faculty of Physics, Moscow State University, Moscow 119991,

Russian Federation (2) Institute of Poymer Science, University of Ulm, Moscow 119991,
Russian Federation
We investigate how an IL distributes near the phase boundary of two incompatible nonionic
liquids and how it influences the surface tension, having supposed that cations
have higher affinity to one of the non-ionic components and anions, vice versa, – to the
other one, i.e. the IL is “amphiphilic”. We determine the components concentrations and
the electrostatic potential profiles. Our method is applicable for any ions concentration
(i.e. in an IL case when ions volume fraction is of order unity and in the case of low ions
concentration). We show that a double electrostatic layer is formed at the boundary.
The layer width increases as the ions concentration approaches either zero or the value
corresponding to the critical point. The ratio of the maximal ions concentration in the
layer to their concentration in the bulk is the larger the lower is the IL concentration and
the higher is the difference of the cations and anions affinities to the two non-ionic
components. The surface tension is the lower the higher is the affinities difference and
the higher is the IL concentration. The surface tension can even reach zero at an IL
concentration lower than the critical point concentration, which means that the mixture
can be microheterogeneous. Hence, an “amphiphilic” IL behaves as a surfactant, but
instead of a monomolecular layer it forms at the phase boundary a double electrostatic
layer which can be up to several hundred molecules thick. This work was supported by
the Education and Science Ministry of the Russian Federation (contract No. Π1365 for
the realization of the federal task program “Scientific and scientific-educational
personnel of innovational Russia”, 2009-2013). Aerov, A.A.; Khokhlov, A.R.; Potemkin,
I.I JPC B, 2010, 114, 15066; 2006, 110 , 16205; 2007, 111, 10189; 3462; Aerov, A.A.;
Potemkin, I.I JPC B, 2009, 113, 1883.
COIL-4:113
Ionic-Liquid Catalyzed Urea Synthesis by the Carboxylation of Amine: A
Mechanistic Consideration
Yuna Shim (1) , ssyuna@naver.com, 1 Hoegi-dong, Dongdaemun-gu, Seoul 130-701,
Republic of Korea ; Dinh Quan Nguyen (1) ; Minserk Cheong (1) ; Hoon Sik Kim (1) ; Je Seung
Lee (1) . (1) Department of Chemistry, Kyung Hee University, Seoul 130-701, Republic of
Korea
The roles of ionic liquids(ILs) in the syntheses of 1,3-disubstituted ureas from the
carboxylation of amines by CO2 were investigated. Experimental results demonstrated
that the carboxylation reactions of 1,3-dibutylurea (DBU) was greatly influenced by the
types of both cations and anions of ILs used. As a whole, for the carboxylation of n-butyl
amine, imidazolium- and phosphonium-based ionic liquids exhibited higher activities
than those of pyrrolidinium-, piperidinium-, and ammonium-based ILs. This suggested
the importance of the interaction between cation of ILs employed and the carbonyl
oxygen of CO2. For the imidazolium series ILs, the yield of DBU increased with
increasing basicity of the anion. Computational study on the mechanistic aspects of the
carboxylation with methyl amine with or without the presence of an IL, 1-ethyl-3-

methylimidazolium chloride ([EMIm]Cl), clearly demonstrates that the IL plays a pivotal
role in lowering the activation energy of the transition states, thereby facilitating the
carboxylation reaction.
COIL-4:114
Absorption of Sulfur Dioxide in Ether-Functionalized Ionic Liquids
Sung Yun Hong (1) , tjddbs727@nate.com, 1 Hoegi-dong, Dongdaemun-gu, Seoul 130-
701, Republic of Korea ; Hyunjoo Lee (2) ; Kwang-Deog Jung (2) ; Minserk Cheong (1) ; Hoon
Sik Kim (1) ; Je Seung Lee (1) . (1) Department of chemistry, Kyung Hee University, Seoul
130-701, Republic of Korea (2) Clean Energy Research Center, Korea Institute of
Science and Technology, Seoul 136-791, Republic of Korea
Fossil fuel burning power plant is one of major producers of sulfur dioxide emissions
worldwide. To mitigate the emissions of SO2, scrubbing process employing liquid
absorbents is considered as an alternative method in addition to the flue gas
desulfurization (FGD). Room temperature ionic liquids (RTILs), ether-functionalized
imidazolium methane sufonates were found to exhibit extremely high SO2 solubility, at
least 2 moles of SO2 per mole of RTIL at 30 o C and at atmospheric pressure. The
solubility of SO2 in these RTILs increases with increasing number of tethered ether
oxygen atoms and also with the pressure rise. FT-IR spectroscopic and quantum
mechanical calculation results show that such high SO2 solubility in ether-functionalized
RTILs is originated from the combined interactions of SO2 with ether oxygen atom or
atoms on the imidazolium ring and methane sulfonate anion. The absorbed SO2 gas
can be completely desorbed from the RTILs by heating at 100 o C in a N2 flow, thereby
allowing the RTILs to be reused up to 5 cycles without loss of their initial capacity.
COIL-4:115
Understanding the Dissolution Power of Polyols by Ionic Liquids Using the
Example of a Well-Defined Model Compound

Ralf Ludwig (1) , ralf.ludwig@uni-rostock.de, Dr.-Lorenz-Weg 1, Rostock D-18059,
Germany ; Zakar Papanyan (1) ; Christian Roth (1) ; Dietmar Paschek (1) . (1) Institute of
Chemistry, Physical and Theoretical Chemistry, University of Rostock, Rostock D-
18059, Germany
For understanding the dissolution power of ionic liquids and traditional solvents for
cellulose we have chosen the alcohol pentaerythritol C(CH2OH)4 (PET) as well-defined
solute model compound.[1-3] With cellulose it shares a strong hydrogen bond network
resulting in high melting points and unfavourable solubility in water. We demonstrated
that even high polarity of solvents is not sufficient to breakdown the H-bond network of
the alcohol pentaerythritol C(CH2OH)4. Obviously, the ionic character as given in ionic
liquids is mandatory for the dissolution process. The dissolutions power mainly depends
on the anion ability to disrupt the H-bond network in PET. This is indicated by a
characteristic shift of the infrared OH stretch frequencies of the solute to lower and
higher wavenumbers in respect to the solid describing less effective or effective
solvents respectively. Supported by DFT calculations it is shown that the dissolution
power of a molecular solvent such as DMSO or weaker interacting ILs such as
[C2mim]EtSO4 is not strong enough to overcome the PET network significantly. It needs
strongly interacting anions such as acetate in the IL or fluoride in DMSO/TBAF
trihydrate to disrupt the strong PET-PET H-bonds. 1 R. P. Swatloski, S. K. Spear, J. D.
Holbrey, R. D. Rogers, J. Am. Chem. Soc. 2002, 124, 4974-4975. 2 A. Pinkert, K. N.
Marsh, S. Pang, M. P. Staigeer, Chem. Rev. 2009, 109, 6712-6728. 3 L. Pauling, The
Nature of the Chemical Bond, 3 rd ed., 1960, Cornell University Press, Ithaca, New York.
COIL-4:116
Ambient Pressure X-Ray Photoelectron Pectroscopy Studies of the Gas-Liquid
Interface of Ionic Liquids
Alexandria M Margarella (1) , amargare@uci.edu, 1102 Natural Sciences II, Irvine Ca
92697, United States ; Theresa M McIntire (1) ; Ming H Cheng (1) ; Hendrik Bluhm (2) ; John
C Hemminger (1) . (1) Department of Chemistry, University of California, Irvine, Irvine Ca
92697, United States (2) Chemical Sciences Division, Lawrence Berkeley National
Laboratory, Berkeley Ca 94720, United States
Ambient pressure x-ray photoelectron spectroscopy (AP-XPS) performed using
synchrotron light at the Advanced Light Source was used to study the ion composition
at the surface and bulk of different room temperature ionic liquids (ILs). Utilizing
synchrotron radiation, elemental depth profiles of ILs containing alkyl-imidazolium
cations with halide or tetrafluoroborate anions were obtained by varying the
photoelectron kinetic energy. Correlating well with previous research, ion composition
as a function of depth showed that both cations and anions are present at the surface,
also revealing significant carbon enhancement at the surface, most likely due to the
alkyl chains of the cation protruding into the gas phase. AP-XPS offers the advantage of
doing photoelectron spectroscopy under higher pressures, up to a few torr, so the
sample can be exposed to a variety of gas-phase chemical environments. ILs are

considered hygroscopic and this uptake of water from the atmosphere can hinder the
success of ILs in potential applications. XP spectra of ILs in the presence of water vapor
show an uptake of water by all ILs. Similar to other experiments in the literature, the
interaction and water uptake behavior depends on the nature of the anion of the IL, as
well as the temperature of the sample. ILs also offer the ability as a way to capture CO2
by absorbing or reacting with the gas and preliminary AP-XPS experiments evaluating
the use of ILs as adsorption media for CO2 capture will also be presented.
COIL-4:117
Polyesterification of a Hydroxyacid in Brønsted Acid Ionic Liquids
Shaodong Zhang (1)(2) , shaodong.zhang@upmc.fr, 3 rue Galilée, Ivry sur seine Ile de
France, France ; Hervé Lefebvre (1)(2) ; Martine Tessier (1)(2) ; Alain Fradet (1)(2) . (1) UPMC
Univ Paris 06, Ivry sur seine Ile de France 94200, France (2) CNRS, Ivry sur seine Ile
de France 94200, France
In the present work, Brønsted acid ionic liquids (BAILs) based on 3-alkyl-1-(butyl-4sulfonic
acid)imidazolium cation were found to be very efficient polyesterification
solvents and catalysts. At 90-110 °C, only 5-30 min was required to obtain high molar
mass poly(12-hydroxydodecanoic acid) (Mw up to 40000 g.mol -1 ). The polyesterification
was faster in BAILs with the anion Tf2N - , but small amounts of ethers and double bonds
arising from side reactions were detected in final polymer. On the other hand, no side
reactions took place in the BAIL with the anion H2SO4 - , except the formation of a
sulfonate ester intermediate that can further react with carboxylic acid groups to yield
the expected ester. This intermediate, not observed in Tf2N-based BAILs, might be
involved in the protection of hydroxy end groups from etherification in HSO4-based
BAILs. Considering the acidity of H2SO4 is much higher than that of Tf2NH, it is
suggested that the structure of these BAILs could be different: Alkylsulfonic acid–
substituted imidazolium for the former, while just a mixture of imidazolium–sulfonate
zwitterion and Tf2NH for the latter. The influence of reaction temperature, water
elimination method and BAIL concentration are also discussed.
COIL-4:118

Synthesis of Novel Poly(isobutylene)-Based Ionic Liquids
Parvin Zare (1) , parvin.zare@chemie.uni-halle.de, Von-Danckelmann-Platz 4, Halle
(Saale) Saxony anhalt 06120, Germany ; Wolfgang H. Binder (1) . (1) Department of
Chemistry, Martin-Luther-Universität Halle-Wittenberg, Halle (Saale) Saxony anhalt
06120, Germany
Outstanding characteristics of ionic liquids make them very popular compounds with a
very wide range of applications. Among all of the synthesized ILs, those with shorter
chain length are widespread because of their simplified synthetic procedure 1 . Recently
polymer-based ionic liquids also received a lot of attention 2 . However, it is almost
impossible to synthesize ionic liquids containing hydrophobic polymer chains via
common quaternerization reaction. We therefore explored a different strategy to
synthesis such kind of ionic liquids using poly(isobutylene) [PIB]. Besides
biocompatibility and the low Tg value of PIB [~(-78°C)] 3 which keeps it as liquid at room
temperature, the possibility of achieving moderated viscosity by controlling the degree
of polymerization was our motivation to design PIB-based ionic liquids.
In this work, novel ionic
liquids based on poly(isobutylene) containing imidazolium, pyrolidinum and amunim
cations with different anions have been synthesized. Poly(isobutylene) synthesized via
living cationic polymerization. After modifynig the end group, it was reacted with the
desired ionic spesies. The obtained polymeric-ILs was characterized via 1 H, 13 C NMR
and ESI-TOF/MS. Furthermore the thermal properties of the synthesized ionic liquids
was investigated by DSC and TGA. [1] Wasserscheid, P.; Welton, T.; Ionic Liquids in
Synthesis, Wiley-VCH, 2003. [2] Lu. J.; Ya. F.; Texter. J. Prog. Polym. Sci. 2009, 431-
448 [3] Kunal, K.; Paluch, M.; Roland, C. M.; Puskas, J. E.; Chen, Y.; Sokolov, A. P. J.
Polym. Sci. Part B: Polymer Physics 2008,46 (13), 1390-1399
COIL-4:119
Non-Toxic Ionic Liquids for New Applications: Toxicological Investigations of
Ionic Liquids
Florian Stein (1) , florian.stein@uni-rostock.de, Albert-Einstein-Straße 3a, Rostock
Mecklenburg Vorpommern, Germany ; Marian Löbler (2) ; Hiroyuki Ohno (3) ; Udo Kragl (1) .
(1) Department of Chemistry, University of Rostock, Rostock 18059, Germany (2)
Institut für Biomedizinische Technik, University of Rostock, Rostock 18119, Germany
(3) Department of Biotechnology, University of Agriculture and Technology, Tokyo 184-
8588, Japan

The interest in ionic liquids (ILs) has been growing during the last decade, because they
were said to be “green solvents”. But recently many ionic liquids have proven to be
toxic. Current approaches attempt to find solutions to design ILs, which can also be
used in pharmaceutical and food industries. In our studies we are testing ionic liquids for
their biocompatibility in order to find non-toxic ILs. A number of 19 different ionic liquids
were tested with mouse fibroblasts (L 929) in order to determine their effect on cell
proliferation and viability. Additionally the amounts of endotoxin within the ionic liquids
were analyzed. Several ionic liquids, based on substances found in nature, showed only
low cytotoxicity, while ionic liquids with long alkyl chains were found to be highly toxic to
cells. Nevertheless, highly concentrated ionic liquid solutions, mainly synthesized from
natural products, seem to be toxic to cell lines, due to high osmolality. The highest EC50
values were determined for ionic liquids made of amino acid esters and by [C2mim]BF4,
resulting in the survival of 50% of the mouse fibroblasts in 32 mM solution of IL. The
most toxic ionic liquid was [C10mim]Cl whit an EC50 of 0.04 mM.
Name
Viability
log EC50
Proliferation
log EC50
Viability
EC50 [mmol/L]
Ammoeng 110 -2.65 -2.75 2.240 1.780
[P4444][Pro] -3.5 -3.4 0.316 0.398
[P4444][Val] -3.7 -3.0 0.200 1.000
[P4444][Gly] -3.65 -2.9 0.240 1.260
[P4444][Leu] -3.6 -2.95 0.251 1.120
[Demim]Cl -4.5 -4.4 0.032 0.032
[GlyC1] NO3 -1.5 -1.5 31.60 31.60
[AlaC1] NO3 -1.5 -1.5 31.60 31.60
[C4mim]Cl -2.2 -2.25 6.310 5.620
[Amim] Br -2.0 -1.9 10.00 12.60
[C4mim][PF6] -2.5 -2.1 3.160 7.940
[C2mim][BF4] -1.5 -2.3 0.316 5.010
[C2mim][SCN] -2.2 1.8 6.310 15.80
COIL-4:120
Enzymatic Hydrolysis of Cellulose in Ionic Liquids
Proliferation
EC50 [mmol/L]
Andrea Mele (1)(2) , andrea.mele@polimi.it, Via L. Mancinelli, 7, Milano Italy 20131, Italy ;
Paola D’Arrigo (1)(2) ; Cristina Formantici (3) ; Yves Galante (3) ; Franca Castiglione (1)(2) ;
Loredano Pollegioni (2) ; Stefano Tamborrini (2) . (1) Dipartimento di Chimica, Materiali,
Ingegneria Chimica “G. Natta”, Politecnico di Milano, Milano, Italy (2) The Protein

Factory, Politecnico di Milano and Università dell’Insubria, Milano, Italy (3) Laboratory of
Biotechnology, Lamberti spa, Albizzate (VA), Italy
Green alternatives to fossil-based fuels are very attractive and can be produced from
cellulosic materials 1 . Cellulose is the primary product of photosynthesis in plants and is
the most abundant renewable polymer in the biosphere. The production of biofuels
starting from cellulose is gaining increasing attention and obviously implies the partial or
total hydrolysis of cellulose: enzymatic processes are considered the most promising
technology. Cellulases are the enzymes most commonly employed to selectively
depolymerize cellulose in buffered aqueous solvents. Because of the very low solubility
of cellulose due to its highly organized structure, enzymatic conversions proceed at very
slow reaction rates. To improve the yield of fermentable monosaccharides, pretreatments
of cellulose, such as thermal, chemical or physical treatment, have been
applied to afford a better enzymatic conversion. An emerging chemical pre-treatment
relies on the use of ionic liquids. 2 However, it was previously demonstrated that ionic
liquids are able to efficiently solubilise cellulose, but often inhibit the enzymatic activity
of native cellulases. 3 The present study describes the development of an enzymatic
hydrolysis reaction of commercial celluloses in aqueous-ionic liquid media, in order to
produce in one-step low molecular weight intermediates which could be successively
used for further industrial modifications and/or applications. Two recombinant, monocomponent
endocellulases from Trichoderma reesei or Streptomyces sp. have been
tested. This work provides a comparison between the stability and the activity of these
endocellulases in the presence of three commercial ionic liquids, namely 1-ethyl-3methylimidazolium
diethylphosphate ([Emim][DEP]), 1-ethyl-3-methylimidazolium
acetate ([Emim][OAc]), 1-butyl-3-methylimidazolium chloride ([Bmim][Cl]). 1 Klemm D,
Heublein B, Fink HP, Bohn A. 2005 Angew Chem Int Ed 44, 2-37. 2 Swatloski RP,
Spear SK, Holbrey JD, Rogers RD 2002 J. Am. Chem. Soc. 124, 4974-4975. 3 Turner
MB, Spear SK, Huddleston JG, Holbrey JD, Rogers RD 2003, Green Chem 5, 443-447.
COIL-4:121
Maxwell-Stefan Diffusivities in Mixtures of Ionic Liquids with DMSO and H2O
Thijs JH Vlugt (1) , t.j.h.vlugt@tudelft.nl, Leeghwaterstraat 44, Delft Delft 2628CA, The
Netherlands; Xin Liu (1)(2) ; Andre Bardow (1)(2) . (1) Process & Energy Department, Delft
University of Technology, Delft 2628CA, The Netherlands (2) Lehrstuhl fur Technische
Thermodynamik, RWTH Aachen University, Delft 2628CA, The Netherlands
Slow diffusion of absorbed components in ionic liquids (ILs) often restricts their
applicability. A thorough understanding of transport diffusion in ionic liquids is therefore
highly desirable. The slowness of diffusion makes it difficult to study both in experiments
and simulations. Previous research mainly focused on self-diffusion, while for
applications, transport diffusion is far more important. In this work, transport diffusion in
ionic liquids is studied using the Maxwell-Stefan (MS) approach. This approach is
commonly used as it correctly accounts for the chemical potential gradient as driving
force. MS diffusivities Dij describe the friction between components i and j in a mixture.

Unfortunately, it is difficult to obtain MS diffusivities from experiments. MS diffusivities
can be directly extracted from Molecular Dynamics (MD) simulations. MS-diffusivities
were computed in binary systems containing 1-alkyl-3-methylimidazolium chloride
(CnmimCl), water and/or dimethyl sulfoxide (DMSO). The dependence of MS diffusivities
on mixture composition were investigated. Our results show that: (1) For solutions of ILs
in water and DMSO, MS diffusivities exponentially decrease with increasing IL
concentration. (2) ILs stay in a form of isolated ions in CnmimCl-H2O mixtures, however,
dissociation into ion pairs is less observed in CnmimCl-DMSO systems. This has a large
effect on the concentration dependence of MD diffusivities. (3) Recently, we proposed a
new model for predicting the MS diffusivity at infinite dilution, Dij x k →1 . This quantity
describes the friction between components i and j when both are infinitely diluted in
component k. In contrast to earlier empirical models, our model is based on the linear
response theory and the Onsager relations which allows a clear interpretation of the
results. The present study clearly shows that velocity cross-correlation functions in ionic
liquids cannot be neglected and that the dissociation of ILs into ion pairs has a strong
influence on diffusion.
COIL-4:122
Phosphors on the Nanoscale Made from Ionic Liquids
Anja-Verena Mudring (1) , anja.mudring@rub.de, NCDF 04/398, Bochum NRW 44780,
Germany . (1) Anorganische Chemie I - Festkörperchemie und Materialien, Ruhr-
Universität Bochum, Bochum 44780, Germany
A very important goal for environmentally benign lighting is the development of new
luminescent materials with high quantum efficiencies, sometimes even higher than
100%. The most promising system for the realization of such a quantum cutting material
where one VUV photon is converted to two VIS photons is the system of GdF3:Eu. In
order to obtain a system with such a high quantum yield it is very important to
synthesize the compounds under strict inert conditions to exclude any contamination of
oxygen. In the case of Eu 3+ oxygen would allow for non-radiative relaxation via
europium–oxygen charge transfer states followed by emission from these levels. In
order to synthesize the europium doped GdF3 nanocrystals, the corresponding acetate
precursors were converted in the desired molar ration via microwave irradiation in the
task-specific ionic liquid [C4mim][BF4] (C4mim = 1-butyl-3-methylimidazolium). The
optical properties of the obtained materials will be presented in detail. [1] C. Lorbeer,
J. Cybinska, A.-V. Mudring, Chem. Commun. 2010, 46, 571. [2] C. Lorbeer, J.
Cybinska, A.-V. Mudring, Cryst. Growth & Des. 2011, in press. Funding for this work
provided by ERC (no. 200475).
COIL-4:123
Glassy State of the Quaternary Ammonium Type Ionic Liquid-H2O Mixtures

Yukihiro Yoshimura (1) , muki@nda.ac.jp, 1-10-20 Hashirimizu, Yokosuka Kanagawa
239-8686, Japan ; Hiroshi Abe (2) ; Tomonori Hanasaki (3) ; Yusuke Imai (2) . (1) Department
of Applied Chemistry, National Defense Academy, Yokosuka Kanagawa 239-8686,
Japan (2) Department of Materials Science and Engineering, National Defense
Academy, Yokosuka Kanagawa 239-8686, Japan (3) Department of Applied Chemistry,
Ritsumeikan University, Kusatsu Shiga 525-8577, Japan
One of the current topics room temperature ionic liquids (RTILs) is that a polar/nonpolar
nano-phase separation occurs and the phenomenon is also observed even in a RTIL-
H2O mixture [1]. As the glassy state is a frozen state of the liquid structure at low
temperatures, we can expect that the nano-phase separation may be detected, e.g., as
multiple glass transitions. Typically, there are imidazolium, pyridinium and aliphatic
ammonium-based RTILs, however, fundamental researches of aliphatic ammoniumbased
RTILs are still scarce. In this study, we have investigated the glassy state of two
quaternary ammonium type ionic liquids, N, N-diethyl-N-methyl-N-(2-methoxyethyl)
ammonium tetrafluoroborate ([DEME][BF4]) and iodide ([DEME][I]) -H2O mixtures. We
measured glass transition temperatures of quick pre-cooled samples as a function of
water concentration (x mol% H2O) and also the glassy Raman spectra of the mixtures.
We found that two glass transitions (Tgs) were observed at 16.5 < x < 30.0 in the
[DEME][BF4] mixtures. Thus, small amount of H2O molecules in the [DEME][BF4]-H2O
mixtures may enhance the nano-phase separation at the specific concentrations, and,
at least, two different species (phases) exist at 16.5 < x < 30.0. On the other hand, we
could also observed two glass transitions in the [DEME][I]-H2O mixtures, but the two-Tgs
region lies to a water-rich side of 77.5 ≤ x ≤ 85.0. The glassy Raman spectra in the OH
stretching vibrational region from 3100-3800 cm -1 are very different between the
[DEME][BF4] and the [DEME][I] solutions. Even at 77 K, the spectrum of [DEME][BF4]
solution displays a nearly-free hydrogen bonded band (NFHB) of water molecules,
which exist as single molecules (not self-associated state) without forming the
hydrogen-bonding network as in pure H2O liquid. There is no water molecule due from
the NFHB in the [DEME][I]-H2O mixture. [1] W. Jiang, Y. Wang, G. A. Voth, J. Phys.
Chem. B, 111, 4812 (2007).
COIL-4:124
New Hexaethylene Glycol and Poly(Ethylene Glycol) Based Ionic Liquids as
Potential Lubricants
Maria Mahrova (1) , mahrova@uvigo.es, Campus Universitario, s/n, Vigo 36310, Spain ;
Parvin Zare (2) ; Wolfgang Binder (2) ; Emilia Tojo (1) . (1) Department of Organic Chemistry,
University of Vigo, Vigo Pontevedra 36310, Spain (2) Faculty of Natural Sciencies
II/Institute of Chemistry, Macromolecules Chemistry, Martin-Luther University, Halle-
Wittenberg, Halle (Saale) 06120, Germany
Due to the unique physico-chemical properties of ionic liquids (non-volatility, nonflammability,
as well as high chemical and thermal stability), ionic liquids have gained
increasing intention as potential novel lubricants in the past decades. However, there is

a few knowledge about the appropiate formulation of a lubricant based on polymeric
ionic liquids. 1-4 In this work we report the synthesis and characterization of a series of
hexaethylene glycol and poly(ethylene glycol) based ionic liquids with two types of
anions: tosylate and methanesulfonate. These ionic liquids were prepared according to
the azide/alkyne „click“ reaction in presence of base e.g. N,N-diisopropylethylamine,
DIPEA and a catalyst such as copper(I) bromide (CuBr) under microwave irridation
(Figure 1). The purity of all prepared ionic liquids was determined by 1 H, 13 C NMR and
ESI-TOF/MS. Furthermore, tribology data were measured, indicated favourable
properties of the highly interesting new ionic liquids. Keywords: ionic liquids, „click“
reaction, synthesis. Figure
1. Synthesis of hexaethylene glycol and poly(ethylene glycol) based ionic liquids.
Aknowledges: The authors are grateful to MINILUBES Network-European Commission
Research FP7 for financial support. References: (1) Plechkova, N. V.; Seddon, K. R.
Chem. Soc. Rev. 2008, 37, 123-150. (2) Minami, I. Molecules. 2010, 14, 2286-2305. (3)
Binder, W. H.; Sachsenhofer, R. Macromol. Rapid. Commun. 2007, 28, 15-54. (4)
Binder, W. H.; Sachsenhofer, R. Macromol. Rapid. Commun. 2008, 29, 952-981.
COIL-4:125
Anisotropically Ion-Conductive Fluorohydrogenate Ionic Liquid Crystals
Fei Xu (1) , fei.xu@ky3.ecs.kyoto-u.ac.jp, Yoshida, Sakyo-ku, Kyoto Kyoto 606-8501,
Japan ; Kazuhiko Matsumoto (1) ; Rika Hagiwara (1) . (1) Graduate School of Energy
Science, Kyoto University, Kyoto 606-8501, Japan
Ionic liquid crystals are interesting candidates to design anisotropic ion-conductive
materials owing to their anisotropic structural organization containing ion-conductive
channels and insulating sheets. Fluorohydrogenate ionic liquids have excellent
properties such as low viscosity and high conductivity. In this study, 1-alkyl-3methylimidazolium
fluorohydrogenate ionic liquid crystals (CxMIm(FH)2F, x = 10, 12, 14,
16, and 18 and C12MIm(FH)nF, n = 1.0 ~ 2.3) have been synthesized and characterized.
Differential scanning calorimetry reveals these fluorohydrogenate ionic liquid crystals
show liquid crystalline mesophases around ambient temperature, and the temperature
range of the mesophase monotonously increases with the increase of the carbon
number or the decrease of the n value. Smooth focal conic texture observed by
polarized optical microscopy and sharp peaks in X-ray diffraction patterns suggest the
ionic liquid crystals show a smectic A mesophase with an interdigitated bilayer structure.
The distance between the two layers in the smectic structure monotonously increases

with increasing alkyl chain length and decreases with increasing temperature. For
CxMIm(FH)2F, conductivity parallel to the smectic layers is around 10 mS cm −1
regardless of the alkyl chain length, whereas that perpendicular to the smectic layers
decreases with increasing alkyl chain length. For C12MIm(FH)nF, conductivities of both
the directions decrease with the decrease of the n value.
COIL-4:126
Understand the Organic Reactivity in Ionic Liquids: The Supermolecular Scheme
Christian S Pomelli (1) , cris@dcci.unipi.it, Via Risorgimento 35, Pisa Pisa 56126, Italy ;
Cinzia Chiappe (1) . (1) Department of Chemistry and Industrial Chemistry, University of
pisa, Pisa Pisa 56126, Italy
The use of ionic liquids as medium for organic reactions is nowadays a common
practice. The main reasons of this popularity are the lack of volatility and the positive
effects on a large number of reactions. The interpretation and the rationalization of the
effects of Ionic Liquids on organic reactivity is a less explored field. In fact scholars have
tried, and try, to classify ionic liquids solvent effects using the parameters and tools
developed for molecular solvents with alternating results. In fact Ionic Liquids introduces
a total new “coordinate” in the solvent space that is not yet well defined. In the
supermolecolar scheme one or more ions of the solvent are enclosed in an extended
molecular system that is studied with a computational method. This approach permit to
evaluate the specific effects of the nearest neighbors ions on the reaction. From the
computational point of view this approach presents some difficulties: the supermolecolar
system can be constituted by 3 or more molecular fragments that are not easy to
handle. The starting geometrical structures must be accurately prepared. This require
an expertise in both the fields of computational and organic chemistry. The
interpretation of the results is complex for the same reasons. In our interdisciplinary
group several studies of this kind has been performed about different kinds of organic
reactions [1-7]. The results of calculations has been compared with experimental results
obtaining a good agreement. Using the information derived from these studies we try to
sketch some preliminary general concepts about effects of ionic liquids on organic
reactivity at molecular scale.
COIL-4:127
Electrochemistry in Vacuo: In situ Monitoring of Electrochemically Generated
Species by X-Ray Photoelectron Spectroscopy
Alasdair W. Taylor (1) , Alasdair.Taylor@nottingham.ac.uk, University Park, Nottingham
Nottinghamshire NG7 2RD, United Kingdom ; Fulian Qiu (1) ; Shuang Men (1) ; Peter
Licence (1) ; Ignacio J Villar-Garcia (2) . (1) School of Chemistry, University of Nottingham,
Nottingham NG7 2RD, United Kingdom (2) School of Chemistry, Addis Ababa
University, Addis Ababa PO Box 1176, Ethiopia

The negligible volatility and intrinsic electrolytic capacity of ionic liquids have been
exploited to perform spectroelectrochemistry under ultrahigh vacuum (UHV) conditions.
It has been demonstrated for the first time that the UHV spectroscopic technique X-ray
photoelectron spectroscopy (XPS) can be used to monitor electrochemically induced
oxidation state changes in situ. This unique combination of electrochemistry and XPS,
EC-XPS, has the power to observe changes in the electronic and chemical environment
of elements upon electrochemical oxidation or reduction. EC-XPS experiments were
performed in a cell consisting of a modified XPS sample stub fitted with a platinum wire
working electrode. The platinum wire was insulated from the stub, which in turn acted as
counter electrode. Separate electrical contacts could then be made between the
electrodes and the external potentiostat. In a proof-of-principle EC-XPS investigation,
clear spectroscopic evidence of the reduction of Fe III to Fe II was observed when
analysing a solution of [C4C1Im][Fe III Cl4] in [C2C1Im][EtOSO3]. 1 A second study has
looked at the electrodissolution of a copper wire in ionic liquids. In situ XPS identified
that the electrogenerated species was Cu + and uncovered the rapid diffusion of these
copper ions across the surface of the liquid droplet. 2
5817-5819 2. Qiu et al., PCCP, 2010, 12, 1982-1990
COIL-4:128
1. Taylor et al., Chem. Commun., 2009,
Ionic Liquid Crystals for Nanochemistry, Gene Delivery and Radiation Detection
Laurent Douce (1) , Laurent.Douce@ipcms.u-strasbg.fr, 23 rue du Loess, BP-43,
Strasbourg 67034, France . (1) IPCMS/DMO, IPCMS/DMO, University of Strasbourg, 23
rue du Loess, BP-43, Strasbourg 67034, France
Rapid development of the field of ionic liquid or molten salt chemistry has occurred over
the past decade due to the applications found for ionic liquids as solvents for organic
synthesis and catalysis and for electrochemistry. A particularly important group of these

materials has been based on salts of imidazolium cations, where the structure of both
the cations and their counteranions can be adapted to various processes and to the
induction of properties such as mesomorphism. From the perspective of supramolecular
chemistry, many avenues still remain to be explored along these lines for the
development of new materials. Our group has been interested in the development of a
strategy of synthesis providing access to a wide range of imidazolium derivatives in
which the substituents incorporate both rigid and flexible units, so enabling the control of
the emergence of mesomorphism, as well as of the particular forms it may take. Three
examples of our research will be discussed; 1) The nanochemistry arising when
cyanometallates are involved as the counteranions to imidazolium cations in ionic liquid
crystals. Electrochemical reduction of the anions in these media enables the anions to
be used as both precursors and templates for the formation of metal
nanocrystals/nanoparticles. 2) A biological application in the development of an
imidazolium-based amphiphile capable of inducing membrane transport of si-RNA and
so inhibiting gene expression. 3) Detection of neutrons and gamma rays through the
use of imidazolium salts functionalised with particle-specific chromophores. 1) L.
Douce et al., Angew. Chemie Int. Engl. Ed., 2006, 45, 4179-4182. 2) L. Douce et al., J.
Am. Chem. Soc., 2009, 131 (37), 13338–13346. 3) WIPO PatentApplication
WO/2010/004228 (01/14/2010).
COIL-4:129
Universalization of Molecular Volume and Refractive Index of Room-Temperature
Ionic Liquids
Shiro Seki (1) , s-seki@criepi.denken.or.jp, 2-11-1, Iwado-kita, Komae Tokyo 201-8511,
Japan ; Seiji Tsuzuki (2) ; Kikuko Hayamizu (2) ; Yasuhiro Umebayashi (3) ; Nobuyuki
Serizawa (1) ; Katsuhito Takei (1) ; Hajime Miyashiro (1) . (1) Central Research Institute of
Electric Power Industry, Komae Tokyo 201-8511, Japan (2) National Institute of
Advanced Industrial Science and Technology, Tsukuba Ibaraki 305-8565, Japan (3)
Kyushu University Fukuoka 812-8581, Japan
Room-temperature ionic liquids (RTILs) have many kinds of cations and anions, and
show the wide range of physicochemical properties and the opportunity of application
fields. Extractions of commonality for physicochemical parameters are very important
for future molecular design due to infinite cations & anions combinations. We
investigated the universilizations of molecular volume (van der Waals volume, excluded
volume) and refractive index of RTILs. Temprature dependences of density and
refractive index of various RTILs were measured by experimentally. Van der Waals radii
of various cations and anions, and polarizability of various cations and anions were
calculated, respectively. Figure 1 shows the relationships between Vintra (van der
Waals molecular volume) and Vmeasure (from density measurements and Mw of
RTILs), Vinter (Vmeasure – Vintra).

And Figure 2 shows the
relationships between refractive index of various RTILs and polarizability / molecular
volume. Both Figures 1 and
2 showed high linearity in all commonly RTILs, and possibilities of universalization for
some physicochemical parameters were expected.
COIL-4:130

Experimental Thermodynamic Properties of Pyridinium Tetrafluoroborates and
their Mixtures with Water and Alkanols, as well as their Interpretation Using 1 H-
NMR Spectroscopy and COSMO-RS
Remko Vreekamp (1) , rvreekamp@ramonycajal.ulpgc.es, Parque Científico-
Tecnológico, Campus Tafira, Las Palmas de Gran Canaria Canary Islands 35071,
Spain ; Luís Fernández (1) . (1) Laboratorio de Termodinámica y Fisicoquímica,
Universidad de las Palmas de Gran Canaria, Las Palmas de Gran Canaria Canary
Islands 35071, Spain
In our laboratory we have studied the thermophysical properties of a series of closelyrelated
pyridinium-based ionic liquids, both in their pure state and in mixtures with water
and small, linear alkanols. This study was done to determine both structure-property
relationships as well as structure-activity relationships. The ionic liquids studied were
butylpyridinium tetrafluoroborate, and 2-, 3-, and 4-methylbutylpyridinium
tetrafluoroborate. As basic properties we determined density, refractive index and
viscosity, all as a function of temperature. After having assessed the miscibility as a
function of temperature, the mixing properties, excess volumes and excess enthalpies,
of these four ionic liquids in combination with water, methanol, ethanol, 1-propanol, 1butanol,
and 1-pentanol were determined at 298.15 K and 318.15 K. The results show
that the picolinium isomers behave similarly, that the non-methylated pyridinium differs
slightly, and that the effect of the substituent is not the same for the mixing properties.
For the elucidation of the interactions at a molecular level we applied 1 H-NMR
spectroscopy. The study of all of the above mixtures at the complete range of
compositions by this technique allowed us to determine which protons are most strongly
involved in the interactions and in what way. It also permitted us to determine the
existence or absence of aggregates. The quantum-chemical method COSMO-RS was
applied to predict excess properties of the mixtures. The methodology assists to
interpret and understand the processes that occur on a molecular level and which stand
at the basis of the observed phenomena. The analysis based on COSMO-RS shows a
significant contribution of hydrogen bonding interactions. From the combined results of
the above studies we derive conclusions about the effect of the presence and the
position of the methyl-substituent on the pyridine ring. The results further give us insight
in the effect of temperature on these effects.
COIL-4:131
Electrical Impedance of Spin Coatable Ion Gel Films
Keun Hyung Lee (1) , leex3432@umn.edu, 414 Amundson Hall, 421 Washington Avenue
SE, Minneapolis MN 55455, United States ; Sipei Zhang (1) ; Timothy P Lodge (1)(2) ; C.
Daniel Frisbie (1) . (1) Department of Chemical Engineering and Materials Science,
University of Minnesota, Minneapolis MN 55455, United States (2) Department of
Chemistry, University of Minnesota, Minneapolis MN 55455, United States

The electrical properties (capacitance, resistance and conductivity) of ion gel films were
investigated as a function of film geometry and temperature by using impedance
spectroscopy. Ion gel films, which consist of a triblock copolymer, poly (styrene-bmethyl
methacrylate-b-styrene) [SMS], and an ionic liquid, 1-ethyl-3-methylimidazolium
bis(trifluoromethylsulfonyl)amide, [EMI][TFSA], were deposited by spin coating from
ethyl acetate solution. The thickness and the area of the film sandwiched between two
gold electrodes were varied systematically to examine the relation between the
electrical properties and the geometry of the film. The resistance (R) shows a linear
dependence on the thickness of the film and is inversely proportional to the area of the
film, as expected, whereas the specific capacitance (C') and conductivity are
independent of the film geometry. Conductivity values of ~1 mS/cm are achieved which
is ~10 times higher than that of traditional polymer electrolytes based on poly(ethylene
oxide) and lithium salts. Importantly, the gel polarization time constant (RC, where C =
C' × Area) of few μs is achieved by simply reducing the ion gel thickness. Conductivity
and capacitance of the film both increase with increasing temperature, with conductivity
following the Vogel-Fulcher-Tamman equation, indicating entropically activated
behavior, and capacitance at 10 Hz displaying Arrhenius-type activation. Our results
demonstrate that spin coatable ion gel films can serve as high capacitance, high
conductivity, solution processable solid electrolytes with short polarization response
times.
COIL-4:132
Ultrathin Ionic Liquid Films - Accessing the IL/SolidInterface
Till Cremer (1) , till.cremer@chemie.uni-erlangen.de, Egerlandstrasse 3, Erlangen
Bayern 91058, Germany ; Michael Stark (1) ; Florian Maier (1) ; Alexey Deyko (1) ; Hans-Peter
Steinrück (1) . (1) Department Chemistry and Pharmacy, Friedrich-Alexander-University
Erlangen-Nuremberg, Erlangen Bayern 91058, Germany
The IL/solid interface is of fundamental importance in many fields such as
electrochemistry, tribology and heterogeneous catalysis. Recently, increasing efforts
have been made to understand IL/solid interfaces on a molecular level through
theoretical and experimental studies. 
 In this study we present angle resolved X-ray
photoelectron spectroscopy (ARXPS) results using an ultra-high vacuum (UHV) based
physical vapor deposition process developed in our group 1 , which allows preparation of
thin IL films with thicknesses even below one monolayer. For these films, electronic
structure, wetting and growth behavior, and molecular orientation effects are
investigated. When [C8C1Im][Tf2N] (1-methyl-3-ocytlimidazolium
bis(triflouromethyl)imide) is deposited onto a Au(111) single crystal the ions adsorb next
to each other on the surface, and IL growth proceeds in a layer-by-layer fashion. For
small surface coverages the entire cation lays flat on the surface, but upon completion
of one closed IL layer the C8-alkyl chain looses contact to the gold substrate and starts
pointing away from the surface towards the vacuum. 2 The results are compared to other
systems such as glass 1
and Ni(111).

1 T. Cremer, M. Killian, J. M.
Gottfried, N. Paape, P. Wasserscheid, F. Maier, H.-P. Steinrück, ChemPhysChem 9
(2008) 2185.
 2 T. Cremer, M. Stark, A. Deyko, H.-P. Steinrück, F. Maier, Langmuir,
2011, DOI: 10.1021/la105007c
COIL-4:133
Purification and Recycling of Ionic Liquids by Crystallization
Philipp Keil (1) , philipp.keil@cbi.uni-erlangen.de, Egerlandstr. 3, Erlangen 91058,
Germany ; Axel König (1) . (1) Chair of Separation Science and Technology, University of
Erlangen-Nuremberg, Germany
Several applications of ILs have been developed up to industrial scale in the recent
years. However, only few contributions on large-scale purification and recycling of ILs
are published. This is remarkable, as for a number of promising applications was shown
that certain impurities at ppm-levels impact the overall process. [1] Melt crystallization is
suitable to provide highly pure ILs and has several advantages, e.g. low operation
temperatures and stereo selectivity. [2] This technique has also been successfully
implemented for the recycling of spent chloroaluminate electrolytes. [3]

Figure 1: Impurity MIM in
product (261 ppm) and residue (878 ppm) The presentation points out the advantages
of melt crystallization processes for the purification and recovery of Ionic Liquids at
different scales. Zone melting and normal freezing are introduced as techniques in a
systematic approach to determine exact and consolidated thermodynamic and effective
distribution coefficients of individual impurities in the crystallization of organic
substances from melts. [4] Concentrations of impurities at ppm-levels are determined by
an analytical IC with multidetection analysis conductivity/UV-Vis/mass spectrometry to
quantify charged and uncharged impurities and to identify unknown species. [1]
Schmeisser, M.; Eldik, R.; Inorg. Chem. 2009, 48(15), 7466-7475 [2] König, A.;
Stepanski, M. et al.; Chem. Eng. Res. Des. 2008, 86 (7), 775-780 [3] Sola, J.L., König,
A.; Chem. Eng. Technol. 2010, 33 (12) 1979–1988 [4] Sola, J.L., Keil, P.; König, A.;
Chem. Eng. Technol. 2010, 33 (5) 821-826
COIL-4:134
Changes in Properties of Ionic Liquid with Large Anion Confined in Nano-Porous
Silica Matrix
Rajendra Kumar Singh (1) , rksingh_17@rediffmail.com, Department of Physics,
Banaras Hindu University, Varanasi U.P. 221 005, India ; Manish Pratap Singh (1) . (1)
Physics, Banaras Hindu University, Varanasi U.P. 221 005, India
Properties of the ionic liquid (1-butyl-3-methyl imidazolium octyl sulfate [BMIM]
[OcSO4]), composed of large anion (octyl sulfate) with size comparable to cation (1butyl-3-methyl
imidazolium) has been investigated upon confinement in porous silica gel
matrix. IL confined porous silica gel matrices have been synthesized by one step sol-gel
technique using tetraethyl orthosilicate (TEOS) as starting precursor. The synthesized
gel has been characterized by BET, Differential Scanning Calorimetry (DSC), TEM and
FTIR. The FTIR spectra show changes in many vibrational bands on confinement.
Particularly, the vibrational bands related to the imidazolium ring, aliphatic chain and

SO3 - of the IL are found to shift upon confinement. The DSC results show a large
change in the melting point ( Tm ~ 54 0 C) and crystallization temperature of confined IL.
A new approach which takes into consideration the shape of confined system (IL in this
case) for explaining the change in melting temperature has been suggested.
COIL-4:135
Density Functional Theory Affinities Related to Experimental Styrene -
Ethylbenzene Distribution Coefficients and Selectivity in Ionic Liquids
Thijs J. H. Vlugt (1) , t.j.h.vlugt@tudelft.nl, Leeghwaterstraat 44 k 0.30, Delft Zuid-Holland
2628CA, The Netherlands; Henri K Ervasti (1)(2) ; Maaike C. Kroon (3) ; Cor J Peters (1)(4) . (1)
Department of Process and Energy, Delft University of Technology, Delft 2628CA, The
Netherlands (2) Institute for Sustainable Process Technology, Delft 2628CA, The
Netherlands (3) Department of Chemical Engineering and Chemistry, Eindhoven
University of Technology, Eindhoven Noord-Brabant 5612 AZ, The Netherlands (4)
Petroleum Institute, Delft 2628CA, The Netherlands
It is possible to predict certain properties of ionic liquids directly from ab initio
calculations. Recently the anion-cation interaction energies have been linked to
vaporization enthalpy, molar volume, viscosity, melting point and conductivity in ionic
liquids. In our work we compare selectivity and distribution coefficients from styrene -
ethylbenzene separation experiments with our simulated anion-cation pair and ion-pair
dimer affinities of 22 ionic liquids, based on quantum Density Functional Theory. Nine of
the simulated ionic liquids were based on 2, 3 and 4-methyl substituted 1-pyridinium
cations and 13 were based on 1-ethyl and 1-butyl substituted 3-methylimidazolium
cations, with various anions. The computed anion-cation affinities correlate with the
experimental selectivity with coefficient of determination (R 2 ) value of 0.63 for the
regression line. This implies a qualitative correlation between these two properties. The
computed ion-pair dimer affinities in turn show correlation both with distribution
coefficients and selectivity. This correlation is found to be dependent on the cation type
for both properties. The R 2 values for the correlation with selectivity are 0.62 for the 3methylimidazolium
based ionic liquids and 0.80 for the 1-butylpyridinium based ionic
liquids. Therefore, both the computed anion-cation affinities and dimer affinities are
shown to qualitatively correlate with selectivity. Combining the computed anion-cation
and dimer affinity results gives a similar correspondence to the dimer affinity-toselectivity
case. It is apparent from the results that lower dimer affinity corresponds to
higher distribution coefficient for the solutes, while stronger anion-cation affinity implies
better selectivity, and these can be qualitatively predicted. The drawback of the method
is that it does not seem to be able to distinguish cations with longer alkyl chains. With
longer alkyl chains sterical effects and polar and non-polar region segregations seem to
become increasingly important effects affecting the ionic liquid properties.
COIL-4:136
Preparation of Alkaline Ionic Liquids

Pasi Virtanen (1) , pasi.virtanen@abo.fi, Biskopsgatan 8, Turku Finland FI-20500,
Finland ; Eero Salminen (1) ; Jyri-Pekka Mikkola (1)(2) . (1) Department of Chemical
Engineering, Åbo Akademi University, Turku FI-20500, Finland (2) Department of
Chemistry, Umeå University, Turku FI-20500, Finland
Alkalinity is an important function in many chemical reactions. In this study three
different alkaline ionic liquids were prepared. For ionic liquids containing a strong
alkaline anion a challenge is to find a suitable cation which can tolerate the harsh
conditions caused by the anion. A suitable cation benzalkonium was used in preparation
of the alkaline ionic liquids, namely benzalkonium methoxide [BA][MeO], benzalkonium
tert-butoxide [BA][tBuO] and benzalkonium hydroxide [BA][OH] (Fig. 1.).
Ionic liquids were prepared by
the metathesis procedure from benzalkonium chloride and suitable sodium salt of the
replacement anion. The precipitated salt and un-reacted starting material were filtered
off and solvent was evaporated. Then the ionic liquids were washed with a small
amount of water. Synthesized alkaline ionic liquids were characterized by means of
TGA, DSC, IR- and NMR-spectroscopy and their mutual solubility with different solvents
were tested. Applicability of the new ionic liquids in catalysis was tested in citral
hydrogenation by means of supported ionic liquid catalysis. The new catalysts showed
improved activity as well as selectivity towards citronellal.
COIL-4:137
Application of Ionic Liquid and High-pressure Carbon Dioxide for Recovery of
Erythromycin from Aqueous Solutions
Marina S Manic (1) , marina.manic@dq.fct.unl.pt, Quinta de Torre, Caparica 2829-516,
Portugal ; Manuel Nunes da Ponte (1) ; Vesna Najdanovic-Visak (1) . (1) Department of
Chemistry, REQUIMTE/FCT/UNL, Caparica 2829-516, Portugal

Erythromycin, a broad-spectrum polypeptide (macrolide) antibiotic is industrially
produced by the aerobic fermentation, yielding to the low concentrations aqueous
solutions. Solvent extraction involving hazardous volatile organic solvents is the mostly
used technique. Therefore, ionic liquids, due to their non-flammable nature and
negligibly small vapor pressure become a replacement for conventional solvents.
Recovery of erythromycin from aqueous solutions was studied in this work. A single-
and multi-stage extraction of erythromycin from an aqueous solution by 1-butyl 1methylpyrrolidinium
bis(trifluoromethylsulfonyl)imide, [BMPyrro][NTf2], hydrophobic ionic
liquid as a function of pH, extraction time and volume ratio of feed to IL were performed,
followed by high-pressure CO2 extraction of erythromycin from ionic liquid as a function
of pressure, temperature and presence of water. Results achieved in this work indicate
that coupling ionic liquids and supercritical CO2 may be used as alternative solvent in
separation processes, offering more effective and clean solvent system for recovery of
erythromycin from aqueous solution. Acknowledgments: M. S. Manic is grateful to
Fundação para Ciência e Tecnologia, Portugal, for the fellowship
SFRH/BD/45323/2008.
COIL-4:138
Interactions of Transition Metal Ions with Protic Ionic Liquids of
Alkylethylenediamine and Alkyldiethylenetriamine Cations
Masayasu Iida (1) , iida@cc.nara-wu.ac.jp, Kita-uoya-nishi-machi, Nara Nara 6308506,
Japan ; Sayaka Kawakami (1) . (1) Department of Interdisciplinary Materials Science,
Nara Women[apos]s University, Nara Nara 6308506, Japan
Ionic liquids containing transition metal ions are one of functional soft materials which
are applicable to inorganic and analytical chemistry. [1,2] Protic ionic liquids (PILs) are
generally more hydrophilic than aprotic ionic liquids (AILs) and tend to dissolve metal
ions or metal complex ions to a larger extent. We have prepared monoprotic alkylethylenediamine
[2] and diethylenetriamine ionic liquids, which are particularly favorable
for dissolving transition-metal salts or metal complexes to interact with selective sites of
the PILs. Anions (A - ) used are bis(trifluoromethanesulfonyl)amide (= TFSA) and
trifluoroacetate (= TFA). On the basis of the studies on the physical properties of the
PILs, the interactions of transition metal ions (Mn 2+ , Co 2+ , Ni 2+ , and Cu 2+ ) and metal
complexes with the PILs have been studied using paramagnetic 13 C and 15 N NMR
spectrum broadenings and visible absorption spectra. 15 N NMR spectra showed that in
the PILs the protonation preferentially occurs at the secondary amine site rather than
the primary amine (Figure 1) while the metal-ions prefer the terminal primary amine. A
difference in the position of interacting metal ions between the ethylenediamine head
group and the diethylenetriamine was systematically detected. The PILs with TFSA
effectively extracted Cu 2+
from aqueous layer.

References [1] M. Iida, C.
Baba, M. Inoue, H. Yoshida, E. Taguchi, H. Furusho, Chem.-Eur. J., 14, 5047 (2008) [2]
M. Iida, S. Kawakami, E. Syouno, H. Er, E. Taguchi, J. Colloid Interf. Sci., 356, 630
(2011).
COIL-4:139
Structure-Property Relationships in the Dynamics of Ionic Liquids
Mark Kobrak (1) , mkobrak@brooklyn.cuny.edu, 2900 Bedford Ave., Brooklyn NY 11210,
United States ; Hualin Li (1) . (1) Department of Chemistry, Brooklyn College of the City
University of New York, Brooklyn NY 11210, United States
The transport properties of ionic liquids are important in many applications, but
questions remain concerning the link between the dynamics of an ionic liquid and the
chemical structure of its component ions. We use a combination of fundamental theory
and molecular dynamics simulations to demonstrate a strong link between the relative
distributions of charge and mass within the ions and the behavior of the salt. The results
are used to interpret experimentally-observed viscosities.
COIL-4:140
Catalytic C-N, C-O, and C-S Bond Formation Reactions Promoted by Task
Specific Ionic Liquids
Zhen Li (1) , zhenli@licp.cas.cn, No.18,Tianshui Middle Road, lanzhou gansu, China ;
Lei Yang (1) ; Jing Chen (1) ; Chungu Xia (1) ; Feng Han (1) . (1) State key laboratory for Oxo
Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese
Academy of Sciences, lanzhou gansu 730000, China
Ionic liquids (ILs) have received widespread attention as an environmentally benign
reaction media or catalyst for a variety of reactions due to its unique properties such as
good solvating ability, tunable polarity, high thermal stability, and ease of recyclability. 1
ILs are organic or inorganic salts being composed of distinct cations and anions that are

capable of facilely tuning. Task specific IL is a subset of ILs, which can be designed for
task-specific applications through smart choice of the respective cations and anions. 2
We have reported a highly efficient basic ILs catalyzed aza-Michael reaction of aromatic
amines and N-heterocycles. 3a We next found that SO3H-functionalized ILs were able to
catalyze the hydroamination of sulfonamides, aromatic amines and carbamates with
olefins. 3b Here, we will report our recent progress in task-specific ILs catalyzed C-X
bonds formation reactions such as hetero-Michael of various N-, O- and S- nucleophiles
with α, β-unsaturated substrates, amination of alcohols with nitrogen nucleophiles, and
its application in the synthesis of nitrogenous heterocyclic compounds.
References: 1 P.
Wasserscheid.; T.Welton. Ionic liquids in synthesis, Wiley-VCH, 2008. 2 (a) J. H. Davis,
Jr. Chem. Lett. 2004, 9, 1072. (b) T. L. Greaves.; C. J. Drummond. Chem. Rev. 2008,
108, 206. 3 (a) L. Yang.; L. W. Xu.; W. Zhou.; L. Li.; C. G. Xia. Tetrahedron Letters.
2006, 47, 7723. (b) L. Yang.; L. W. Xu.; C. G. Xia. Synthesis 2009, 12, 1969
COIL-4:141
Binary and Ternary Liquid-Liquid Equilibrium for the Mixtures Methylcyclohexane
(1) + Toluene (2) + 1-Hexyl-3-Methylimidazolium Tetracyanoborate (3)/1-Butyl-3-
Methylimidazolium Tetracyanoborate (3)
Juan P. Gutiérrez Hernández (1) , j.p.gutierrez-hernandez@tue.nl, Den Dolech 2,
Eindhoven North Brabant 5600MB; André B. de Haan (1) ; Wytze Meindersma (1) . (1)
Department of Chemical Engineering and Chemistry, Eindhoven University of
Technology, Eindhoven 5600MB, The Netherlands
Separation of aromatic/non-aromatics mixtures is one of the most important processes
in the chemical industry. Ionic liquids (ILs) have been proposed as solvents in extractive
distillation (ED) processes for the separation of aromatic mixtures, however, there are
few solubility and phase equilibria measurements. In this work, the ILs 1-hexyl-3methylimidazolium
tetracyanoborate ([HMIM][TCB]) and 1-butyl-3- methylimidazolium
tetracyanoborate ([BMIM][TCB]) are studied and toluene and methylcyclohexane were
chosen as representative components for aromatics and non-aromatics, respectively.
Binary and ternary liquid-liquid equilibria were measured for the mixture
methylcyclohexane + toluene + IL at different temperatures (293.15, 313.15 and 333.15
K). The NRTL and UNIQUAC parameters were regressed taking into account binary

and ternary data sets. The results showed that organic components are forming two
liquid phases with the ILs. As expected, the solubility of methylcyclohexane is lower
than the solubility of toluene in ILs. The solubility of methylcyclohexane increased
slightly with the temperature and the solubility of toluene decreased. The solubility of the
organic components in [HMIM][TCB] is higher than in [BMIM][TCB].
The NRTL and UNIQUAC
parameters were regressed; however, NRTL showed lower deviations and better
predictions. The NRTL model gave an average deviation of 5.6% and 6.1% for
[HMIM][TCB] and [BMIM][TCB], respectively. Because their lower molecular weight,
selectivities and non-fluorinated anion, the ILs studied are promising solvents in
extractive distillations processes. However, their biggest disadvantage is the partial
miscibility with the organic compounds.
COIL-4:142
Desulphurisation and Denitrogenation of Gasoiline and Diesel Fuels by Means of
Ionic Liquids
Wytze Meindersma (1) , g.w.meindersma@tue.nl, P.O. Box 513, Eindhoven 5600 MB,
The Netherlands; Antje R. Hansmeier (1) ; André B. de Haan (1) . (1) Department of
Chemical Engineering & Chemistry/SPS, Eindhoven University of Technology,
Eindhoven 5600 MB, The Netherlands
Ionic liquids can extract mono- and poly-aromatic sulphur and nitrogen components
from gasoline and diesel and they perform better than conventional solvents, such as
sulfolane. Petrochemical streams contain next to mono and/or poly aromatic
components also heterocyclic components comprising sulphur and nitrogen. Since
these compounds are responsible for the formation of smog, sour gases, acid rain and
NOx emissions, the heterocyclic components have to be removed. From all refinery
streams contributing to the gasoline blending pool, FCC Gasoline is with up to 2.5 wt-%
sulphur content the main sulphur source for carburant fuels. In order to meet the current
compulsory limits for the sulphur content in carburant fuels, i.e. gasoline (petrol) and
diesel fuels, the sulphur content has to be reduced to 10 ppm. The ionic liquids [3mebupy]N(CN)2,
[4-mebupy]N(CN)2, [4-mebupy]SCN and [bmim]C(CN)3 are superior for
sulphur removal compared to sulfolane which has been used as benchmark. These
ionic liquids exhibit an up to 20 % higher capacity in case of thiophene and in the case
of dibenzothiophene even up to 53 %. Furthermore, it has been shown that nitrogen
containing hetero-aromatic components are significantly better extracted than sulphur
components, see Table 1.

Solvent Removal thiophene Removal DBT Removal pyrrol Removal indole
[ppm] [%] [ppm] [%] [ppm] [%] [ppm] [%]
Sulfolane 1747 65 9717 78 2400 >99 3100 >99
[3-mebupy]N(CN)2 2108 78 10642 86 2400 >99 3100 >99
[bmim]C(CN)3 2072 77 10673 86 2400 >99 3100 >99
[4-mebupy]N(CN)2 2047 76 10544 85 2400 >99 3100 >99
[bmim]N(CN)2 1664 62 9565 77 2400 >99 3100 >99
[4-mebupy]SCN 1902 70 10453 84 - - - -
COIL-4:143
Use of Ionic Liquids for Depolymerization of Waste Plastics
Akio Kamimura (1) , ak10@yamaguchi-u.ac.jp, 2-16-1, Tokiwadai, Ube Yamaguchi 755-
8611, Japan ; Shigehiro Yamamoto (1) ; Kazuo Yamada (1) . (1) Department of Applied
Molecular Bioscience, Yamaguchi University, Ube Yamaguchi 755-8611, Japan
Development of an effective method for the chemical recycling of waste plastic is one of
the important problems. The chemical recycling is the most ideal feedstock recycling
process. We have recently developed a new method for the conversion of plastic to
monomers by using ionic liquids. 1 Non-volatile and less-flammable properties of ionic
liquids are ideal as a reaction solvent for the reaction. In this presentation we report the
first use of ionic liquids for depolymerization of waste plastics.
Treatment of nylon 6 with
[PP13][TFSA] at 300 ºC resulted in the smooth depolymerization of polyamide linkage,
giving caprolactam in good yield. The presence of catalytic amounts of DMAP enhanced
the efficiency of the reaction. Ionic liquids effectively worked in iteration use for several
times. Ionic liquids were also useful for decomposition of fiber-reinforced plastics
(FRP). 2 Heating by microwave irradiation was very important for the effective progress
of the reaction. Pure glass fiber and phthalic anhydride were recovered from the
reaction. Ionic liquids were useful for iteration use. Ionic liquids were useful as a
reaction solvent for the depolymerization reaction for several times. Use of ionic liquids
provides a new and useful method for the chemical recycling of waste plastics.

References 1. Kamimura, A.; et. al. Org. Lett. 2007, 9, 2533; Chem. Lett. 2009, 39,
1016. 2. Kamimura, A.; et. al. submitted.
COIL-4:144
Low Temperature N-Alkane Isomerization Catalysts: Superacidic Ionic Liquids in
a Liquid-Liquid Biphasic or Supported Ionic Liquid Phase (SILP) Slurry Reaction
System
Carolin Meyer (1) , carolin.apfel@crt.cbi.uni-erlangen.de, Egerlandstr. 3, Erlangen
Bavaria 91058, Germany ; Peter Wasserscheid (1) ; Marco Haumann (2) . (1) Chair of
Chemical Reaction Engineering, University Erlangen-Nuremberg, Erlangen 91058,
Germany (2) Chemical Reaction Engineering, FAU Busan Campus, Busan 618-230,
Republic of Korea
Due to increasing environmental regulations in recent years, the addition of a number of
Research Octane Number (RON) booster compounds to automotive fuels has been
stopped or severely restricted. This development has considerably increased the
interest in the large-scale refinery production of highly branched alkanes which combine
high RON with benign toxicological and ecotoxicological properties. The key feature of
acidic ionic liquid (IL) catalysts that are based on chloroaluminate ions is their ability to
form liquid-liquid biphasic systems with unpolar organic product mixtures, thus enabling
recycling of the acidic IL reaction phase by simple phase separation. Acidic
chloroaluminate ILs are known to form superacids when contacted with HCl [1].
Superacidic ILs are active n-alkane isomerization catalysts, even at low reaction
temperatures. These mild reaction conditions favor the formation of branched alkanes
thermodynamically. n-Octane, a model compound of the light naphtha refinery cut, was
used as reactant. The optimum superacidic IL composition was determined to ensure
the most active catalyst [2]. Selectivity to branched alkanes and catalytic activity are
presented. Another focus of the work was the immobilization of the superacidic IL on
an inorganic support with a large specific surface area. SILP catalysts offer the
advantage to get a macroscopically heterogeneous system while still preserving all
benefits of the homogeneous catalyst nature [3]. The interaction of the solid support and
acidic IL influence strongly the catalytic activity. We assume these optimized
[cation]Cl/AlCl3/H2SO4 systems to be indeed highly attractive homogeneous catalysts for
alkane isomerization processes in a liquid–liquid biphasic or slurry-phase reaction
mode. 1. G.P. Smith, A.S. Dworkin, R.M. Pagni, S.P. Zingg, J.Am. Chem. Soc., 111,
525-530, 1989; 2. C. Meyer, P. Wasserscheid, Chem. Commun., 46, 7625-7627, 2010.
3. A. Riisager, R. Fehrmann, S. Flicker, R. van Hal, M. Haumann, P. Wasserscheid,
Angew.Chem. Int. Ed., 44, 815, 2005.
COIL-4:145
Activity and Stability of α-Chymotrypsin in Biocompatible Ionic Liquids

Pannur Venkatesu (1) , pannuruv@yahoo.com, North Campus, Delhi Delhi 110 007,
India . (1) Chemistry, University of Delhi, Delhi 110 007, India
In the view of wide scope of structural information of biomolecules in biocompatible ionic
liquids (ILs) in various applications, including chemical and biochemical it is essential to
study the productive preferential interactions between biological macromolecules and
biocompatible ILs. We have therefore explored the stability and activity of αchymotrypsin
(CT) in the presence of five ILs from different families, such as triethyl
ammonium actetate (TEAA), triethyl ammonium phosphate (TEAP) from ammonium
salts, 1-benzyl-3-methylimidazolium chloride ([Bzmim][Cl]), 1-benzyl-3methylimidazolium
tetrafluoroborate ([Bzmim][BF4]) from imidazolium salts and tetrabutyl
phosphonium bromide (TBPBr) from phosphonium families. Circular dichroism
(CD) and UV-VIS spectrophotometer experiments have been used to study the CT
stabilization by ILs, related to the associated structural changes and enzyme activity
studies, respectively. We observed that all ILs have a dominant contribution to the
stabilization of CT while not enhancing its enzyme activity. The stability and activity of
CT depends on the structural arrangement of ions of ILs. Our experimental results
explicitly elucidate that more hydrophobic imidazolium and phosphonium cations
carrying longer alkyl chains of ILs ([Bzmim][Cl], [Bzmim][BF4] and TBPBr) were weak
stabilizer for CT, while small alkyl chain molecules of triethyl ammonium salts (TEAA
and TEAP) are strong stabilizers and therefore more biocompatible for CT stability. Our
CD and NMR measurements reveal that TEAA is a refolding additive for CT from a
quenched thermal unfolded of enzyme structure. Reference: · Pankaj Attri, and P.
Venkatesu, Phys.Chem.Chem.Phys., 2010 (In press) · Pankaj Attri, P. Venkatesu and
A. Kumar, Phys.Chem.Chem.Phys., 2010 (DOI:10.1039/C0CP01291B) · Pankaj Attri,
P. Venkatesu and A. Kumar, J. Phys. Chem. B, 2010, 114, 13415-13425). · Pankaj
Attri, P. Venkatesu and M. J. Lee, J. Phys. Chem. B, 2010, 114, 1471-1478. · Pankaj
Attri, P. M. Reddy, P. Venkatesu, A. Kumar and T. Hofman, J. Phys. Chem. B, 2010,
114, 6126-6133.
COIL-4:146
Efficient Tandem Oxidation of Cyclohexanol to ε-Caprolactone in Ionic Liquids as
Solvents
Anna Chrobok (1) , anna.chrobok@polsl.pl, ul. Krzywoustego 4, Gliwice 44-100, Poland ;
Stefan Baj (1) . (1) Department of Organic Technology and Petrochemistry, Silesian
University of Technology, Gliwice 44-100, Poland
The tandem reaction concerning the one-pot oxidation of secondary alcohols to
lactones would be beneficial for organic chemists and for industry. Only limited
information concerning this problem can be found in the literature. Among known
lactones, the synthesis of ε-caprolactone is crucial. The great majority of ε-caprolactone
is used for the production of policaprolactone. This is biodegradable polyester which is
used as an additive for resins or as an implantable biomaterial. Currently, most εcaprolactone
is prepared by oxidation of cyclohexanone which is obtained from

cyclohexanone/cyclohexanol mixture (KA- oil). The use of KA-oil as a raw material for εcaprolactone
synthesis would allow avoiding both the separation of KA-oil and the
consequence dehydrogenation of cyclohexanol to cyclohexanone, particularly because
the cyclohexanol content of KA-oil is higher than cyclohexanone. This problem is
important from a synthetic and an industry point of view. Herein, a new method for the
one-pot tandem oxidation of alcohol to lactone is presented. The method is based on
the use of m-CPBA or Oxone ® (commercial source of potassium peroxomonosulfate) as
oxidants together with TEMPO radical and tetrabutylammonium bromide (TBAB) as an
oxidant system in ionic liquids as solvents. It is possible to obtain ε-caprolactone with
high yields using m-CPBA and broad spectrum of ionic liquids as reaction medium.
Although the oxidation of cyclohexanol with Oxone ® is strongly solvent dependent. Only
[bmim]BF4 was found to be an efficient solvent for this system. Looking for green
solutions in organic oxidations to minimize the environmental impact resulting from the
use of oxidizing agents and solvents, implementation of Oxone ® and ionic liquid is an
effective combination. The simplicity of the methodology, high yields, mild conditions,
lack of by-products as well as the possibility of recycling the ionic liquids can make this
reaction attractive as synthetic method for lactone formation.
COIL-4:147
Hydrolysis of a Triarylmethylpicolinium Salt in Transition State Analogue
Templated IonicLliquid: Evidence for Homogeneous Molecular Templating
Cameron C Weber (1) , c.weber@chem.usyd.edu.au, Laboratory of Advanced Catalysis
for Sustainability, School of Chemistry, Building F11, The University of Sydney, Sydney
NSW 2006, Australia ; Anthony F Masters (1) ; Thomas Maschmeyer (1) . (1) School of
Chemistry, The University of Sydney, Sydney NSW 2006, Australia
Ionic liquids (ILs), particularly those based on imidazolium cations, have been shown to
perform as 'supramolecular solvents', an observation based on their wide variety of
intermolecular interactions. The ability of ILs to form aggregates and inclusion
compounds has been demonstrated to affect various physicochemical properties,
including the solubility of aromatic substrates and reaction outcomes, when the IL is
used as a solvent. 1 Reports also indicate that ILs exhibit mesoscopic ordering that is
much more extensive than can be found in non-ionic solvents – ordering across
distances that are much greater than those between simple cation-anion contacts. 2 At
present, however, no generalized method exists for utilizing this ordered,
supramolecular character of the IL solvent to accelerate reaction rates. Our proposed
solution involves the use of transition state analogues (TSAs). They are stable mimics
of high energy transition state structures. They have been successfully employed in the
generation of catalytic antibodies and in the synthesis of structured materials for
separations and catalysis. 3,4 We will examine whether or not the TSA is able to preorganise
the IL to stabilise the activated transition state species, leading to an increase
in rate. In particular, the hydrolysis of N-(p-fluorophenyldiphenylmethyl)-4-picolinium
chloride in the IL [BMIM][NTf2] will be discussed as a model reaction for the examination
of this concept. The variation of the reaction rate within this system on addition of

varying concentrations of (p-fluorophenyl)diphenyl(p-tolyl)phosphonium template, where
a maximum rate is reached with a very low template loading, and evidence for the
formation of aggregates within the IL will be outlined. (1) Leclerq, L.; Schmitzer, A. R.
Supramol. Chem. 2009, 21, 245. (2) Weingartner, H. Angew. Chem. Int. Ed. 2008, 47,
654. (3) Alexander, C.; Davidson, L.; Hayes, W. Tetrahedron 2003, 59, 2025. (4) Xu, Y.;
Yamamoto, N.; Janda, K. D. Bioorgan. Med. Chem. 2004, 12, 5247.
COIL-4:148
Ethiopian Ionic Liquids with Exceptional Metal Compounds Solubilities
Ignacio J. Villar Garcia (1) , ivillar@chem.aau.edu.et, Arat Kilo Science Campus, Addis
Ababa Addis Ababa PO BOX 1176, Ethiopia ; Atakilt Abebe (1) ; Yonas Chebude (1) . (1)
Chemistry Department, Faculty of Chemical and Physical Sciences, College of Natural
Sciences, Addis Ababa University, Addis Ababa Addis Ababa PO BOX 1176, Ethiopia
Ionic liquids exhibit a unique set of properties that make them advantageous solvents
for applications involving metal compounds as diverse as catalysis, nanoparticle
synthesis, metal extractions and electrodeposition. The majority of ionic liquids in
common use are based on a limited number of cations, mostly dialkylimidazolium,
alkylpyridinium, dialkylpyrollidinium, tetralkylammonium and tetraalkylphosphonium.
Unfortunately, the low solubilities of metal compounds, such as metal complexes and
metal salts in these types of ionic liquids are hindering their successful application in
many areas. The solubility of metal compounds can sometimes be enhanced by
functionalising either the ligands or the ionic liquids themselves. However, these
strategies require further amount of synthetic work and render the final application more
laborious, expensive and less environmental friendly. In the Chemistry Department at
Addis Ababa University, Ethiopia, we have synthesised two new families of ionic liquids
(Figure 1) following the usual two step synthetic route used for commonly used ionic
liquids: - 1,10-Phenanthrolinium ionic liquids exhibiting excellent solubilities for
phenanthroline and its metal complexes: over 50% weight! - 4,4-Bipyridinium ionic
liquids exhibiting excellent solubilities for metal salts thanks to their capacity to
coordinate to metal centres: over 20 % weight!
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Figure 1 a) 1,10-
Phenanthrolinium based ionic liquids, b) 4,4-Bipyridinium based ionic liquids This
presentation will concentrate on the synthetic route, characterisation, properties and
metal compound solubility and stability studies of these novel ionic liquids.
COIL-4:149

Improved Electrical Energy Storage with Electrochemical Double Layer
Capacitance Based on Novel Carbon Electrodes
Oana A. Cojocaru (1) , oacojocaru@crimson.ua.edu, The University of Alabama,
Tuscaloosa Alabama 35487; Julia L. Shamshina (1) ; Jonathan P. Edgeworth (2) ; Gabriela
Gurau (1) ; Rodney S. Ruoff (2) ; Robin D. Rogers (1) . (1) Department of Chemistry and
Center for Green Manufacturing, The University of Alabama, Tuscaloosa Alabama
35487, United States (2) Department of Mechanical Engineering and Cockrell School of
Engineering, The University of Texas, Austin, Austin Texas 78712, United States
Almost every form of alternative energy and energy system being implemented today,
e.g., wind, solar, hybrid electric and hydrogen fuel cell vehicles, depends on electrical
energy storage. Recently, a new carbon material that has been termed “chemically
modified graphene” (CMG) has been developed and has demonstrated its utility in
electrochemical double layer capacitance (EDLC) systems. 1 These new graphenebased
material may lead to remarkable improvements in specific capacitance and
energy density. This presentation will discuss the efforts and the results toward the
development of a library of IL-based electrolytes with high values of specific
capacitance and energy density in electrochemical double layer capacitance systems.
As electrolytes, ILs possess important advantages as compared to the more traditional
aqueous and organic solutions: low volatility, non-flammability, high thermal stability,
and broad electrochemical windows. A new class of custom-designed azolium azolates
is being investigated to enhance the interaction of both cation and anion to graphene
surfaces. Spectroscopic methods have been developed to characterize the electrolytes
(particularly ILs) and to investigate electrolyte-electrode interactions.
Acknowledgement. Research supported by the U.S. Department of Energy, Office of
Basic Energy Sciences, Division of Materials Sciences and Engineering under Award
ER46657 1. Stoller, M. D.; Park, S. J.; Zhu, Y. W.; An, J. H.; Ruoff, R. S. Nano Letters
2008, 8, 3498.
COIL-4:150
Commercialization of Ionic Liquid Processes; From Idea to Implementation
Megan O[apos]Meara (1) , megan.omeara@basf.com, 100 Campus Drive, Florham Park
NJ 07932, United States ; Uwe Vagt (1) . (1) BASF, Germany
The main focus of this presentation is to elaborate on 'the state of ionic liquid business'
as seen from BASF's perspective. More specifically, this will include a discussion of
application areas, process scale-up and optimization, production capabilities, and
chemical registration status and potential barriers. Successful commercial
implementation of an ionic liquid based process relies heavily on the unique value of
ionic liquids in applications from aluminum plating to electrolytes to hydraulic fluids to
textile production. Each process must be attractive on both a technical and an economic
basis; the ionic liquid must offer something that cannot be achieved with other
technologies, processes or chemicals. While the scope of application fields has been

efined from our point of view it certainly does not mean that all opportunities have been
identified, only that assessment of the potential can be more easily vetted. Realization
of industrial processes from proof-of-concept phase is time consuming and resource
intensive generally requiring a substantial long-term commitment from all parties
involved. In order to accommodate the ionic liquid demand for these industrial
processes BASF is well versed in producing material on tons scale for and looks for
optimization of our processes to continue to produce the highest quality materials.
Regulatory requirements will continue to increase moving forward and implementation
of processes utilizing new materials, such as ionic liquids, will have to account for the
impact of these requirements on budgets and start-up timelines. As a natural
progression from on-going learnings portfolio refinement continues to be a moving
target as it is necessary to offer customers the best material for their application while
also addressing cost and environmental factors. Finally, the value of academic and/or
institute research to realizing industrial success will be highlighted.
COIL-4:151
Enabling the Next-Generation of Advanced Biofuels: The Joint BioEnergy
Institute
Seema Singh (1) , ssingh@lbl.gov, 5885 Hollis Street, Emeyville California 94608. (1)
Material Science & Dynamic Studies of Biomass Pretreatment Joint Bienergy Institute,
Sandia National Laboratories, Emeryville California 94608, United States
Today, carbon-rich fossil fuels provide 85 percent of the energy consumed in the United
States. Fossil fuel use increases CO 2 emissions, increasing the concentration of
greenhouse gases. The high energy content of liquid hydrocarbon fuels makes them the
preferred energy source for all modes of transportation. In the US alone, transportation
consumes around 13.8 million barrels of oil per day and generates over 0.5 gigatons of
carbon per year. This has spurred research into alternative, non-fossil energy sources.
Among the various options available, only biomass has the potential to provide a highenergy-content
transportation fuel. Biomass is renewable resource that is carbonneutral.
Currently, biofuels such as ethanol are produced largely from grains, but there
is a large, untapped resource (estimated at more than a billion tons per year) of plant
biomass that could be utilized as a renewable, domestic source of liquid fuels. Wellestablished
processes convert the starch content of the grain into sugars that can be
fermented to ethanol. Plant-derived biomass contains cellulose, which is more difficult to
convert to sugars. The development of cost-effective and energy-efficient processes to
transform cellulose in biomass into fuels is hampered by significant roadblocks,
including the lack of specifically developed energy crops, low activity of enzymes used
to deconstruct biomass, and the inhibitory effect of fuels and processing byproducts on
organisms responsible for producing fuels from biomass monomers. The Joint
BioEnergy Institute (JBEI) is one of three US Department of Energy Bioenergy
Research Centers that addresses these roadblocks in biofuels production. This talk will
present a summary of the efforts at JBEI on the discovery and development of novel
biomass pretreatment methods that enable the efficient conversion of biomass into

next-generation biofuels. Specifically, I will talk about ionic liquid pretreatment, enzyme
optimization and fuel production from ionic liquid pretreated biomass.
COIL-4:152
Structure-Induced Effects: Moving from Experimental Observations to an
Understanding of Interactions
Anne Stark (1) , annegret.stark@uni-leipzig.de, Linnéstr. 3, Leipzig 04103, Germany ;
Diana Imhof (2)(3) ; Alesia Miloslavina (3) . (1) Insitute for Technical Chemistry, University of
Leipzig, Leipzig 04103, Germany (2) Pharmaceutical Institute, University of Bonn, Bonn
53119, Germany (3) Center for Molecular Biomedicine, Department of Biochemistry,
Friedrich-Schiller University Jena, Bonn 53119, Germany
In the past years, ionic liquids have started to undergo the transition from curiosities to
multifunctional and tunable materials, in particular when used as solvents. Hence, many
of the observations noticed in the initial stages of ionic liquid research can nowadays be
assigned to specific ion-solute interactions. This, in turn allows for the specific design of
structure-induced effects. This contribution will focus on the effect of the ionic liquid
configuration on two examples: peptide-chemical and acid-catalyzed reactions (Fischertype
esterification). The first example will report the effect of anion basicity on the
efficient oxidative folding of disulfide-bridged bioactive peptides, leading to several
advantages such as higher selectivity and yield, higher rate of reaction, lower additive
consumption and separation effort. The anion is proposed to be involved in the
stabilization and arrangement of the reduced peptide molecules which facilitates the
selective intramolecular oxidation to the correctly folded secondary structure. The high
efficiency of the synthesis of cysteine-rich oligopeptides and miniproteins in ionic liquids
is expected to significantly promote industrial production and application of those
candidates possessing therapeutic potential and thus, may have a strong impact on
future developments in this field of research. The second example demonstrates in a
systematic study the influence of the anion basicity on the Fischer-type esterification.
This reaction is characterized by three sensitive features, i.e. selectivity, rate of reaction
and equilibrium position. The ideal ionic liquid would therefore simultaneously act as a
solvent, quasi-organo-catalyst, and water-scavenger. Hence, both the reaction rates
and equilibrium yields were investigated as functions of solute concentration, ionic liquid
anion, and auxiliary acid catalyst concentration. The effects observed were interpreted
using 1 H-NMR-spectroscopy, leading to the major conclusion that ionic liquids may act
as buffers in acid-catalyzed reactions, depending on the anion's hydrogen bond
acceptor property.
COIL-4:153
Predicting Kamlet-Taft Hydrogen-Bonding Parameters for Ionic Liquids

Patricia Hunt (1) , p.hunt@imperial.ac.uk, South Kensington Campus, London England
SW7 2AZ, United Kingdom ; Tom Welton (1) ; Heiko Niedermeyer (1) . (1) Chemistry,
Imperial College London, London SW7 2AZ, United Kingdom
One of the key advantages of ionic liquids is the ability to tune the properties of a
solvent through adjustment of the cation and anion. However, there are a huge number
of possible cation/anion combinations, and it is not viable to synthesise and physically
characterise every combination. Chemically altering ionic liquid ions via functionalisation
leads to ionic liquids which can enhance or participate in a chemical process or
reaction. However, the significant effort of synthesising a new ionic liquid can go to
waste if the proposed functionalisation impacts too negatively on key properties.
Solvents can be characterised through solvent-solute interactions, one well established
method is the Kamlet-Taft approach which utilises solvatochromic dyes to determine α
(hydrogen bond donor ability), β(hydrogen bond acceptor ability) and
π*(dipolarity/polarisability) parameters for a solvent. These parameters also offer a well
established method of measuring the physical and chemical results of “fine tuning” in
ionic liquids, these parameters have also been successfully employed in rationalising
reactivity within ionic liquids. 1,2 This presentation will report on, and discuss, the
development of a method for computationally predicting the α and β parameters of ionic
liquids. Quantum chemical calculations on simple component ions can be used to
establish a qualitative, and in certain cases a quantitative relationship with the Kamlet-
Taft parameters. This opens up opportunities for pre-screening and influencing the
design of novel ionic liquids for use as solvents and electrolytes. In applying this method
a connection is also established between the electronic and structural properties of
individual ions and a macroscopic physiochemical property thus enhancing our
understanding of ionic liquids in general. 1 L. Crowhurst, R. Falcone, N. L. Lancaster,
V. Llopis-Mestre and T. Welton, J. Org. Chem., 2006, 71, 8847 2 G. Ranieri, J. P.
Hallett and T. Welton, Ind. Eng. Chem. Res, 2008, 47, 638
COIL-4:154
From Molten Salts to Ionic Liquids: A "Nano" Journey
Jairton Dupont (1) , Jairton.dupont@ufrgs.br. (1) Laboratory of Molecular Catalysis -
Institute of Chemistry, Federal University of Rio Grande do Sul, Porto Alegre RS 91501-
970, Brazil
It is now well accepted that imidazolium ionic liquids (IL) may provide a favorable
environment for the formation of metal nanoparticles with, in most cases, a small
diameter and size distribution under very mild conditions. In this respect, transitionmetal
NPs in imidazolium ILs are stabilized by protective layers of discrete
supramolecular {[(DAI)x(X)x-n)] n+ [(DAI)x-n(X)x)] n- }m (DAI is the dialkylimidazolium cation
and X the anion) species through the loosely bound anionic moieties and/or NHC
carbenes together with an oxide layer when present on the metal surface. These loosely
surface-bound protective species are easily displaced by other substances present in
the media. This on the one hand is responsible to some extend for their catalytic

activity, but on the other hand explains their relatively low stability that leads to
aggregation/agglomeration and eventually to the bulk metal. Therefore the stability and
the catalytic activity of transition-metal NPs in IL are also highly influenced by
coordinative strength of the aggregates with the metal surface and the type and nature
of the substrates/products. The nature of these supramolecular aggregates was
investigated in the condensate phase (X-Ray and ESI-MS) and in the gas phase by MS
experiments. The shape and size of the nanoparticles can be modulated by playing with
the structural organization of the polar and non-polar regions of the 1-alkyl-3methylimidazolium
IL and the ionicity of the metal precursor.
COIL-4:155
Ionic Liquids in Separations and Mass Spectrometry, a New Frontier
Daniel W. Armstrong (1) , sec4dwa@uta.edu, Arlington, Arlington 76019, United States .
(1) University of Texas at Arlington, Arlington Texas 76019, United States
ILs are interesting because of their other useful and intriguing physicochemical
properties. Most common RTILs are composed of unsymmetrically substituted
nitrogen-containing cations (e.g., imidazole, pyrrolideine, pyridine) with inorganic anions
(e.g., C1¯, PF6¯, BF4¯). More recently, many ILs containing a variety of cations and
anions of different sizes have been synthesized to provide specific characteristics that
are beneficial for analytical applications. Over the past few years, research and
applications of ILs have expanded tremendously. The initial impetuses for this
expansion were organic synthesis and the growth of green chemistry. In this
presentation an overview of the structure and properties of ILs and a description of their
expanding use in various applications in separations and mass spectrometry will be
given . ILs constitute the first new class of GC stationary phases in over 30 years.
Their unique aspects will be presented. ILs have proven to be the best liquid Maldi MS
matrix since we introduced them as such a few years ago. The properties of ILs that
make them effective will be discussed. Further, the dications developed for high
stability IL GC stationary phases have found another novel use in electrospray MS as a
reagent for ultra sensitive anion analysis. Different analytical approaches, uses and
mechanism of this new method will be considered.
COIL-4:156
Lipid-Inspired Ionic Liquids: Significant Progress in the Systematic Control of
Structure-Property Relationships in ILs with Long Alkyl Appendages.
James H Davis, Jr. (1)(2) , jdavis@jaguar1.usouthal.edu, 307 N University Blvd., Mobile
Alabama 36688, United States ; Kaila M Mattson (1) ; Arsalan Mirjafari (1) ; Samuel M
Murray (2) ; Richard A O[apos]Brien (1) ; Alan Salter (1) ; Kevin N West (2) ; Andrzej
Wierzbicki (1) . (1) Department of Chemistry, University of South Alabama, Mobile
Alabama 36688, United States (2) Department of Chemical and Biomolecular
Engineering, University of South Alabama, Mobile Alabama 36688, United States

We recently disclosed a new family of imidazolium-based ionic liquids that are
simultaneously very low-melting and highly lipophilic, a combination of attributes that is
frequently antithetical but highly desirable from a number of application-specific
standpoints. The designs of these new ILs were informed by well-known structureproperty
relationships that allow phospholipid compositions to dictate the fluidity of cell
membranes (cf., the fluid mosaic model and homeoviscous adaptation). Specifically, we
found that the incorporation of double-bonds in these side chains– each of which is up
to 22 carbons in length– significantly lowers Tm values relative to counterparts with fully
saturated side chains. During the year that has elapsed since that initial report, we
have dramatically expanded our efforts to map key lipid structure-property relationships
into new ILs, and we have now prepared > 150 variants using natural lipid design
principles and structural features. Because the volume of results is too large to fully
report in this talk, we will focus on our replacement of the O2-sensitive but Tm-lowering
double bonds in the long alkyl groups of our first generation lipid-inspired ILs with
strategically-placed side-chain branches and more oxidatively robust but still Tm
lowering thioether groups. Significantly, even when the latter is part of a normal chain as
opposed to being an element of a side-chain branch, Tm is still lowered appreciably by
its presence. Accordingly, we will present findings from ab initio calculations showing
why these in-chain thioether groups are effective Tm-lowering substitutes for side-chain
double bonds, and why they are predicated to be more effective in this regard than
'normal' ether groups.
COIL-4:157
Bis(Imidazolium)Alkane Bolaamphiphilic Ionic Liquids as Templates for the
Formation of Supermicroporous and Mesoporous Silica
Antony J. Ward (1) , ward_a@chem.usyd.edu.au, F11, Sydney New South Wales 2006,
Australia ; Alex K. L. Yuen (1) ; Falk Heinroth (1) ; Anthony F. Masters (1) ; Thomas
Maschmeyer (1) . (1) School of Chemistry, University of Sydney, Sydney New South
Wales 2006, Australia
A series of bis(imidazolium)alkane bromide salts (alkane = C12 (1), C16 (2), C24 (3)) were
prepared. The salts 1, 2 and 3 can be classified as ionic liquids as they possess melting
points of 47–49 ºC, 77–78 ºC, and 104–105 ºC, respectively. Their critical micelle
concentrations (cmc) were determined and flooding experiments were used to probe the
nature of the mesophases formed by each bolaamphiphile. Using this information,
tetraethoxysilane was hydrolysed in basic media using each of the bolaamphiphiles at
concentrations four times the determined cmc to afford nanoporous silica. In each case,
three different synthesis protocols were used: (i) 2 h at 80 ºC; (ii) 72 h at 100 ºC; and,
(iii) 72 h at 100 ºC at autogenous pressure. Nitrogen sorption of the obtained silicas
show those templated by 1 and 2 are Type I microporous, and the silicas templated by 3
are Type IV mesoporous: for 1-templated silicas the pore size was 6–15 Å; for 2templated
silicas 17–18 Å; and, for 3-templated silicas 24–33 Å. Their surface areas
increased with increasing chain length of the template: from 500–600, to 700–850, to
900–1050 m 2 g -1 when 1, 2, or 3 were used respectively. In the case of silica prepared

y hydrothermal treatment templated with 3, a material possessing a 2-D hexagonal
arrangement with p6mm symmetry was obtained (Figure 1).
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COIL-4:158
Biocompatible Choline Carboxylate Ionic Liquids: Influence of Chain Length and
Double Bound on the Thermotropic Phase Behavior
Doris Rengstl (1) , doris.rengstl@chemie.uni-regensburg.de, Universitätsstraße 31,
Regensburg Bavaria 93040, Germany ; Regina Klein (1) ; Werner Kunz (1) . (1) Department
of Physical and Theoretical Chemistry, University of Regensburg, Regensburg Bavaria
93040, Germany
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Figure 1: Molecular
structure of choline oleate and ChCm with m=10-2 Choline is one of the rare “green”
organic cations. It was formerly known as vitamin B4 and has some important key
functions in the human body. To confirm the low cytotoxicity of choline carboxylates,
cytotoxicity was tested with Hela- and Keratinocytes cell-lines in MTT-assays. Hela cells

can be seen as an alternative to eye irritancy test on rabbit and Keratinocytes examine
skin irritancy power [1] . From R. Klein's work it is shown that the long chain choline
carboxylates (ChCm with m=12-18) behave as valuable surfactants and that the choline
cation increases the water solubility of the respective salts without lowering the
biocompatibility [2] . Short chain choline carboxylates (ChCm with m=2-10) posses all
melting points below 100°C and thus belong to the class of ionic liquids [3] . From choline
hexanoate to choline octanoate a change from a pure ionic liquid behavior to a liquid
surfactant behavior takes place. We also show that the long-chain choline oleate is
liquefied at 30°C compared to the non-ionic liquid, pure surfactant choline
octadecanoate. In the present contribution we present the thermotropic phase
behavior of choline octanoate, choline decanoate and choline oleate as evaluated by
differential scanning calorimetry, light microscopy and small angle X-ray scattering.
[1]N. Vlachy, D. et all, Colloids and Surfaces B: Biointerfaces, 2009, 70, 278-280 [2]R.
Klein submitted to Green Chemistry [3]Petkovic, M. et all, Green Chem., 2009, 11, 889–
894.
COIL-4:159
Functional Chromoinspired Ionic Liquids as smart materials
Luis C Branco (1) , lbranco@dq.fct.unl.pt, Faculdade de Ciências e Tecnologia, UNL,
Caparica Lisboa 2829-516, Portugal ; Aida Branco (1) ; Sandra Gago (1) ; César Laia (1) ;
Fernando Pina (1) . (1) Dept of Chemistry, REQUIMTE, FCT/UNL, Caparica Lisbon 2829-
516, Portugal
The development of smart functional materials that can combine one or more properties
is one of the major challenges in the industrial and research modern applications.
Several smart materials have been developed in recent years where their properties
can be significantly changed in a controlled fashion by external stimuli such as
temperature, pH, electric or magnetic fields, among others. Recently, our group have
described some examples of functional smart materials based on intrinsically
photochromic [1] and electrochromic [2] ionic liquids. Photochromic ILs [1,3] were
developed by the combination of known photochromic anions (e.g. methyl orange or
methyl red) and the appropriate organic cations (e.g. imidazolium, guanidinium,
ammonium, sulfonium and phosphonium) in order to render the ensemble liquid.
Electrochromic ILs [2] were developed by the combination of electrochromic anions
(e.g. cobalt(III), iron(III), chromium(III) complexes) and the appropriate organic cations
(e.g. imidazolium, ammonium and phosphonium). The compounds prepared with these
cations and anions encompass the usual conductivity of the ILs together with the
change of colour characteristic of an electrochromic material. In addition, according to
the metal, it is possible to switch from diamagnetic to paramagnetic states upon
oxidation or reduction, defining novel magneto-electrochromic ionic liquids. These novel
class of functional organic materials based on photochromic, electrochromic, and/or
magnetic ILs can be applied in several scientific fields such as material science
(electrochromic devices and batteries), medicine (MRI contrast agents), within others
(sunglasses, clothing, toys and cosmetics). Acknowledgments: We would like to

thanks Fundação Ciência e Tecnologia (PTDC/QUI/70902/2006 and
PTDC/CTM/103664/2008) [1] Branco, L.C.; Pina, F., Chem. Comm. 2009, 6204. [2]
Branco A.; Branco L.C.; Pina, F. Chem. Commun. 2011, 2300. [3] "Photochromism in
Ionic Liquids"; Luis C. Branco, Fernando Pina, in Ionic Liquids, Theory and Applications,
Intech, 2011.
COIL-4:160
Evaluation of the Long-Term Stability of Ammonium Based Ionic Liquids by Mass
Spectrometry.
Lucia Pisarova (1)(2) , pisarova@ac2t.at, Viktor Kaplan Strasse 2, Wiener Neustadt 2700,
Austria ; Christoph Gabler (1) ; Nicole Doerr (1) ; Ernst Pittenauer (2) ; Guenter Allmaier (2) . (1)
AC2T research GmbH, Wiener Neustadt 2700, Austria (2) Institute of Chemical
Technologies and Analytics, Vienna University of Technology, Wiener Neustadt 2700,
Austria
1 INTRODUCTION Ionic liquid (IL) research accelerated in many field of expertise
since the IL commercialization. Nevertheless, the base knowledge still has extensive
gaps even though some IL already entered into industrial applications. It is essential
that IL remain chemically stable and exerting constant properties throughout the applied
life cycles. However, the knowledge on IL long-term stability seems to be scarce, mostly
gained by thermo-gravimetrical analysis (TGA). This work revealed IL degradation
mechanisms under thermo-oxidative stress utilizing specially developed artificial ageing.
High end mass spectrometric techniques proved to verify the formation and to identify
the chemical structure of the IL degradation product. 2 STUDY OF IL DEGRADATION
MECHANISMS A systematic study of IL chemical stabilities is presented. The selection
of IL comprised ammonium based ionic liquids with and without side chain
functionalization as well as with variation of the anion moiety. The selected IL structures
were based on the structural recommendations supporting the eco-sustainable
approach in terms of low (eco)toxicity and high biodegradability. IL were supplied to
small scale artificial alteration experiment specially developed. For the simulation of
long-term thermo-oxidative stress, several subsequent steps at elevated temperature
were applied. IL were subsequently analyzed by several high end mass spectrometric
techniques to select an appropriate technique revealing IL degradation mechanisms on
the molecular level. 3 CONCLUSIONs The comparison of the IL ionization properties
and mass spectra obtained elucidated laser desorption ionization time-of-flight mass
spectrometry (LDI-TOF-MS) as the most straightforward approach. IL degradation
mechanisms – in particular thermally induced transmethylation at cation moiety - were
elucidated by the structural confirmation of degradation products using fragmentation
patterns obtained by collision induced dissociation (CID). Furthermore, the results
recommend that the presence or absence, respectively, as well as the nature of the
degradation products detected require a joint consideration of both ionic liquid moieties.
COIL-4:161

Ionic Liquid Electrolyte for Lithium Ion Batteries Based on 1-Hexyl-3-Methyl-
Imidazolium Bis(Trifluoromethylsulfonyl)imide
Hélène Rouault (1) , helene.rouault@cea.fr, 17 rue des martyrs, grenoble France, France
; Catherine C Santini (2) ; Nelly Giroud (1) ; Hassan Srour (1) . (1) CEA-Liten, Grenoble 38054
cedex 9, France (2) UMR 5265 C2P2, CNRS, Villeurbanne 69616, France
For cell-phones and laptop-computers several nomad energy storage and converse
devices are necessary for storing the electric energy. Lithium batteries have many
advantages, such as higher energy density, longer cyclability and lower self-discharge
than other rechargeable batteries. 1-3 CEA-Liten has an expertise in the field of
alternative energies devices (fuel cells, photovoltaic and batteries). Since around ten
years, CEA-Liten has thus investigated new electrolytes such as ILs 4-5 . In this
communication, we reported the mobility of the ions in [C1C6Im][NTf2] and the binary
[C1C6Im][NTf2]+Li[NTf2] at different concentrations of LiNTf2 ranging from 0.5 to 1.6
mol.L -1 (M) and at 25, 60 and 79 °C. Likewise, the ionic conductivity, viscosity, potential
window, and ion self-diffusion coefficients in [C1C6Im][NTf2] with or without Li[NTf2] were
also measured [figure 1]. Then, the self-diffusion coefficient (D) of the individual
components, [C1C6Im] + , NTf2 - , and Li + were determined by 1 H, 19 F, and 7 Li pulsed
gradient spin-echo NMR, respectively. The experimental values obtained in this study
were analyzed by the classical Stokes-Einstein, Nernst-Einstein (NE), and Stokes-
Einstein-Debye equations. Moreover, Walden plots were also calculated for the neat
and binary mixtures to clarify the physical and mobile properties of individual ions. [1]:
J.-M. Tarascon, M. Armand, Nature 414, 359, (2001). [2]: M. Armand, F. Endres, D. R.
MacFarlane, H. Ohno, B. Scrosati, Nature Mater. 8, 621, (2009). [3]: K. Hayamiz, S.
Tsuzuki, S. Seki, K. Fujii, M. Suenaga, Y. Umebayashi, J. Chem. Phys. 133, 194505,
(2010). [4]: N. Giroud et al. Electrochem. Soc. Trans. 16, 75, (2009), [5]: N. Giroud et al.
Patents (2010), WO 2010004012, WO2010023185, WO 2010037640.
COIL-4:162
Electrochemical Properties of Sulfur in Ionic Liquid Electrolytes for Li-S Batteries
Jun-Woo Park (1) , d10sa591@ynu.ac.jp, 79-5 Tokiwadai Hodogaya-ku, Yokohama
Kanagawa 240-8501, Japan ; Kento Yamauchi (1) ; Eriko Takashimam (1) ; Naoki
Tachikawa (1) ; Kaoru Dokko (1) ; Masayoshi Watanabe (1) . (1) Department of Chemistry,
Yokohama National University, Yokohama Kanagawa 240-8501, Japan
Sulfur is a promising cathode material for rechargeable lithium batteries because of the
high theoretical capacity of 1672 mA h g -1 though the multi-step reactions from S8 to
8S 2- . However, Li-S batteries have not been widely used because of the poor chargedischarge
performance. One of the drawbacks of Li-S batteries is the poor chargedischarge
cycle stability due to the dissolution of lithium polysulfides (Li2Sn: n = 2-8),
which are generated by electrochemical reduction of sulfur electrolyte during discharge
and charge. Room-temperature ionic liquids (RTILs), which consist of entirely cations
and anions, have attracted much attention, owing to their unique properties such as low

volatility, high thermal stability, high ionic conductivity, wide potential window, and high
chemical stability. One of the characteristics of typical aprotic RTILs is that they are
consisting of weakly Lewis acidic cation and weakly Lewis basic anion. It is anticipated
that the weakly Lewis acidic/basic nature induces less coordination ability. In this
respect, RTILs become interesting media to control solubility of lithium polysulfide.
Sulfur-carbon composite cathodes were prepared by a simple melt-diffusion procedure,
namely, the fused S and carbon (Ketjen black) was simply mixed at the temperature of
155 °C. The sulfur-carbon composite and a binder polymer were mixed in an N-methyl
pyrrolidone (NMP) solvent to form slurry, and then, this slurry was coated onto Al
current collectors. The electrolyte was a binary RTIL consisting of 0.64 mol dm -3 lithium
bis(trifluoromethylsulfonyl)amide (LiTFSA) dissolved in N,N-diethyl-N-methyl-N-(2methoxyethyl)
ammonium bis(trifluoromethylsulfonyl)amide (DEMETFSA). Li-S battery
with the RTIL electrolyte exhibited a reversible capacity of 600 mAh g -1 even after 50
cycles and a good Coulombic efficiency of more than 98%, suggesting that the
dissolution of the lithium polysulfide is efficiently suppressed by using RTIL.
COIL-4:163
Novel Electrolytes for Lithium-Ion Batteries
Tom F. Beyersdorff (1) , beyersdorff@iolitec.com, 720 2nd Street, AIME, Tuscaloosa
Alabama 35401, United States ; Thomas J. S. Schubert (2) ; Frank Stiemke (2) . (1) IoLiTec
Inc., Tuscaloosa Alabama 35401, United States (2) IoLitec GmbH, Heilbronn Baden-
Wuerttemberg 74076, Germany
The most important advantages of lithium ion batteries (LIBs) are their high energy-toweight-ratio,
lack of memory effect and low discharge when not in use. This makes
them the energy source of choice for many applications in consumer electronics.
However, over the past years serious problems occurred as a consequence of shortcircuit
currents which led to overheating and ignition of the organic solvents used in the
formulation of the electrolytes. Therefore, new types of electrolytes are currently under
investigation worldwide. Important requirements for the electrolytes include large
electrochemical stabilities and sufficient to good conductivities as well as low viscosities.
Many ionic liquids (ILs) – salts that are liquid at temperatures below 100°C – show very
large electrochemical, chemical and thermal stabilities. In addition, they are
incombustible at temperatures below their decomposition point. Together with their
tunable viscosities and conductivities this makes them to promising substances for safe
electrolytes in batteries. In this presentation we will report on our recent developments
in the field of electrolytes for LiBs based on ionic liquids. The focus of this talk will be the
tunability of the viscosity and the conductivity by using pure ionic liquids with different
functionalities, mixtures of ionic liquids and additives. We will also put some light on
their ability to dissolve lithium-salts.
COIL-4:164
Phase Behavior to Applications for Gases in Ionic Liquids

Mark B. Shiflett (1) , mark.b.shiflett@usa.dupont.com, Experimental Station, Wilmington
Delaware 19880-0304, United States ; A. Yokozeki (1) . (1) Chemical Sciences and
Engineering, DuPont Central Research and Development, Wilmington Delaware 19880-
0304, United States
Ionic liquids (ILs) are generally defined as salts composed of discrete cations and
anions with melting points below 100°C, and many are liquid at ambient temperature.
Interest in commercial use of ILs in the chemical industry is expanding rapidly, but
commercialization is hampered by a lack of physical property data, particularly for
mixtures of ILs with ordinary gases and liquids. Our research has focused on accurately
measuring vapor-liquid equilibria (VLE) and liquid-liquid equilibria (LLE) and using
thermodynamic models to understand the phase behavior of binary gas mixtures in ILs.
This presentation will focus on the importance of characterizing the global phase
behavior of gases in ionic liquids and how this can provide insight into new applications.
Solubility measurements of several gases in ILs will be discussed and important
experimental details regarding VLE measurements using a gravimetric microbalance
and VLLE measurements using a mass-volume technique will be highlighted. VLE data
have been successfully correlated with a modified Redlich-Kwong equation of state
(EOS), and in certain cases (e.g. hydrofluorocarbons) the EOS predicts partial
immiscibilities (LLE) with lower critical solution temperatures (LCSTs) in the
fluorocarbon-rich side solutions. In addition to the phase behavior, we will discuss
unusually large negative excess molar volumes discovered in the present LLE
experiments. We have also found that gases such as CO2 can exhibit different solubility
behaviors in ILs (i.e. physical and chemical absorption) and that these behaviors can be
analyzed with the EOS using a simple association model and excess thermodynamic
functions. Recent ternary phase behavior (e.g. CO2/SO2/IL) experiments and model
calculations will also be examined. Knowledge of these gas and IL phase behaviors
has led to several practical applications including separation of azeotropic mixtures and
absorption cooling cycles. These along with a few new examples for future applications
will be discussed.
COIL-4:165
Long Term Pilot Plant Experience on Aromatics Extraction with Ionic Liquids
Wytze Meindersma (1) , g.w.meindersma@tue.nl, P.O. Box 513, Eindhoven 5600 MB,
The Netherlands; Ferdy S.A.F. Onink (1) ; Antje R. Hansmeier (1) ; André B. de Haan (1) . (1)
Department of Chemical Engineering & Chemistry/SPS, Eindhoven University of
Technology, Eindhoven 5600 MB, The Netherlands
Since 2004, we are conducting pilot plant trials with various contactors and different
ionic liquids for petrochemical model feeds as well as real refinery feeds. Our pilot plant
contains several columns (RDC, Kuhni, PDDC) with a height of 6 m and 60 mm
diameter. Up to 100 kg of ionic liquid and 200 L of feed are applied in experiments. The
hydrodynamic and mass transfer performance of a rotating disc contactor has been
characterized for a toluene/n-heptane mixture, a model FCC feed and a real LCCS

efinery feed using 3-methyl-N-butyl-pyridinum dicyanamide as the ionic liquid.
Experiments with the real LCCS feed demonstrated comparable extraction performance
to the model FCC feed. The removal rate of benzene from LCCS was 81% and that of
toluene 71%, compared to 89% and 75%, respectively, for the model FCC (Figure 1).
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Figure 1. RDC concentration
profiles at T = 313.15 K and 700 rpm at a solvent-to-feed ratio S/F = 4; weight fraction
aromatic ∆ in extract (IL) and ◊ in raffinate (feed). Over the past 5 years, the same
batches of ionic liquids have been repeatedly regenerated by evaporation and reused.
Our studies revealed that, although coloration occurs, the extraction performance of the
ionic liquids has not changed even after several years of usage. After the real LCCS
refinery feed experiments, validation with the toluene/n-heptane model feed confirmed
unchanged extraction performance.
COIL-4:166
Solubilities of Sour Gases in Ionic Liquids and Their Non-ideality and Prediction
using Flory-Huggins Model
Pedro J. Carvalho (1) , quijorge@ua.pt, Campus Universitário de Santiago, Aveiro Aveiro
3810-193, Portugal ; João A.P. Coutinho (1) . (1) Departamento de Química, CICECO,
Universidade de Aveiro, Aveiro 3810-193, Portugal
Ionic liquids (ILs) are a class of neoteric solvents composed of large organic cations and
organic or inorganic anions that cannot form an ordered crystal and thus remain liquid at
or near room temperature. The outstanding characteristics of these fluids, and the easy
manipulation of their properties due to the possibility of interchange among thousands
of cations and anions, make of the ILs “designer” solvents with a wide range of
foreseeable applications.Nonetheless, and despite of the promising properties of ILs,
further research is still required in order to make them solvents feasible candidates for
real applications. Being a key parameter in the design of equilibrium stage– and rate–
based separations, reliable gas solubility data is of most interest and a fundamental

step towards the development of industrial applications, either by the data itself or by
developing predictive and simulation tools to aid in the development of such
applications.Using a high pressure cell, previously used for extensive studies of CO2
solubilities, VLE isotherms up to 363 K and pressures up to 100 MPa were measured
for mixtures of CO2 or CH4 with several aprotic and protic ionic liquids. Furthermore, the
nonideality of sour gases (CO2 , NH3, SO2, and H2S) solutions in ionic liquids is here
investigated and shown that these systems present negative deviations to the ideality in
the liquid phase, that these deviations are dominated by entropic effects and that the
gas solubility can be predicted using the Flory-Huggins model. Acknowledgments
Pedro J. Carvalho acknowledges the financial support from Fundação para a Ciência e
a Tecnologia through his PhD. (SFRH/BD/41562/2007).
COIL-4:167
Modification of Ionic Liquids for Carbon Dioxide Capture
Anthony E Rosamilia (1) , anthony.rosamilia@csiro.au, Bayview Avenue, Clayton
Victoria 3168, Australia ; Junhua Huang (1) ; Hanming Liu (1) . (1) Department of Energy
Technology, Commonwealth Sceintific and Industrial Research Organisation, Clayton
Melbourne 3168, Australia
Chemical sorbents in post combustion capture is one approach that attempts to reduce
carbon dioxide (CO2) emissions from coal-fired power plants. Ionic liquids (ILs) are
potentially good CO2 absorbents as they have high selectivity for CO2 over other gases.
Coupled with their high thermal and chemical stability, non-corrosivity, non-volatility and
the ease of regeneration (CO2 desorption), they make potentially good alternatives to
the currently used aqueous amine or ammonia solutions. ILs, however, suffer from
having comparatively lower sorption capacities and slow rates of sorption. 1 When ILs
are doped with metal salts CO2 sorption capacity can be increased. 2 [EMIM][NTf2]
containing Zn(NTf2)2(1:1 mol:mol) has a CO2 solubility 25 times greater (weight%) than
that of [EMIM][NTf2]. The system however still suffers from slow sorption owing to its
high viscosity. 3 We have investigated a range of additives, aiming to lower viscosity and
increase rate of sorption while maintaining the beneficial properties of ionic liquids. Our
research shows promising results with one such additive, 1-methylimidazole (MeIm).
When MeIm is added into Zn(NTf2)2[EMIM][NTf2] (1:1 mol:mol), e.g. 16 wt %, the
dynamic viscosity (η) (Table 1) is decreased (7-fold) and the CO2 diffusion co-efficient
(D) is increased by >50-fold (Table 1), accounting for a faster sorption rate. The volatility
of MeIm becomes negligible in the zinc ion-containing system. A decrease in CO2
sorption capacity is observed (Table 1); however, the amount of additive can be tuned
to obtain an optimum balance of beneficial sorbent properties.
Sorbent System
η (cP) at Absorption Capacity D (CO2) (m
40°C (wt%)
2 •s -
1
)
Zn(NTf2)\[EMIM][NTf2] (1:1) 3 1758 5.78
2.3×10 -13
(±1.6×10 -14 )
16 wt% MeIm in237 2.54 1.3×10 -11

Zn(NTf2)\[EMIM][NTf2] (1:1) (±4.9×10 -14 )
EMIM= 1-ethyl-3-methylimidazolium NTf2= bis(trifluoromethylsulfonyl)imide 1.
Huang, J.; Rüther, T. Aust. J. Chem. 2009, 62, 298-308. 2. Patent Application WO
2011/011830. 3. Liu, H.; Huang, J.; Pendleton, P. Energy Procedia 2011, 2, in press.
COIL-4:168
Improvement of the Selectivity of Hydrogenations by a Solid Catalyst with Ionic
Liquid Layer (SCILL-concept)
Andreas Jess (1) , jess@uni-bayreuth.de, Universitätsstraße 30, FAN A, Bayreuth
Bayern 95444, Germany ; Wolfgang Korth (1) . (1) Chair of Chemical Engineering,
University of Bayreuth, Bayreuth 95440, Germany
The concept of a solid catalyst with ionic liquid (IL) layer (SCILL) as a method to
improve the selectivity is presented. In the SCILL concept, a porous catalyst is coated
with an IL. The activity and selectivity is changed by the coating in two ways: (1) The IL
may has a positive influence on the chemical properties of the catalyst (cocatalytic
effect). (2) The IL changes the concentrations of educt(s) and inter-me-di-ate(s),
compared to the uncoated catalyst (solvent effect). For example, the selectivity to the
intermediate is favored if the intermediate is less soluble in the IL than the educt. At
first, the hydrogenation of cyclooctadiene to cyclooctene (COE) and cyclooctane on a
Ni-catalyst coated with the ILs [BMIM][OcSO3] and [TBA][ Br] was tested. The coating of
the internal sur-face with the IL strongly enhances the maximum intrinsic COE yield
from 40% to 70 %. Similar results were obtained with other ILs. It is important to note
that the SCILL effect is even reached for ILs, which are solid at the reaction temperature
of 50°C ([TBA][ Br]). The SCILL-concept was also tested for other reactions, the Nicatalyzed
hydrogenation of 1-octine and cinnamaldehyde, and the Ru-catalyzed
hydrogenation of cinnamonaldehyde. In all cases, the yield of the intermediates
increase. The IL layer is robust and no leaching into the organic phase was detectable.
The pores structure was characterized by BET- and Hg-porosimetry of the coated and
uncoated catalysts. With increasing IL-loading, the pore volume and the surface
decrease. The modelling of the coating process shows a good agreement with the
measurements. If bigger catalyst particles (1 mm) are used, the influence of pore
diffusion leads to a decrease of the maximum yield of the COE both for the uncoated
and IL-coated catalyst. Nevertheless, the advantage of the IL coating is still present.
COIL-4:169
Interface Segregation of Metal ions in Ionic Liquids Studied by Photoelectron
Spectroscopy
Akihito Imanishi (1)(2) , imanishi@chem.es.osaka-u.ac.jp, 1-3, Machikaneyama,
Toyonaka Osaka 560-8531, Japan ; Takayuki Nose (1) ; Tetsuya Tsuda (3) ; Susumu
Kuwabata (3)(2) ; Ken-ichi Fukui (1) . (1) Department of Chemistry, Graduate School of

Engineering Science, Osaka University, 1-3 Machikaneyama Osaka 560-8531, Japan
(2) CREST/JST, 1-3 Machikaneyama Osaka 560-8531, Japan (3) Department of
Applied Chemistry, Graduate School of Engineering, Osaka University, Suita Osaka
332-0012, Japan
It is interesting subject to investigate the behaviour of metal ions in ionic liquids.
Especially, the behaviour of ions at the interface of IL is largely different from those at
the interface of conventional solvents such as water and organic solvent, because
strong coulomb interaction between metal ions and IL plays an important role in the
chemical behaviour of metal ions. On the other hand, it is known that most of the ionic
liquids show extremely low vapour pressure, which will enable us to investigate the
reaction of the ionic liquids (or the solute they contain) under high vacuum conditions.
Especially, the photoelectron spectroscopy is valuable for investigating the chemical
state and concentration of ions at the interface. Here, we report the investigation of the
interface segregation of metal ions in ionic liquids studied by XPS. BMI-TFSI and BMI-
BF4 containing Ag + ions were prepared. XPS measurement was carried out for the
prepared IL solution. In the case of BMI-TFSI solution, the concentration of Ag + ions at
the interface (i.e. IL/vacuum interface) was slightly larger than that in the bulk. This
indicates that the segregation of metal ions occurs at the interface of IL. On the other
hand, in the case of BMI-BF4 solution, the concentration of Ag + ions at the interface was
much larger than that in the bulk. In other words, the degree of the enhancement of
interface segregation strongly depends on the kinds of IL. We also carried out the same
experiment using some other metal ions, and found that observed segregation
phenomena of metal ions in IL could be explained by the affinity between metal ions
and anionic species of IL.
COIL-4:170
Ionic Liquids as Silica Deactivating Agents in Gas Chromatography for Direct
Analysis of Primary Amines in Water
Agnieszka Krzyzaniak (1) , a.krzyzaniak@tue.nl, Den Dolech 2, Eindhoven Noord
Brabant 5600 MB, The Netherlands; Wilko Weggemans (1) ; Boelo Schuur (1) ; André B. de
Haan (1) . (1) Department of Chemical Engineering and Chemistry, Eindhoven University
of Technology, Eindhoven 5600 MB, The Netherlands
Analysis of primary amines in aqueous samples remains a challenging analytical issue.
The preferred approach by gas chromatography is hampered by interactions of free
silanol groups with highly reactive amine groups, resulting in inconsistent
measurements. Here, we develop a method for direct analysis of aliphatic amines and
diamines in aqueous samples by gas chromatography (GC) with silanol deactivation
using ionic liquids (ILs). ILs including trihexyl(tetradecyl)phosphonium bis 2,4,4-
(trimethylpentyl)phosphinate (Cyphos IL-104), 1-methyl-3-propylimidazolium bis
(trifluoromethylsulfonyl) imide [pmim][Tf2N] and N”-ethyl-N,N,N',N'tetramethylguanidinium
tris(pentafluoroethyl) trifluorophosphate [etmg][FAP] were
tested as deactivating media for the GC liner. Solutions of these ILs in methanol were

injected in the system prior to the analysis of primary amines. Butane-1,4-diamine
(putrescine, BDA) was used as a reference amine. The best results were obtained using
the imidazolium IL [pmim][Tf2N] . With this deactivator, excellent reproducibility of the
analysis was achieved, and the detection limit of BDA was as low as 1mM. The
applicability of the method was proven for the analysis of three different primary amines
(C3-C5) and their diamine-equivalents.
COIL-4:171
Ionic Liquid Thin Film Technologies
Peter Wasserscheid (1) , peter.wasserscheid@crt.cbi.uni-erlangen.de, Egerlandstrasse
3, Erlangen 91058, Germany . (1) Chemical and Biological Engineering, UNIV
Erlangen-Nuremberg, Erlangen D-91058, Germany
There is no doubt that the synthesis and purification of most ionic liquids is more
demanding in chemicals and energy than – for example - the production of the same
amount of a common volatile solvent, such as e. g. methanol. This has led to
discussions about the sustainability of ionic liquids in solvent applications, and indeed,
there is little sense from a Green Chemistry point to substitute methanol by an ionic
liquid if the first performs as well as the latter. In the last five years a large number of
new ionic liquid applications have been published. Many of these build successfully on
the unique property profile of these low melting salts to enable processes of much
higher efficiency or products of much better functionality. It is quite clear that for any
technical IL application the enhanced performance created by the ionic liquid has to
justify the higher effort of the IL synthesis. This raises the important question about the
minimum amount of ionic liquid that is required to create the desired “ionic liquid
performance” in a given application. Rigorous attempts to minimize the IL volume in a
broad range of applications have led to Ionic Liquid Thin Film Technologies. The
contribution will present preparation technologies, characterization techniques and
application scenarios of these technologies. Special attention will be given to the
development and use of “Supported Ionic Liquid Phase (SILP)” materials and “Solid
Catalysts with Ionic Liquid Layer (SCILL)” systems.
COIL-4:172
The Origin of the Prepeak and Other Intermolecular Features in the X-ray
Scattering of Amorphous Room-Temperature Ionic Liquids
Claudio J Margulis (1) , claudio-margulis@uiowa.edu, 118 IATL, Iowa City Iowa 52242,
United States ; Harsha V.R. Annapureddy (1) ; Hemant K Kashyap (1) ; Pablo De Biase (1) .
(1) Department of Chemistry, University of Iowa, Iowa City Iowa 52242, United States
First sharp diffraction peaks (the so-called prepeaks) in the x-ray and neutron scattering
of ionic liquids have frequently been equated with large scale mesoscopic organization.
The most common interpretation of these peaks is in terms of nanoscale segregation

and the formation of domains of different morphologies. Careful mathematical analysis
(J. Phys. Chem. B, 2010, 114, 16838–16846; J. Chem. Phys., 2011, 134, 064501) and
recent experiments (J. Chem. Phys. 2010, 133, 74510–74517) have revisited this
interpretation and found that in many cases, the prepeak is not related to large scale
organization, instead is a simple consequence of solvation anisotropy. We find that
the signature of ionic liquid morphology is the presence of two or if there is a prepeak
three peaks in the low q intermolecular region of the x-ray structure functions S(q). If
present, the prepeak is often indicative of scattering from bright (electron rich) anions
organized in an anisotropic fashion by dark cations. A second peak is often present that
arises from ions of the same charge and the absence at that spatial frequency of ions of
opposite charge. Finally the most prominent intermolecular peak often arises from close
contact neighbors. These can either be of opposite charge, organized by Coulomb
forces, or of the same charge when contacts are hydrophobic in nature.
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Figure 1: S(q) in the low q
region for liquids [C6MIM][Cl] and [P14,666][NTf2] at 300K from our computer
simulations. This figure highlights the three signature peaks in two very different ionic
liquids.
COIL-4:173
Morphology of Poly(Ethylene Oxide)-RTILs Mixtures: SAXS and MD Studies.
Alessandro Triolo (1) , triolo@ism.cnr.it, via Fosso del Cavaliere, 100, Rome Lazio
00133, Italy ; Olga Russina (2) ; Lorenzo Gontrani (2) ; Lo Celso Fabrizio (3) ; Ruggero
Caminiti (2) . (1) Istituto Struttura Materia, Consiglio Nazionale delle Ricerche, Rome, Italy
(2) Department of Chemistry, Università di Roma, Sapienza, Rome, Italy (3) Department
of Physical Chemistry, Università di Palermo, Palermo, Italy
Poly(ethyleneoxide) is one of the few polymers that are soluble in room temperature
ionic liquids. Some years ago, we highlighted the good solvent nature of RTILs towards
PEO, using SANS technique [1], and Ribeiro simulated the morphology of PEO-rich

mixtures [2]. Recently the activities of Watanabe's [3], Rogers's [4] and Lodge's [5]
groups focused on the phase diagram of PEO-RTIL binary mixtures, detecting the
existence of a LCST for these systems and screening the role of RTIL's chemical details
on this complex behavior. Here we show recently obtained results from both Small
Angle X-ray and Neutron Scattering from PEO-RTILs mixtures at ambient temperature,
as a function of polymer concentration, for a variety of RTILs. We screened the role of
alkyl chain length, methylation of position 2 in the imidazolium ring and other chemical
details of the RTIL on the morphology of the macromolecule, extracting information as
interesting as its average size, the persistence length and chain rigidity.
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These results have been
complemented with MD simulation study of PEO dissolved in C2mimTf2N and
C2C1mimTf2N, to explore the role of hydrogen bonding on microscopic organization.
SAXS data for another polymer/IL mixture (PMMA/C2mimTf2N) will be presented and
compared with PEO/C2mimTf2N. [1] Triolo, JPCB 110, 1513 (2006) ; [2] Ribeiro, JCP
124, 184902 (2006); [3] Watanabe, Chem. Comm. 4939 (2008); [4] Rogers, PCCP 11,
1096 (2009); [5] Lodge, JPC-Letters 1, 1962 (2010)
COIL-4:174
High-Energy X-ray Diffraction Study on Liquid Structure of 1-Ethyl-3-
Methylimidazolium Based Ionic Liquids with the Aid of MD Simulations
Yasuhiro Umebayashi (1) , yumeb@chem.kyushu-univ.jp, Hakozaki, Higashi-ku,
Fukuoka Fukuoka 812-8581, Japan ; Hiroshi Hamano (1) ; Kenta Fujii (2) ; Shiro Seki (3) ;
Yasuo Kameda (4) ; Babak Minofar (1) . (1) Department of Chemistry, Faculty of Science,
Kyushu University, Fukuoka Fukuoka 812-8581, Japan (2) Institute for Solid State
Physics, The University of Tokyo, Kashiwa Chiba 277-8581, Japan (3) Central
Research Institute of Electric Power Industry, Komae Tokyo 201-8511, Japan (4)
Department of Material and Biolgical Chemistry, Faculty of Science, Yamagata
University, Yamagata Yamagata 990-8560, Japan

Ionic liquids have been applied to electrolyte for the electric storage devices such as
lithium ion secondary batteries, high performance electric double layer capacitors and
fuel cells. For these applications, relatively high viscosity of ionic liquids is one of the
problems to achieve higher energy density. According to modern liquid theory, transport
properties of liquids and/or electrolyte solutions such as viscosity and ionic conductivity
can be described with static and dynamic structure factors, which can be evaluated by
neutron/X-ray scattering techniques experimentally. Thus, it is indispensable to reveal
static and dynamic structure factors of ionic liquids to improve their transport properties.
In this contribution, we will present static and dynamic X-ray structure factors of 1-ethyl-
3-methylimidazolium based ionic liquids with various anions. High-energy X-ray
diffraction (HEXRD) experiments were performed with 9 ionic liquids, and thus obtained
static X-ray structure factors were analyzed with the aid of MD simulations. Inelastic Xray
scattering (IXS) experiments were also carried out to elucidate dynamic structure
factors of the ionic liquids.
COIL-4:175
Effect of Cation Symmetry on the Morphology and Physical Properties of
Imidazolium Ionic Liquids
Edward L. Quitevis (1) , edward.quitevis@ttu.edu, Box 41061, Lubbock Texas 79409,
United States . (1) Department of Chemistry & Biochemistry, Texas Tech University,
Lubbock Texas 79409, United States
The morphology and physical properties of 1,3-dialkylimidazolium
bis{(trifluoromethane)sulfonyl}amide ([(CN/2)2im][NTf2]) are compared to that of 1-alkyl-3methylimidazolium
bis{(trifluoromethane)sulfonyl}amide ([CN-1C1im][NTf2]) for N = 4, 6,
8, and 10. For a given pair of ionic liquids (ILs) with the same N, the ILs differ only in the
symmetry of the alkyl substitution on the imidazolium ring of the cation. Small-wide
angle X-ray scattering measurements indicate that for a given symmetric/asymmetric IL
pair, the size of the structural heterogeneities are larger in the asymmetric IL than in the
symmetric IL. Symmetric IL pairs with N = 4 and 6 easily crystallize, whereas longer
alkyl chains and asymmetry hinder crystallization. Interestingly, the glass transition
temperature scales inversely with the correlation length of the structural heterogeneities
and with the length of the longest alkyl chain. Whereas the densities for a
symmetric/asymmetric IL pair with a given N are nearly the same, the viscosity of the
asymmetric IL is greater than that of the symmetric IL. Also an even-odd effect

previously observed in molecular dynamics simulations is confirmed by viscosity
measurements.
COIL-4:176
Analytical Methods for Analysis of Ionic Liquids Components in Various Matrices
Piotr Stepnowski (1) , sox@chem.univ.gda.pl, ul. Sobieskiego 18, Gdańsk, Poland ;
Stephanie Steudte (1) ; Stefan Stolte (2) . (1) Department of Enviromental Analytics,
University of Gdańsk, Gdańsk 80-952, Poland (2) Department for sustainable chemistry,
University of Bremen, Center for Environmental Research and Sustainable Technology
(UFT), Bremen 28359, Germany
Research of considerable practical importance, such as investigations into purity,
applicability, robustness and stability of ionic liquid based products and technologies,
will require relatively simple and reproducible analytical techniques. These methods
must not only be applicable to different matrices but also to the very low concentrations
likely to be present in products, technological solutions, wastes, wastewaters and other
materials. The main aim of this presentation is to summarize hitherto methodologies
developed for analysis of ionic liquids anions and cations in various matrices of natural
and artificial origin. Most of the methods reported so far for separating and determining
ionic liquid cations involve high-performance liquid chromatography (HPLC) in reversed
phase mode (RP-HPLC), ion chromatography (IC-HPLC), ion pair chromatography (IP-
HPLC), as well as capillary electrophoresis (CE). Applied detection systems involve
spectrophotometry, mass spectrometry as well as conductometry. Anions analytics is
today based solely on ion chromatography with conductometric detection, both in the
suppressed and non-suppressed mode. Additionally methods using solid phase
extraction of ionic liquids cations from highly diluted solutions are presented. In addition
methods for extraction of ionic liquids from solid samples using mixtures of phosphoric
or trifluoroacetic acid with saturated solutions of ammonium salts are discussed.
COIL-4:177
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Solubility of Gases in Imidazolium-Based Ionic Liquids: Understanding by
Molecular Dynamics Simulations

Daniela Kerlé (1) , daniela.kerle@uni-rostock.de, Dr.-Lorenz-Weg 1, Rostock 18059,
Germany ; Dietmar Paschek (1) ; Ralf Ludwig (1) . (1) Physical and Theoretical Chemistry,
University of Rostock, Rostock 18059, Germany
The solvation process of gases in Ionic Liquids is of fundamental interest for gas
separation processes and flue gas decontamination. In particular, the phase behaviour
of CO2 with ILs could be instrumental for the development of potential carbon
sequestration applications. To improve existing solvents, however, it is important to fully
understand their solvation behavior. We focused on a certain class of ILs, the
imidazolium-based 1-n-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide
([Cnmim][NTf2]) with varying chain length n = 2, 4, 6, 8. Based on molecular dynamics
simulations covering a broad temperature range (300 K to 500 K), we determine the
solubility of "light" gases such as CO2, O2, N2, H2 and the noble gases from their
solvation free energies. Based on their size and, more importantly, their interaction
strength with the solvent, the temperature dependence of the solubility of light gases is
found to change in a systematic fashion, linking the absolute solvation free energy of a
certain gas with its temperature dependence over a broad temperature range. Based on
our simulation data we can provide a simple picture depending only on a few
parameters, predicting consistently the temperature dependence of all those gases.
More importantly, we can now provide advice with respect to the reliability of published
data in cases where experimental data from different sources report different
temperature dependence.
Fig. 1: Simulated solubilities of different gases in [C6mim][NTf2].
COIL-4:178
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Selective Removal of Troublesome Natural Gas Components Utilising a Blend of
Ionic Liquids
Peter Janiczek (1) , peter.janiczek@proionic.com; Roland Stefan Kalb (1) ; Gerhard
Thonhauser (2) ; Thomas Gamse (3) ; Leopold Braeuer (4) . (1) Research and Development,
proionic GmbH, Grambach 8074, Austria (2) Chair of Drilling Engineering, Mining
University Leoben, Leoben 8700, Austria (3) Institute of Chemical Engineering and
Environmental Technology, Graz University of Technology, Graz 8010, Austria (4)
Technology Development and Application, OMV Exploration & Production, Vienna
1020, Austria
Removing certain components of natural gas streams is a crucial step in meeting
specifications of sales gas. Aqueous amine solutions are commonly known as washing
media for this purpose, but show a series of disadvantages. This fact brings Ionic
Liquids (ILs) in the centre of interest. A screening test for gas absorption at atmospheric
and high pressure initiated this project. The focus for IL selection was driven by nontoxicity
and a feasible large scale and competitive high quality production. One blend of
ILs was analysed for gas selectivity, influence of water and gas components.
Furthermore, stability of this IL-Blend was intensively checked with different methods. A
series of physical parameters, among them absorption enthalpies, were also
determined. Furthermore, we were able to identify the absorption mechanism. Finally,
the IL-Blend, synthesised using CBILS® method, was successfully tested in a technical
plant for recycling behaviour and its feasibility.
COIL-4:179
Studying Ionic Liquids Through Gas Solubility
Margarida F Costa Gomes (1) , margarida.c.gomes@univ-bpclermont.fr, BP 80026,
Aubière Aubière 63171, France ; Dimitrios Almantariotis (1) ; Yun Deng (1) ; Alfonso S.
Pensado (1) . (1) Université Blaise Pascal Clermont-Ferrand & CNRS, Laboratoire
Thermodynamique et Interactions Moléculaires (UMR 6272), Aubière 63171, France
In addition to the numerous possible applications of ionic liquids, they offer an
interesting research subject on how the macroscopic properties of complex fluids can
be related to their molecular structures. Ionic liquids are a vast family of liquids, with a
large chemical diversity leading to a range of molecular interactions that determine their
unique macroscopic properties. Ionic liquids are also structured, with persistent domains
in the liquid phase: one formed by aggregates of the non-polar side chains, and the
other by a network composed by the charged head groups and dominated by
electrostatic interactions. This segregation of polar and nonpolar domains changes the
way in which solvation can be understood in these liquids. Ionic liquid solutions of
simple molecular compounds, that are often gaseous at ambient conditions, can be
used to assess the microscopic features (both structural and energetic) that control the
dissolution process. We present several examples for which gas solubilities have
provided insights on the structure and properties of different families of ionic liquids, for

example, ester functionalized or partially fluorinated. We also show how this knowledge
can be used in the development of new ionic liquids capable of selectively dissolving
different molecular solutes.
COIL-4:180
Temperature and Pressure Dependence of the Viscosity of Phosphonium Ionic
Liquids
Daisuke Kodama (1) , dkodama@chem.ce.nihon-u.ac.jp, 1 Nakagawara, Tokusada,
Tamura-machi, Koriyama Fukushima 963-8642, Japan ; Mitsuhiro Kanakubo (2) ;
Kensuke Ohashi (1) ; Kenneth R. Harris (3) ; Takashi Makino (2) ; Tatsuya Umecky (2) ; Akira
Suzuki (2) ; Masashi Sugiya (4) ; Shun Kodama (4) . (1) Department of Chemical Biology and
Applied Chemistry, College of Engineering, Nihon University, Koriyama Fukushima 963-
8642, Japan (2) Research Center for Compact Chemical System, National Institute of
Advanced Industrial Science and Technology, Sendai Miyagi 983-8551, Japan (3)
School of Physical Environmental and Mathematical Sciences, University of New South
Wales at Australian Defence Force Academy, Canberra ACT 2600, Australia (4)
Organic Chemicals R&D Department, Organic Chemicals Division, Nippon Chemical
Industrial Co., Ltd., Kameido Tokyo 163-8515, Japan
Room-temperature ionic liquids (RT-ILs), which are liquid at room temperature and
composed entirely of ions, have attracted much attention because of their unique
properties such as no flammability, low volatility, high chemical stability and high ionic
conductivity. RT-ILs are expected to be applied to some industrial materials such as fuel
cells, electric double layer capacitors, solar cells, and lithium ion batteries; however,
there have been very few studies of the viscosity of RT-ILs at high pressure. In the
present study, the viscosity and density of ionic liquids triethylpentylphosphonium
bis(trifluoromethylsulfonyl) imide ([P2225][Tf2N]) and triethyloctylphosphonium
bis(trifluoromethylsulfonyl)imide ([P2228][Tf2N]) have been measured over a wide
temperature range between 273.15 and 363.15 K at atmospheric pressure. Highpressure
viscosity measurements were made at (303.15, 313.15, 323.15, and 333.15) K
to a maximum pressure of 50 MPa with falling-ball viscometer. The temperature and
pressure dependence for the viscosity was analyzed by the Arrhenius, Vogel–Fulcher–
Tammann (VFT), and Litovitz equations. The experimental viscosity data agree fairly

well with the correlated results by VFT and Litovitz equations, as shown in Fig.1.
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COIL-4:181
Thermal Stability of [BF4] - - and [PF6] - -Based Ionic Liquids
Alasdair W. Taylor (1) , alasdair.taylor@nottingham.ac.uk, University Park, Nottingham
Nottinghamshire NG7 2RD, United Kingdom ; Kevin R. J. Lovelock (1) ; Thomas J.
Sanderson (1) ; Coby J. Clarke (1) ; Richard A. Bourne (1) ; Simon Puttick (1) ; Peter Licence (1) .
(1) School of Chemistry, The University of Nottingham, Nottingham Nottinghamshire
NG7 2RD, United Kingdom
Understanding thermal stability is paramount for any long-term elevated temperature
application of an ionic liquid. A combinatorial approach is described that uses both bulk
distillation 1,2 and mass spectrometry 3,4 to yield a greater insight into vaporisation and
decomposition processes. Excellent agreement is demonstrated between the two
techniques. This study focuses upon [CnC1Im][BF4] and [CnC1Im][PF6] ionic liquids; with
[C4C1Im][BF4] used as a case study. Using high vacuum (~10 -6 mbar) distillation
apparatus we have achieved high rates of distillation of ionic liquids (~5 g.hr -1 ). Heating
[C4C1Im][BF4] in the distillation apparatus at reduced pressure yields different products,
dependent upon temperature (see figure).

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At lower temperatures, the
distillate is mostly [C4C1Im][BF4]; at higher temperatures the carbene-borane 1-butyl-3methylimidazolium-2-trifluoroborate
is produced. Mass spectrometry of [C4C1Im][BF4]
showed only neutral ion pairs (NIPs) over the temperature range of 500 to 600 K. At
higher temperatures, 1-butyl-3-methylimidazolium-2-trifluoroborate detected.
Methylation of the imidazolium ring at the C 2 position prevents formation of the carbeneborane
leading to vaporisation only. Similar chemistry is observed when using
[CnC1Im][PF6] ionic liquids in place of [CnC1Im][BF4]. (1) Phys. Chem. Chem. Phys.
2010, 12, 1772-1783. (2) Dalton Trans. 2011, 40, 1463-1470. (3) Phys. Chem. Chem.
Phys. 2007, 9, 982-990. (4) J. Phys. Chem. B 2008, 112, 11734-11742.
www.nottingham.ac.uk/ionicliquids
COIL-4:182
Pretreatment of Corn Stover with Solvent-Ionic Liquid Binary Mixtures
Eva K Brown (1) , ekbrown2@ncsu.edu, 911 Partners Way, Raleigh North Carolina
27695, United States ; Xinglian Geng (1) ; Jennifer Lewis (1) ; Wesley A Henderson (1) . (1)
Department of Chemical and Biomolecular Engineering, North Carolina State University,
Raleigh North Carolina 27695, United States
Ionic liquids (ILs) are effective solvents for various structural components of
lignocellulosic biomass, such as cellulose and lignin. While certain benefits not realized
with other methods are seen in IL pretreatment, including fractionation of components
and a reduction in cellulose crystallinity, ILs are prohibitively expensive, preventing
processing of cost competitive biofuels using this pretreatment method. Through the
addition of co-solvents to four ILs, [C2mim][Ac], [C2mim][Cl], [C4mim][Ac] and
[C4mim][Cl], it was found that dilute solutions of ILs dissolve substantial amounts of
cellulose (in some cases >15 wt%) (Fig. 1). This drastically reduces the amount of IL
needed and subsequently reduces the cost of the overall pretreatment method. Based
upon the ability of these dilute IL systems to dissolve cellulose, pretreatment of a
lignocellulosic substrate, corn stover, has been examined in IL co-solvent systems.

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Fig. 1 From left to right:
[C2mim][Ac] with 10 wt% cellulose, 80 mol% GBL-20 mol% [C2mim][Ac] with 10 wt%
cellulose and GBL with 1 wt% cellulose. After heating/stirring at 90ºC for 45 min., the
cellulose is completely dissolved in the first two vials, but none of the cellulose has
dissolved in the pure GBL.
COIL-4:183
Kinetic Investigations of Diels-Alder Reaction in Ionic Liquid-Molecular Solvent
Systems
Nageshwar Khupse (1) , nd.khupse@ncl.res.in, Dr. Homi Bhabha Road, Pashan, Pune
Maharashtra 411008, India . (1) Physical Chemistry Division, National Chemical
Laboratory, Pune maharashtra 411 008, India
For the past decade in finding suitable substitutes of volatile organic compounds
responsible for environmental pollution, room temperature ionic liquids are shown to be
such suitable candidates. 1 However, high viscosity of ionic liquids and the resulting low
conductivity render them unsuitable for numerous applications. 1 It is significant to
synthesize low viscous ionic liquids or to lower the viscosity of ionic liquids by the
addition of cosolvents. Recent studies from our group have shown that the effect of
viscosity of ionic liquids on organic reactions is complex. 2 We have carried out Diels-
Alder reaction of Anthracene-9-carbinol with N-ethyl maleimide (Scheme 1) in the binary
mixtures of pyridinium based ionic liquids [BP][BF4], [3-MBP][BF4], [4-MBP][BF4] with
molecular solvents, water, methanol and chloroform. These results are correlated with
viscosity and polarity of the medium. 3,4 The results give a clear evidence that the
bimolecular reaction influenced by a number of factors and not just viscosity alone and
the ionic liquids – cosolvent binary mixtures, which appeared promising due to low
diffusion barriers. Temperature dependence study of the kinetics of Diels-Alder reaction
in binary mixtures of [BP][BF4] in water. The entropy enthalpy compensation effect
demonstrates that process is entropy driven. References 1. Tiwari, S.; Kumar, A.

Angew. Chem. Int. Ed 2006, 45, 4824, 2. Tiwari, S.; Khupse, N.; Kumar, A. J. Org.
Chem. 2008, 73, 9075. 3. Khupse, N. D.; Kumar, A. J. Phys. Chem. B 2011, 115, 711.
4. Khupse, N. D.; Kumar, A. J. Sol. Chem. 2009, 38, 589
COIL-4:184
Investigation the Difference for SO2 And CO2 in THEAL Ionic Liquid
Suojiang Zhang (1) , sjzhang@home.ipe.ac.cn, P. O. Box. 353, Bei Er Tiao No. 1, Zhong
Guan Cun, Beijing, Beijing Beijing, China ; Hongyan He (1) ; Xiaoqian Yao (1) . (1) Institute
of Process Engineering, Beijing 100190, China
Ionic liquids (ILs) are receiving an upsurge of interest in multidisciplinary areas. Despite
design of various task-specific ILs successfully, the lack of knowledge on the connection
between microscopic structures and physiochemical properties of ILs is restricting the
exploitation and application of ILs. So, research on the microscopic structures and the
interaction between cations/anions of ILs with other molecules are of importance.
Recently, it was found that the solubility of SO2 in hydroxyl ammonium ionic liquids at
ambient pressure is high, while the solubility of CO2 in these ILs is relatively small. In
this study, the interaction between sulfur dioxide (SO2) or carbon dioxide (CO2) and
room temperature ionic liquid tri-(2-hydroxy ethyl)-ammonium (THEA) lactate (LAC)
(THEAL) have been investigated theoretically by using quantum chemical calculation
(QM). The relevant geometrical characteristics, energy properties as well as the
characters of the intermolecular hydrogen bonds (HB) have been systematically
discussed. The calculation results give us a deeper understanding of the factors which
determine the high solubility of SO2 and the difference of SO2 and CO2 in the solubility
in THEAL. The most stable geometries and binding energies indicate a strong
association of the SO2 and the THEAL molecule, especially the LAC anion; but also
imply a relatively weak association of CO2 and the THEAL molecule. The THEA cation
will interact with SO2 and CO2 molecules forming N-H…O hydrogen bond. The binding
energies indicate that the interaction with SO2 is stronger than that with CO2. The
results demonstrate that the LAC anion is the main factor for the absorption of SO2.
COIL-4:185
Thermodynamics and Aggregation Behaviour of Pyrrolidinium-Based Ionic
Liquids in Aqueous Solutions
Jose Nuno Canongia Lopes (1)(2) , jnlopes@ist.utl.pt, Av Rovisco Pais, Lisboa Portugal
1049 001, Portugal ; Mohammad Tariq (1)(2) ; Ajda Podgorsek (3) ; Jamie Ferguson (4) ;
Antonio Lopes (2) ; Margarida F. Costa Gomes (3) ; Agilio A. H. Padua (3) ; Luis Paulo N.
Rebelo (2) . (1) Centro de Quimica Estrutural, Instituto Superior Tecnico / UTL, Lisboa
1049 001, Portugal (2) Instituto de Tecnologia Quimica e Biológica / UNL, Lisboa 1049
001, Portugal (3) Laboratoire de Thermodinamique et Interactions Moleculaires,
Universite Blaise Pascal, Aubiere 63177, France (4) QUILL Centre, Queens University
Belfast, Belfast BT9 5AG, United Kingdom

Three pyrrolidinium-based ionic liquids — N-dodecyl-N-methylpyrrolidinium bromide, Nbutyl-N
octylpyrrolidinium bromide, and N-butyl-N-dodecylpyrrolodinium bromide —
were synthesized and characterized by their decomposition temperatures (Td)
measured by thermogravimetric analysis, and by their melting point (Tm), glass
transition (Tg) and crystallization temperatures (Tcryst) determined by differential
scanning calorimetry. Their self-aggregation properties in aqueous solution were
studied and their behavior is compared with that of analogous conventional cationic
surfactants, namely tetra-alkylammonium bromide salts. The critical micellar
concentration, CMCs, were obtained by isothermal titration calorimetry (ITC), which
were further validated by meaurements of interfacial tension, fluorescence and NMR
spectroscopy. Enthalpies of micellization were measured at three different temperatures
using ITC. The Taylor dispersion method and DOSY NMR were used to determine
diffusion coefficients of the ionic liquids surfactants in aqueous solution at 298.15 K.
Several correlations between structural features of the surfactant species, such as the
number and size of their alkyl chains, and the thermodynamic quantities of micellization
— expressed by experimental values of CMC, counter-ion binding fraction, ∆micG, ∆micH,
and ∆micS — are established. We interpret the different contributions of the two alkyl
side chains to the aggregation properties in terms of the balance of interactions in
dissolved and micellar phases, contributing to understanding the aggregation behaviour
of ionic liquids in water and the parallel between these systems and traditional ionic
surfactants.
COIL-4:186
Experimental and Computational Study on the Critical Solution Temperature of
BMIM + -Based Ils
Marta L. S. Batista (1) , batista.m@ua.pt, Campus Universitário de Santiago, Aveiro
3810-193, Portugal ; João A. P. Coutinho (1) ; José R. B. Gomes (1) . (1) Department of
Chemistry, University of Aveiro, CICECO, Aveiro 3810-193, Portugal
Ionic Liquids based on imidazolium cations have shown effective in the removal of
aromatic sulfur compounds from fuels, however, it has been observed that depending
on the anion a different phase behavior may occur with some systems showing upper
critical solution temperature (UCST) while others have a lower critical solution
temperature (LCST). Aiming at better understanding the interactions between ionic
liquids and thiophene, the various types of phase diagrams observed and their impact
upon the extraction processes the systems of thiophene with [BMIM][NTf2] and
[BMIM][SCN] were studied using 1 H, 13 C and 19 F NMR and FTIR spectroscopies,
thermophysical property measurements (density and viscosity) and further
complemented with computer simulations (density functional theory was used for the
study of small models and classical molecular dynamics for the largest ones). By
analyzing the chemical shift deviation (δ), the excess volumes (V E ) and the radial
distribution functions, it was possible to evaluate the interactions between the species
composing the mixtures. A full picture of the molecular interactions between the ionic

liquids and thiophene was drawn allowing understanding the formation of the two types
of phase diagrams (UCST and LCST) observed.
COIL-4:187
Influence of Prolonged Heating Time and Type of Mineralizers on Formation of
Aluminophosphates in Ionic Liquids
Xin Sun (1) , selma@ksu.edu, Room 1005, Durland Hall, Manhattan Kansas 66502,
United States ; Audrey Polifka (1) ; Jennifer L. Anthony (1) . (1) Department of Chemical
Engineering, Kansas State University, Manhattan Kansas 66502, United States
Ionic liquids are used as the solvent to synthesize porous aluminophosphates. Ionic
liquids used in this poster include the commonly used 1-ethyl-3-methylimidazolium
bromide and 1-butyl-3-methylimidazolium bromide. 1-butyl-3-methylimidazolium
hexafluorophosphate and 1-hexyl-3-methylimidazolium bromide which have never been
published in ionothermal synthesis of molecular sieves are also used to synthesize
aluminophosphates. However, 1-butyl-3-methylimidazolium hexafluorophosphate
proves not appropriate to be employed in ionothermal synthesis, since the excess
hydrofluoric acid generated could burn the products into black ashes. Hydrochloric acid
is used as the mineralizer for the first time and it yields the structure AEL which was
believed impossible to make without addition of hydrofluoric acid. No matter which
mineralizer is used in the synthesis, most of the structures formed after a few hours
(such as 2 hours and 4 hours) transform to dense phases after prolonged heating time
(such as 5 days or 10 days). In addition, materials synthesized with sublimated
aluminium isopropoxide are products with smaller size, which can not be separated by
the common filtration method.
COIL-4:188
Volumetric Properties and Enthalpies of Solution of Alcohols in 1-Methyl-3-
Alkylimidazolium Bis(Trifluoromethylsulfonyl)Imide Ionic Liquids
Margarida F. Costa Gomes (1) , margarida.c.gomes@univ-bpclermont.fr, BP 80026,
Aubière 63171, France ; Yun Deng (1) ; Pascale Husson (1) ; Johan Jacquemin (2) ; Tristan
Youngs (3) ; Vicky L Kett (4) ; Christopher Hardacre (3) . (1) Université Blaise Pascal
Clermont-Ferrand & CNRS, Laboratoire Thermodynamique et Interactions Moléculaires
(UMR 6272), Aubière 63171, France (2) Université François Rabelais, Laboratoire
PCMB (EA 4244), Tours 37200, France (3) The QUILL Research Centre, School of
Chemistry and Chemical Engineering, Queen’s University of Belfast, Belfast BT9 5AG,
United Kingdom (4) The School of Pharmacy, The Queen’s University of Belfast, Belfast
BT9 7BL, United Kingdom
The effect of the alkyl chain length in 1-alkyl-3-methylimidazolium
bis(trifluoromethylsulfonyl)imide ionic liquids, [C1CnIm][NTf2] (n = 2 to 10), on the mixing
properties (enthalpy and volume) of ionic liquid+methanol mixtures was investigated.

Small excess molar volumes with highly asymmetric curves as a function of mole
fraction composition, with more negative values in the alcohol-rich regions, were
observed. Furthermore, the excess molar volumes increase with the increase of the
alkyl-chain length of the imidazolium cation of the ionic liquid. The enthalpies of mixing
are positive, and do not vary monotonously with the length of the alkyl side-chain of the
cation on the ionic liquid – increasing from n = 2 to 6 and then decreasing from n = 8.
Molecular dynamics simulations showed more favorable interactions of methanol with
the cation head group of the ionic liquid for alkyl chains longer than 8 carbon atoms.
This implies that methanol preferentially interacts with the imidazolium head group in
[C1C8Im][NTf2] whilst anion interactions dominate in the ionic liquids [C1C2-6Im][NTf2].
Excess properties have been calculated for the mixture [C1C2Im][NTf2] + methanol at
298 K and it was observed that this mixture behaves like a binary mixture constituted by
a non-associating and a non-polar component, with its solution behavior being
determined by the enthalpy.
COIL-4:189
Dual Functional Ionic Liquids as Plasticisers and Antimicrobial Agents for
Medical Polymers
Héctor Rodríguez (1)(2) , hector.rodriguez@usc.es, School of Engineering, Rúa Lope
Gómez de Marzoa, s/n, Santiago de Compostela A Coruña E-15782, Spain ; Seong
Ying Choi (3) ; Arsalan Mirjafari (2) ; Deirdre F Gilpin (4) ; Stephanie McGrath (4) ; Karl R
Malcolm (5) ; Michael M Tunney (4) ; Robin D Rogers (2)(6) ; Tony McNally (3) . (1) Department
of Chemical Engineering, University of Santiago de Compostela, Santiago de
Compostela E-15782, Spain (2) QUILL, School of Chemistry and Chemical Engineering,
Queen[apos]s University Belfast, Santiago de Compostela E-15782, Spain (3) School of
Mechanical and Aerospace Engineering, Queen[apos]s University Belfast, Belfast BT9
5AH, United Kingdom (4) Clinical and Practice Research Group, School of Pharmacy,
Queen[apos]s University Belfast, Belfast BT9 7BL, United Kingdom (5) Drug Delivery
and Biomaterials Group, School of Pharmacy, Queen[apos]s University Belfast, Belfast
BT9 7BL, United Kingdom (6) Department of Chemistry and Center for Green
Manufacturing, The University of Alabama, Belfast BT9 5AG, United Kingdom
Infections arisen from antibiotic resistant pathogens, meticillin resistant Staphylococcus
aureus (MRSA), and coagulase-negative Staphylococci such as Staphylococcus
epidermidis that are able to colonise and form a biofilm on the surface of indwelling
medical devices, have been common problems in hospitals worldwide. An alternative
agent for the treatments is required as device-related infections are recalcitrant to
conventional antimicrobial therapy and host defenses. Poly(vinyl chloride) (PVC), a
polymer widely used in the manufacture of a range of medical devices, has a unique
flexibility derived from the addition of phthalate esters as plasticiser. However, the use
of phthalate esters in PVC has been prohibited in medical devices and toys due to the
potential reprotoxic effects. Ionic liquids, a group of molten salts with high versatility,
have shown in separate experiments to have a plasticizing effect in polymers and
antimicrobial activity. Hence, two dual functional ionic liquids, 1-ethylpyridinium

docusate and tributyl(2-hydroxyethyl)phosphonium docusate were designed and
specifically tailored to provide a plasticizing effect and exhibit antimicrobial and
antibiofilm forming activity to a range of antibiotic resistant bacteria. Based on
experiments carried out, a decrease of glass transition temperature of rigid PVC up to
45°C is achievable upon addition of 30 wt% of the ionic liquids, as well as inhibition on
MRSA and biofilm-forming Staphylococcus epidermidis up to 98%.
COIL-4:190
Application of Novel Copper-Based Supported Ionic Liquid Phase (SILP)
Catalysts in the Gas-Phase Synthesis of Dimethyl Carbonate
Martin J. Schneider (1) , martin.schneider@crt.cbi.uni-erlangen.de, Egerlandstraße 3,
Erlangen Bavaria 91058, Germany ; Marion Stricker (2) ; Jörg Sundermeyer (2) ; Haumann
Marco (1) ; Peter Wasserscheid (1) . (1) Department of Chemical and Bioengineering,
University Erlangen-Nuremberg, Erlangen Bavaria 91058, Germany (2) Philipps-
Universität Marburg, Marburg Hesse 35032, Germany
Dimethyl carbonate (DMC) is an important intermediate in the chemical industry and is
used as substitute for toxic phosgene or toxic dimethylsulfate in the production of
polycarbonates, isocyanates and urethanes. It is synthesised via oxidative carbonylation
of methanol by carbon monoxide and oxygen in the presence of copper(II) catalysts. [1]
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We have synthesized novel copper(I) containing ionic liquids of the type
[Cu(Im12)2][CuX2] (with X = Cl, Br, Im12 = 1-dodecylimidazole) that allow the DMC
synthesis under mild reaction conditions (120 °C, 4 h, 3 bar O2, 50 bar CO) in a batch
reactor. [2] Based on these promising results we have developed advanced Supported
Ionic Liquid Phase (SILP) materials for the gas-phase synthesis of DMC. SILP materials
are dry catalyst powders consisting of an ionic liquid, dispersed as a thin film on the
inner surface of a highly porous solid material. [3] The SILP approach allowed the
efficient immobilisation of the copper(I) containing ionic liquids as well as the synthesis
of DMC under mild conditions of 100 °C and 10 bar reaction pressure. [1] D.
Delledone, F. Rivetti, U. Romano, Appl. Catal. A: General, 2001, 221, 241. [2] M.
Stricker, T. Linder, B. Oelkers, J. Sundermeyer, Green Chem., 2010, 12, 1589–1598.
[3] a) A. Riisager, R. Fehrmann, S. Flicker, R. van Hal, M. Haumann, P. Wasserscheid,
Angew. Chem. Int. Ed. 2005, 44, 185; b) www.silp-technology.de
COIL-4:191
Thermophysical Properties and Solution Behavior of Structural Isomers of
Imidazolium- Bis(Trifluoromethylsulfonyl)Imide-Based Ionic Liquids
Catarina M. S. S. Neves (1) , catarinasn@ua.pt, Campus Universitário de Santiago,
Aveiro Aveiro 3810-193, Portugal ; Mara G. Freire (1) ; Luís M. N. B. F. Santos (2) ; João A.
P. Coutinho (1) . (1) Departamento de Química, CICECO, Universidade de Aveiro, Aveiro

Aveiro 3810-193, Portugal (2) CIQ, Departamento de Química e Bioquímica, Faculdade
de Ciências da Universidade do Porto, Porto 4169-007, Portugal
Low melting organic salts or ionic liquids (ILs) have been extensively investigated in the
last decade. Their intrinsic thermophysical properties, their highly solvating capacity and
their negligible vapor pressures make of them interesting as novel solvents in
separation processes. Therefore, a detailed picture of the ILs physicochemical
properties and solvent behavior will allow their tailoring aiming at defining specific tasks.
In this work, physical properties, such as densities and viscosities, as well as the mutual
solubilities between ILs and water, and their dependence with the temperature, were
determined for selected ILs comprising imidazolium-based cations combined with the
common anion bis(trifluoromethylsulfonyl)imide. The effect of the ILs structural features
in their physical properties and phase behavior - with particular emphasis in the cation
structural isomerism - is analyzed and discussed. The molar thermodynamic functions
such as Gibbs energy, enthalpy and entropy of solution of the ILs in water were derived
and rationalized. It is shown that despite the cation and anion nature contributions, the
effect of the structural isomerism in ILs is a crucial aspect that manages the ILs physical
properties and solution behavior.
COIL-4:192
Density and Mesoscale Structure of [C4mim][Ntf2]-CO2 System from 0.1 To 12 Mpa
Takeshi Morita (1) , moritat@faculty.chiba-u.jp, 1-33 Yayoi, Inage, Chiba Chiba 263-
8522, Japan ; Masayoshi Ushio (1) ; Keiko Nishikawa (1) . (1) Graduate School of Advanced
Integrated Sciences, Chiba University, 1-33 Yayoi, Inage, Chiba Chiba 263-8522, Japan
Structure change of ionic liquid in mesoscale size due to dissolution of CO2 was
investigated for system of imidazolium-based ionic liquids + CO2. Small-angle X-ray
scattering (SAXS) experiments were carried out for [C2mim]NTf2 and [C4mim]NTf2 using
the apparatus set at synchrotron facility along an isotherm under supercritical
conditions. Pressure dependence of the structural fluctuations of the mixtures is
discussed from viewpoint of difference of the alkyl-chain length. Time resolved
simultaneous measurement of density and concentrations of the mixtures was
performed using a new method, energy discriminated X-ray absorption measurements.
COIL-4:193
Structural Investigation of Dicationic 1,4-Diazoniabicyclo[2.2.2]Octane TFSI Salts
Anssi Peuronen (1) , anssi.peuronen@jyu.fi, P.O.Box 35, Jyväskylä FI-40014, Finland ;
Manu Lahtinen (1) ; Jussi Valkonen (1) . (1) Department of Chemistry, University of
Jyväskylä, Jyväskylä P.O.Box 35 FI-40014, Finland
The bis(trifluoromethanesulfonyl)imide (TFSI) anion has become one of the key
counter-ions in the synthesis of new cationic moieties in the ionic liquid research. It also

serves as a yardstick for new anions since it often yields ionic liquids with the broadest
liquid ranges with great thermal stability. In the last ten years numerous investigations
have been published concerning the electronic and structural properties of the TFSI
anion which focus on explaining the improved performance of TFSI in lowering the
melting points of salts. However, the solid state studies mostly focus on the
monocationic ammonium, pyridinium or imidazolium salts which often are the best ionic
liquid candidates. We have synthesized a group of dicationic 1,4-R2-1,4diazoniabicyclo[2.2.2]octane
(DABCO) TFSI salts in which 'R' groups vary from
common functional groups such as alcohols and ethers to long alkyl chains. The
characterization of these salts has been carried out by using X-ray diffraction as well as
thermoanalytical methods. The single crystal structures of the compounds are
presented and discussed in detail.
COIL-4:194
Polymeric Lithium Electrolytes Based on Polymerizable Ionic Liquids
Benedikt Huber (1) , huberb@staff.uni-marburg.de, Hans-Meerwein Strasse, Marburg
Hessen 35032, Germany ; Jörg Sundermeyer (1) ; Bernhard Roling (1) . (1) Department of
Chemistry, Philipps-University of Marburg, Marburg 35032, Germany
Lithium electrolytes, based on mixtures of alkyl carbonates or non conducting polymers
with lithium salts, have been studied for several years. They are widely used as liquid or
gel-like electrolytes in state-of-the-art lithium batteries. We report new polyelectrolytes
which overcome some of the drawbacks of the systems mentioned above, such as
leakage problems and physical instabilities of the gels. These imidazolium
bis(trifluoromethanesulfonyl)imide (TFSI) based electrolytes are polymerized ionic
liquids (ILs), showing most of the advantages of ILs, such as thermal and
electrochemical stability as well as high ionic conductivity. In addition to previous works
[1], our major attention is an enhancement of the lithium transference number.
Promising strategies are the immobilization of imidazolium cations in the polymer chain,
usage of new lithium salts with weakly coordinating anions [2] and addition of suitable
zwitterions [3]. The correlation between the microstructure of the polymers and their
conductivity properties is of special interest. In addition to structural polymer analysis,
we investigated the electrochemical and conducting properties by cyclic voltammetry,
electrochemical impedance spectroscopy and pulse field gradient NMR.
Schematic depiction of an imidazolium based polyelectrolyte and a potential landscape.
[1] R. Marcilla, F. Alcaide, H. Sardon, J. A. Pomposo, C. Gonzalo, D. Mecerreyes,
Electrochem. Commun., 8, 482 (2006). [2] T.Linder, J. Sundermeyer, Chem. Commun.,
2914-2916 (2009). [3] M. Yoshizawa, M. Hirao, K. Ito-Akita, H. Ohno, J. Mater. Chem.,
11, 1057 (2001).
COIL-4:195
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Influence of Bmimntf2 /Organic Solvent Mixtures on the Cerium Oxide Thin Layer
Electrodeposition
Cecile Rizzi (1) , cecile.rizzi@upmc.fr, bât F, porte 531, 4 pl Jussieu, case 51, Paris Paris
75252, cedex 05, France ; Virginie Lair (2) ; Juliette Sirieix-Plenet (1) ; Laurent Gaillon (1) ;
Armelle Ringuede (2) . (1) Department of chemistry, Laboratoire Physicochimie des
Electrolytes, Colloïdes et Sciences Analytiques, PECSA Université Pierre et Marie
Curie-Paris6 UMR 7195 CNRS - ESPCI-UPMC, Paris 75252, cedex 05, France (2)
Department of chemistry, Laboratoire d’Electrochimie, Chimie des Interfaces et
Modélisation pour l’Energie LECIME, UMR 7575 CNRS– ENSCP – Chimie-Paristech,
Paris 75005, France
Room temperature ionic liquids (RTILs) have attracted much attention in the last few
years due to their tunable chemical and physical properties. Indeed, they present high
chemical and thermal stability, negligible vapor pressure, high conductivity, the ability to
dissolve a large variety of organic and inorganic compounds, and a wide
electrochemical window. For this last reason, RTILs have found many applications in
electrochemistry and especially for electrodeposition of nanocrystalline metals and
semiconductors. But so far, very few works were devoted to the effect of addition of
RTILs for inorganic material synthesis, especially for electrodeposited metal oxide thin
films. Ceria is a promising metal oxide material for the surface treatment of different
metals and alloys, because of its corrosion resistance in aggressive media. Because
inorganic crystals chemical reactivity, electronic structure, bonding, and surface energy
are directly related to their surface morphology, the ability to tune their shape is a
challenging research. It is generally achieved by a precise control of the growth
conditions, for a given composition of the solutions or by using surfactants. This work
deals with the cathodic electrodeposition and characterisation of cerium oxide films by
molecular oxygen activation onto stainless steel substrates via Ce(III) nitrate in ionic
liquid (BMImNTf2) / organic solvent (Ethanol, DMSO or Acetonitrile) mixtures solutions.
These new electrolytic compositions, allow obtaining smooth and adherent cerium oxide
thin films. SEM and XRD characterizations enhanced the influence of the electrolyte
composition onto the morphology and the thickness of the obtained films. The deposited
oxide films are composed of small particles of cerium oxide lying on a dense and
compact amorphous phase.
COIL-4:196
Application of Alkoxysilyl-Functionalised Polymerisable Mesylate Ionic Liquids as
Electrolytes in Electrochromic Devices
Metka Hajzeri (1) , Metka.Hajzeri@ki.si, Hajdrihova 19, Ljubljana Slovenia SI-1000
Ljubljana, Slovenia ; Marija Čolović (1) ; Lidija Slemenik Perše (1) ; Matjaž Koželj (1) ; Uwe
Posset (2) ; Boris Orel (1) ; Angela Šurca Vuk (1) . (1) Department of spectroscopy of
materials, National Institute of Chemistry, Ljubljana SI-1000, Slovenia (2) Fraunhofer
Institut Silicatforschung (ISC), Würzburg D-97082, Germany

Functionalisation of imidazolium-based mesylate ionic liquids with sol-gel processable
alkoxysilyl groups yields materials that can be ranked as true organic-inorganic hybrids.
By low-temperature processing and chemical design, hybrids are accessible combining
the hardness of the inorganic domains with the flexibility of the organic part. Both
properties are important when alkoxysilylated ionic liquid precursors transform through
the reactions of solvolysis and condensation into threedimensional silsesquioxane
network 1 . Such gel networks are capable of hosting non-reactive alkyl-functionalised
ionic liquids, as well as of dissolving considerable amounts of lithium salts 2 . The
solubility of the latter can be controlled by the introduction of longer ethyleneoxide
chains. Free alkoxy or silanol groups may generate strong bonds to the electrochromic
WO3 films and various counter electrodes (NiOx, V2O5,...), thus resulting in good
interfacial adhesion. Due to their chemical properties and mechanical flexibility, the
materials can also be applied in devices containing electrochromic conductive polymers
such as poly(3,4-ethylene dioxythiophene) (PEDOT) and even when flexible ITO/PET
film is used as substrate. [1] B. Orel, A. Šurca Vuk, V. Jovanovski, R. Ješe, L. Slemenik
Perše, S.B. Hočevar, E.A. Hutton, B. Ogorevc, A. Jesih, Electrochem. Comm. 7 (2005)
692-696. [2] A. Šurca Vuk, V. Jovanovski, A. Pollet-Villard, I. Jerman, B. Orel, Sol.
Energy Mater. Sol. Cells 92 (2008) 126-135. The research leading to these results has
received funding from the European Community's Seventh Framework Programme
under grant agreement n o 200431 (INNOSHADE).
COIL-4:197
Readily Available and Recoverable Chiral Ionic-Tagged Ligands for Asymmetric
Hydrogenation
Zhen Li (1) , cgxia@licp.cas.cn, Tianshui Middle Rod, Lanzhou Gansu, China ; Yingwei
Zhao (1) ; Hanmin Huang (1)(2) ; Jianping Shao (1) ; Chungu Xia (1) . (1) State Key Laboratory
for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics,
Chinese Academy of Sciences, Lanzhou Gansu 730000, China (2) State Key
Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou Gansu 730000,
China
The application of ionic liquids in catalytic reactions provides the advantage of
reusability for expensive catalysts. Use of ionic-tagged catalysts is a promising
improvement for this strategy. We synthesized novel ionic phosphite ligands (1a-1f)
based on carbohydrate backbone and applied them in asymmetric hydrogenations.
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The reactions were carried out in CH2Cl2 firstly and the results showed that they
exhibited high activities and enantioselectivities. This indicated that the ionic tag has no
significant effect on the conformations of native ligands in Rh-catalyzed reactions.
Entry Substrate Ligand ee (%)
1 2a 1a >99
2 2a 1b >99
3 2a 1c >99

4 2a 1d >99
5 2a 1e >99
6 2a 1f 99
7 2b 1d >99
8 3a 1d 98
9 3b 1d 96
10 4 1d 98
Substrate 0.25 mmol; [Rh(COD)L2]BF4 0.0025 mmol; H2 10 atm; rt; 1 h. All 100%
conversions.
The hydrogenation of 2a was also performed in ionic liquid/toluene system for
examining the reusability of the Rh-catalysts. The results indicated that it depends
strongly on the structure of the ligands. In general, the ionic ligands containing Nmethylimidazolium
cations showed better reusability probably because the structures of
their ionic tags are more similar to that of ionic liquid [bmim][BF4]. In the hydrogenation
of 2a, when the best ligand 1d was used, 95% conversion and 97% ee were still
obtained in the tenth run.
COIL-4:198
Phase Behaviors and Accompanying Structural Changes of 1-Alkyl-3-
Methylimidazolium Hexafluorophosphate
Takatsugu Endo (1) , endo@restaff.chiba-u.jp, 1-33 Yayoi, Inage-ku, Chiba Chiba 263-
8522, Japan ; Keiko Nishikawa (1) . (1) Department of Nanomaterial Science, Chiba
University, Chiba Chiba 263-8522, Japan
It is important to reveal phase behaviors of ionic liquids (ILs) for understanding their
basic physical properties and also the unique thermal properties, e.g., low melting point,
premelting phenomenon, a wide supercooled liquid region, glass formation tendency
and thermal history. Note that the understanding is necessary for applications of ILs in
the solid state such as ion conducting materials. In this study, we report the phase
behaviors and accompanying structural changes of 1-alkyl-3-methylimidazolium
hexafluorophosphate ([Cnmim]PF6, n=1-4) by calorimetry and Raman spectroscopy.
The melting points of [Cnmim]PF6 exhibited the dependence of the alkyl chain length as
found in other imidazolium-based ILs, namely, the melting point decreased with
increasing alkyl chain length. [C2mim]PF6 and [C3mim]PF6 showed typical phase
behaviors and structural changes as imidazolium-based ILs, that is, a wide supercooled
liquid region and the existence of rotational isomers in the liquid state. On the other
hands, the complex phase behaviors were observed in [C1mim]PF6 and [C4mim]PF6.
[C4mim]PF6 shows cold crystallization, and has three crystalline phases with different
cation conformations as previously reported (J. Phys. Chem. B, 2010, 114, 407-411). In
[C1mim]PF6, two crystalline phases with different Raman spectra were obtained even
though there were no conformers in both a cation and an anion. In addition, there is the
difference of 50 K in melting points between them. To the best of our knowledge, this is

the largest difference in melting point reported in ILs which exhibits crystal
polymorphism.
COIL-4:199
Ecotoxicity and Biodegradability of Technological Relevant Ionic Liquid Anions
Stephanie Steudte (1)(2) , steudte@chem.univ.gda.pl, ul. Sobieskiego 18, Gdańsk 80-
952, Poland ; Piotr Stepnowski (1) ; Stefan Stolte (2) . (1) Department of Enviromental
Analytics, University of Gdańsk, Gdańsk 80-952, Poland (2) Department for sustainable
chemistry, University of Bremen, Center for Environmental Research and Sustainable
Technology (UFT), Gdańsk 80-952, Poland
The increasing utilization of ionic liquids (ILs) in technical applications requires
(eco)toxicological hazard and risk assessment. Many results focusing on the cation
moiety and the influence of its side chain or head group are already published.
However, for the impact of the ionic liquid anions only a few data are available. In this
study we investigated the aquatic toxicity of a set of 5 mainly hydrophobic IL anions
combined with 1-alkyl-3-methyl-imidazolium and inorganic cation, respectively (Figure
1). The draining of contaminated process water represents the most likely release of ILs
into the environment. Thus, the aquatic compartment is of particular importance
regarding the hazard assessment and model organisms at different trophic levels such
as luminescent marine bacteria (Vibrio fischeri), green algae (Scenedesmus
vacuolatus), duckweed (Lemna minor) or crustacean (Daphnia magna) were chosen for
ecotoxicity tests. Moreover, the biodegradability according to primary biodegradation
test procedures of these IL anions has been investigated for the first time. The present
study should help to improve the knowledge in the prospective design of inherently
safer ionic liquids by reducing their risk for man and the environment. Figure 1:
Structure of investigated anions (trifluoridotris(pentafluoroethyl)phosphate,
bis(trifluoromethylsulfonyl)amide, dicyanidoamide, tricyanomethide, and
tetracyanoborate anion, all with inorganic and 1-alkyl-3-methyl-imidazolium cation)
COIL-4:200
Eutectic Ionic Liquid Mixtures
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Shohei Saita (1) , 50010641207@st.tuat.ac.jp, 2-24-16 Nakacho, Koganei Tokyo 184-
8588, Japan ; Yuki Kohno (1) ; Hiroyuki Ohno (1) . (1) Tokyo University of Agriculture and
Technology, Japan
One of the next tasks for ionic liquids (ILs) should be the design and control of IL
properties. It is easy to control the properties by mixing some ILs. However, there are
only a few reports on the detailed discussion of phase behavior of the mixed ILs. ILs
have been prepared by coupling tetrabutylphosphonium cation ([P4444]) with various
anions such as bis(trifluoromethanesulfonyl)imide ([Tf2N]), trifluoroacetate ([CF3COO]),

and p-toluenesulfonate ([TsO]). [P4444][Tf2N], [P4444][CF3COO], and [P4444][TsO] were
solid at room temperature. However, when [P4444][CF3COO] or [P4444][TsO] was mixed
with equimolar [P4444][Tf2N], these mixtures turned liquid at room temperature. To
analyze this phase change, melting temperature (Tm) and glass transition temperature
(Tg) of these mixtures were determined with DSC measurements. Fig.1 shows the
phase diagram of the mixed ILs at different mixing ratio. An fTf2N means the mole
fraction of [P4444][Tf2N] in the mixtures. The mixtures of [P4444][CF3COO]/[P4444][Tf2N]
had lower Tm than that of individual IL. In the case of [P4444][TsO]/[P4444][Tf2N] mixture,
Tm decreased in the certain molar ratio (1.0 > fTf2N > 0.67). On the other hand, the
mixture containing equal or excess molar [P4444][TsO] (0.5 ≥ fTf2N > 0.14) had no Tm,
and showed two distinct Tgs on heating. These results indicated that there should be a
micro phase separation (or clusters) in the mixture of [P4444][TsO]/[P4444][Tf2N].
COIL-4:201
Loading Metal Nanoparticles in Energetic Ionic Liquids
Parker D McCrary (1) , pmccrary1@crimson.ua.edu, 250 Hackberry Lane, Tuscaloosa
AL 35487, United States ; Preston A Beasley (1) ; Tommy W Hawkins (2) ; Stefan
Schneider (2) ; Jesus Paulo Perez (3) ; Brandon W McMahon (3) ; Scott L Anderson (3) ; Steven
Son (4) ; Robin D Rogers (1) . (1) Department of Chemistry and Center for Green
Manufacturing, The University of Alabama, Tuscaloosa AL 35487, United States (2)
Space and Missile Propulsion Division, Propulsion Directorate, AFRL/RZSP, Air Force
Research Laboratory, Edwards AFB CA 93524, United States (3) Department of
Chemistry, The University of Utah, Salt Lake City UT 84112, United States (4) School of
Mechanical Engineering, Purdue University, West Lafayette IN 47907, United States
Energetic Ionic Liquids (EILs) are being studied as possible replacements for currently
used energetic materials such as propellants and fuels. Some potential EILs provide an
interesting set of properties, but may lack key features such as high energy density,
oxygen balance, impact resistance, etc. Reactive metal nanoparticles are also being
studied for applications in energetic materials and power generation, but may be
considered to be unsafe due to the same high surface areas that make them interesting
in these fields. We are combining the known property sets of ILs, including the ability of
some ILs to readily suspend nanoparticles, with reactive metal nanoparticles to increase
the overall energy density of the mixture while still providing the benefits of using ionic
liquids. This presentation will detail our progress to date in this area. This research
was supported by the Air Force Office of Scientific Research (Grant F49550-10-1-0521).
COIL-4:202
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Synthesis and Properties of Gemini Imidazolium Ionic Liquids, α,ωdi(chloromethoxy)Alkanes
Derivatives.

Andrzej Skrzypczak (1) , andrzej.skrzypczak@put.poznan.pl, pl.M.Sklodowskiej-Curie 2,
Poznan Wielkopolskie 60-965, Poland . (1) Department of Chemical Technology,
Poznan University of Technology,, Poznan 60-965, Poland
Among the many unique properties of ILs is an extraordinary degree of tunability, with
relatively minor changes in the structure of the constituent cation or anion, frequently
leading to major changes in physicochemical properties. Such tunability is of potential
utility in the aplication of ionic liquids in various separations processes. A new class of
ILs, the so cold gemini has recently attracted considerable interest. In gemini ILs two
conventional or monomeric moieties are connected together close to, or at the level of,
the head groups by a spacer group. These compounds possess a unique structure, a
greater surface activity and even more excellent antimicrobal activity. In that study the
various geminal imidazolium dications were paired with up to several different anions.
Experimental: α,ω-di(chloromethoxy)alkanes were obtained by chloromethylation
reaction. Gaseous hydrogen chloride was passed through mixture of appriopriate α,ωdiol
and paraformaldehyde. Obtained α,ω-di(chloromethoxy)alkanes were used as
quaternization agent for Menschutkin reaction of 1-alkylimidazoles. Next step of
synthesis of geminal ILs was anion exchange reaction: replacement of chloride anion by
tetrafluoroborate, nitrates, formate, acetate, chloroacetates, trifluoroacetate, propionate
and others. The effect of the dication type ILs, the effect of linkage chain, alkyl
substituents and anion type on the surface and biological activity, thermal stability,
refractive index and conductivity of these compounds was examined.
Acknowledgement: This investigation received financial support from the Polish Ministry
of Science and Higher Education NN 209437639.
COIL-4:203
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Optimization of Caffeine Extraction from Guarana Seeds Using Aqueous Ionic
Liquid Solutions
Joao A.P. Coutinho (1) , jcoutinho@ua.pt, University of Aveiro, Aveiro Aveiro, Portugal ;
Ana F.M. Cláudio (1) ; Ana M Ferreira (1) ; Mara G Freire (1) . (1) CICECO, Department of
Chemistry, University of Aveiro, Aveiro Aveiro 3810-193, Portugal
Guarana is a climbing plant especially common in Brazil and its seeds contain about
twice the caffeine found in coffee beans. Caffeine is an alkaloid found in diverse natural
products, namely, beans, leaves, and fruits that due to its antibacterial and antifungal
properties is a natural repellent protecting the plants. In agriculture, products used in
pest control reveal disadvantages to human health, such as high toxicity, high volatility
and related environmental hazards. Caffeine could be used as an alternative and
environmentally safe toxicant for the control of pest on food crops. The utilization of
caffeine for these applications is advantageous compared to synthetic substitutes that
possess adverse effects. Therefore, the caffeine extraction and purification from natural
sources, by cost-effective and environmentally-safe processes, is of considerable
interest. In this work, aqueous solutions of ionic liquids (ILs) were investigated for the

extraction of caffeine from guarana seeds. ILs were selected as co-solvents due to their
unique properties, such as their negligible vapor pressures, high chemical and thermal
stability, and large solvating capacity for the most diverse compounds. Since the
properties of ILs can be tuned by the proper combination of the cation and/or anion, ILs
can be tailored to meet the needs of a particular process, in this work the extraction of
caffeine. Several operational parameters were optimized using a central composite
design: IL concentration, extraction contact time, solid–liquid ratio and temperature of
extraction. Moreover, the effect of the IL cation and anion nature in the yield of caffeine
extraction was evaluated. The data obtained show the high potential of IL-based
systems for the extraction of caffeine from natural matrices.
COIL-4:204
Biodegradable and Nanosized Cellulose Fibers Obtained by Electrospinning
Using Ionic Liquids
Mara G. Freire (1) , maragfreire@ua.pt, Campus Universitário de Santiago, Aveiro Aveiro
3810-193, Portugal ; Ana Rita R. Teles (1) ; José A. Lopes-da-Silva (2) ; João A. P.
Coutinho (1) . (1) Department of Chemistry, CICECO, University of Aveiro, Aveiro 3810-
193, Portugal (2) QOPNA, Chemistry Department, University of Aveiro, Aveiro 3810-
193, Portugal
Electrospinning is an expedite method used to prepare nanosized fibers driven by an
external electric force applied on the surface of polymer solutions (or melts). Cellulose
electrospun fibers have great potential in distinct applications, such as membranes,
biosensors, electronic and optical devices, as well as in enzyme and catalytic supports.
Nevertheless, the intrinsic lack of solubility of native cellulose in water, and most organic
solvents, constitutes a major obstacle for its proficient utilization and electrospinning.
Among new potential solvents for cellulosic biomaterials, ionic liquids (ILs) have been
attracting considerable attention. The aim of this work is the production of nanosized
cellulose fibers from electrospinning using non-volatile ILs as pure solvents, and at
room temperature. From the large array of possible ILs, 1-ethyl-3-methylimidazolium
acetate was selected as the main solvent, as a result of its low viscosity, low melting
temperature, and high cellulose dissolution capacity. Electrospun cellulose fibers with
an average diameter within (470 ± 110) nm were obtained. To further enhance the
solvent thermophysical properties, aiming at reducing the surface tension, a second and
surface active ionic liquid (1-decyl-3-methylimidazolium chloride) was used as an
additive. From the binary mixture of ILs, improved electrospun cellulose fibers with an
average diameter of (120 ± 55) nm were attained. Electrospun cellulose fibers were
analyzed by SEM (scan electron microscopy), X-ray Diffraction Spectroscopy, FTIR
(Fourier Transform Infra-Red Spectroscopy) and TGA (Thermogravimetric analysis) to
evaluate their structural integrity, morphology and crystallinity. Raw cellulose used for
electrospinning was found to be of Type-I polymorph. After the cellulose dissolution in
the ILs, and subsequent regeneration, cellulose fibers are highly amorphous with the
remaining crystalline parts being polymorphs of Type-II. The thermal stabilities of
electrospun fibers are only slightly lower than that of raw cellulose.

COIL-4:205
Ionic Liquids in Syntheses of 1,4-Dihydropyridine Derivatives
Andris Zicmanis (1) , zicmanis@latnet.lv, 19 Rainis Boulevard, Riga Riga LV 1586,
Latvia ; Sanita Pavlovica (1) ; Elina Gzibovska (1) ; Peteris Mekss (1) . (1) Department of
Chemistry, University of Latvia, Riga Riga LV 1586, Latvia
Ionic liquids (ILs) successfully replace organic solvents in the syntheses of different
organic compounds. Their utilization provides plenty of advantages by comparison with
conventional solvents [1]. The possibility to design their optimal structures for the
chosen application, the protection of environment, higher reaction yields are most
frequently referred benefits of the exploitation of ILs. Acetoacetic ester and
hexamethylenetetramine transform into the Hantzsch ester (HE) when stirred at
elevated temperature in different ILs. The mentioned transformations proceed according
to the following equation. The structure of ILs has essential impact on yields and rates
of the cyclization reaction. 1-Alkyl pyridinium, 1,3-dialkyl imidazolium, tetraalkyl
ammonium and 2-hydroxyethyl ammonium salts are examined for ILs in our
experiments. 2-Hydroxyethyl ammonium carboxylates are not only the cheapest ILs
between investigated materials but also have comparatively high biodegradability (up to
90%) and low toxicity (LC50 = 6 – 8.5 g/L). The rates of reactions and yields of HE are
increased in more polar ILs, decreased polarity demonstrating opposite impact. The
cation of IL has serious influence on the result of reaction, the aromatic cations being
more helpful. The type of anion has no significant impact. ILs serve both as reaction
media and catalysts in the investigated reactions. The HE formation takes place in the
absence of any other catalyst. A purposeful addition of traditional catalysts of this
reaction is beneficial, the best extra catalyst being found sodium dihydrogen phosphate.
Accordingly, the application of ILs in the preparation of 1,4-dihydropyridines allows
avoiding exploitation of harmful and dangerous organic solvents. References 1. P.
Wasserscheid and T. Welton, “Ionic Liquids in Synthesis, vol. 1, vol. 2”, Wiley-VCH,
Weinheim, 2008.
COIL-4:206
Compatibility of Ionic Liquids and Polyethers for The Design of Ion Conductive
Polymers
Akiko Tsurumaki (1) , 50010641216@st.tuat.ac.jp, 2-24-16, Nakacho, Koganei Tokyo,
Japan ; Hiroyuki Ohno (1) . (1) Department of Biotechnology, Tokyo University of
Agriculture and Technology, Nakacho, Koganei Tokyo 184-8588, Japan
Polymer electrolytes are smart materials to make electrochemical devices safe and thin.
Ionic liquids (ILs) are potential candidates as additive salts, because they have essential
requirements as additives. However, there is little systematic study on ILs/polymer
composites. In the present study, we analyzed the compatibility between ILs and
poly(ethylene oxide) (PEO) under IL excess condition, and extended the compatibility

study to design IL/PEO composite as ion conductive polymers. The compatibility of
PEO and ILs under salt rich condition has been discussed with Hard and Soft, Acids
and Bases (HSAB) theory under salt rich condition. IL composed of relatively hard acids
such as imidazolium cations, and soft bases such as bis(trifluoromethanesulfonyl)imide,
showed good miscibility with PEO regardless of mixing ratio. Hardness of component
ions was revealed to be effective in controlling the solubility of PEO in the ILs. We
successfully applied HSAB theory to discuss the solubility of PEO in ILs under salt rich
condition. High ionic conductivity was found when PEO was mixed with ILs which have
moderate affinity with PEO probably due to the formation of successive phaseseparated
IL domain. We conclude here that many polymers have chance to act as
potential matrices for ILs when they keep moderate compatibility with ILs.
COIL-4:207
Stimuli-Responsive Polymers in Ionic Liquids
Takeshi Ueki (1) , t-ueki@ynu.ac.jp, 79-5 Tokiwadai Hodogaya-ku, Yokohama Kanagawa
240-8501, Japan ; Masayoshi Watanabe (1) ; Timothy P. Lodge (2) . (1) Department of
chemistry, Yokohama National University, Yokohama Kanagawa 240-8501, Japan (2)
Department of Chemistry and Department of Chemical Engineering and Materials
Science, University of Minnesota, Minneapolis Minnesota 55455, United States
We previously reported that poly(N-isopropylacrylamide) (PNIPAm)—the most wellknown
and widely studied synthetic polymer that exhibits a lower critical solution
temperature (LCST) behavior in an aqueous solution—exhibits upper critical solution
temperature (UCST) behavior in an IL. Intrestingly, poly(benzyl methacrylate) (PBnMA)
was found to exhibit LCST phase separation, i.e., its solubility decreases with an
increase in temperature for a typical hydrophobic IL such as 1-ethyl-3methylimidazolium
bis(trifluoromethane sulfone)imide ([C2mim][NTf2]). Most recently, it
was found for the first time that certain polymer including azobenzene side chain could
change their solubility in ionic liquids induced by light illumination. Here we report
unique block copolymer self-assembly, based on multi stimuli sensitivity of polymer in
ionic liquids as solvent.
COIL-4:208
Seebeck Coefficients in Ionic Liquids - Prospects for Thermo-Electrochemical
Cells
Theodore J. Abraham (1)(2) , theodore.abraham@monash.edu, Clayton Campus,
Wellington Road, Clayton Victoria 3800, Australia ; Douglas R. MacFarlane (1)(2) ; Jennifer
M. Pringle (1)(2) . (1) Chemistry, Monash University, Clayton Victoria 3800, Australia (2)
Monash University, Australian Centre for Electromaterials Science, Clayton Victoria
3800, Australia

Thermo-electrochemical cells are used to directly convert thermal energy into electrical
energy and are therefore of interest currently as a means to convert low grade heat (eg
from geothermal sources) into electricity. Thermo-electrochemical devices are based on
the Seebeck effect, where an electric voltage is induced in response to a temperature
difference between the redox couple in the two halves of the cell. Ionic liquid
electrolytes would be beneficial as electrolytes in thermo-electrochemical cells due to
their broad liquid range, high ionic conductivity and thermal stability. Ionic liquids with
dissolved triiodide/iodide redox couple were examined in this study. The Seebeck
coefficient was found to vary substantially as a function of the ionic liquid, probably as a
result of the solvation environment that the ionic liquid represents for the triiodide/iodide
redox couple species. Figure 1. Schematic of a thermo-electrochemical device.
COIL-4:209
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Hydroxylammonium Azide, a New Fuel with High Performance for Energetic Ionic
Liquids
Charles J. KAPPENSTEIN (1) , Charles.Kappenstein@univ-poitiers.fr, Chemistry building
B27, Faculty of Sciences, 40 Avenue du Recteur Pineau, POITIERS 86022, France ;
Kamal FARHAT (1) ; Yann BATONNEAU (1) . (1) Department of Chemistry, LACCO UMR
CNRS 6503, University of Poitiers, POITIERS 86022, France
Ionic energetic liquids contain ionic oxidizers, ionic fuels and water. 1 The most common
oxidizers are hydroxylammonium nitrate (HAN, [NH3OH] + [NO3] - ); ammonium dinitramide
(ADN, [NH4] + [N(NO2)2] - ); ammonium nitrate (AN, [NH4] + [NO3] - ); hydrazinium nitrate (HN,
[N2H5] + [NO3] - ); and hydrazinium nitroformate (HNF, [N2H5] + [C(NO2)3] - ). Molecular fuels
have been extensively studied, but ionic fuels were limited to the preparation of LGP
(liquid gun propellants), and TEAN (trisethanolammonium nitrate,
[N(C2H4OH)3OH] + [NO3] - ) is a typical example. 2 Beside well known ionic azides as
ammonium azide (AN, [NH4] + [N3] - ) and hydrazinium azide (HA, [N2H5] + [N3] - ), we
propose to use hydroxylammonium azide (HAA, [NH3OH] + [N3] - ) as a new fuel additive.
The calculated performances in term of specific impulse are presented in Table 1 and
display much higher values than hydrazine (230 s) even diluted with 60 wt.-% water.
Table 1: specific impulse (in s) versus water content for HAA associated to different
oxidizers
Composition Water content wt.-%
20 % 40 % 60 %
HAA + HAN 356 319 239
HAA + AND 352 317 246
HAA + HN 354 316 232
We will present the complete performance data, the synthesis of hydroxylammonium
azide, the preparation of different HAA-based monopropellants as well as the first
results concerning the thermal and catalytic decomposition of the prepared propellants

on supported platinum catalysts. 1) Y. Batonneau, C. Kappenstein and W. Keim,
“Catalytic decomposition of energetic compounds: gas generator, propulsion”,
Handbook of Heterogeneous Catalysis, 2nd edition, Eds. G. Ertl, H. Knözinger, F.
Schüth, and J. Weitkamp, Vol. 5, Chapter 12.7, VCh-Wiley, Weinheim, April 2008. 2) G.
Klingenberg, J.D. Knapton, W.F. Morrison, G.P. Wren, “Liquid propellant gun
technology”, Progress in Astronautics and Aeronautics, Vol. 175, AIAA ed., 1997.
COIL-4:210
Hydration State of Choline Dihydrogen Phosphate and its Analogous Ionic
Liquids
Yosuke Nikawa (1) , 50011641219@st.tuat.ac.jp, Tokyo Koganei, Japan ; Kyoko Fujita (1) ;
Hiroyuki Ohno (1) . (1) Department of Biotechnology, Tokyo University of Agriculture and
Technology, Tokyo Koganei 184-8588, Japan
Ionic liquids (ILs) have been expected as novel solvents for proteins. However, proteins
have low solubility in ILs. The hydrated ILs, prepared by adding appropriate amounts of
water to ILs, have been recognized to solubilize proteins. In particular, hydrated choline
dihydrogen phosphate (Hy[ch][dhp]) has been realized to solubilize several proteins. In
addition, these proteins showed thermostability and activity for a long time. The protein
stability in Hy[ch][dhp] was considered to be due to the hydrated state of the IL. In this
study, we synthesized [ch][dhp] and its analogue to analyze their hydration state.
[ch][dhp], 1-butyl-3-methylimidazorium dihydrogen phosphate ([bmim][dhp]) and choline
dibutyl phosphate ([ch][dbp]) were synthesized (Fig1). These ILs were mixed with water
and were characterized with both differential scanning calorimetry (DSC) and water
activity measurement. Hy[ch][dhp] and Hy[bmim][dhp] gave sigmoidal curves in the
relation between water content and the water activity (Fig2●) suggesting the change of
water state. On the other hand, simple saturation curve was observed for Hy[ch][dbp]
(Fig2○). In DSC analysis, in the case of Hy[ch][dhp], a peak for cold crystallization was
seen when molar ratio of IL:water was 1:6 and 1:7. Hy[bmim][dhp] also showed cold
crystallization at IL:water molar ratio of 1:12 and 1:15. No peak for cold crystallization
was found in Hy[ch][dbp] regardless of water content. From these results, the IL
consisted of [dhp] anion is considered to show dramatic changes of hydration state with
water content.
COIL-4:211
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New Class of Bis(Fluorosulfonyl)Amide Ionic Liquids Based on Quaternary
Phosphonium Cations
Katsuhiko Tsunashima (1) , tsunashima@wakayama-nct.ac.jp, 77 Noshima, Nada-cho,
Gobo, Wakayama 644-0023, Japan ; Atsuko Kawabata (1) ; Masahiko Matsumiya (2) ; Shun
Kodama (3) ; Yoshihito Kunugi (4) . (1) Department of Materials Science, Wakayama
National College of Technology, Wakayama 644-0023, Japan (2) Faculty of Education

and Human Sciences, Yokohama National University, Yokohama 240-8501, Japan (3)
Organic Chemicals R&D Department, Nippon Chemical Industrial Co., Ltd., Tokyo 136-
8515, Japan (4) Department of Applied Chemistry, Faculty of Engineering, Tokai
University, Hiratsuka 259-1292, Japan
Recently, interests in room-temperature ionic liquids based on a
bis(fluorosulfonyl)amide anion (N(SO2F)2 - , FSA) have been increasing for their favorable
transport property as lithium battery electrolytes. However, many studies on the FSAbased
ionic liquids have been associated with nitrogen-based ionic liquids such as
imidazolium, quaternary ammonium, pyridinium, pyrrolidinium salts. In this work, the
physical and electrochemical properties of FSA-based ionic liquids based on quaternary
phosphonium cations are presented. The FSA-based phosphonium ionic liquids were
relatively low-melting, low viscous and highly conductive when compared to not only
those of the corresponding bis(trifluoromethylsulfonyl)amide-based ionic liquids but also
those of the corresponding FSA-based ammonium ionic liquids. Particularly, the ionic
liquids containing a methoxy group in the phosphonium cations indicated very low
viscosities and high conductivities. The FSA-based phosphonium RTILs were thermally
stable up to nearly 300 °C. The voltammetric analysis suggested that the FSA-based
phosphonium ionic liquids showed high electrochemical stability similar to the
corresponding bis(trifluoromethylsulfonyl)amide-based ionic liquids.
COIL-4:212
Measurement of Excess Enthalpies of Ionic Liquid/Alcohol and Ionic Liquid/Water
Mixtures by Calorimetry
Marjorie Massel (1) , massel.2@nd.edu, 310 Stinson Remick Hall, Notre Dame Indiana,
United States ; Lindsay E Ficke (1) ; Joan F Brennecke (1) . (1) Department of Chemical and
Biomolecular Engineering, University of Notre Dame, Notre Dame Indiana 46556,
United States
The thermodynamics of mixtures of ionic liquids (ILs) and water or various organic
compounds is important for a wide variety of potential applications. These include
absorption refrigeration systems and liquid-liquid extraction systems. Current
absorption/refrigeration systems rely on water and lithium bromide but this has many
disadvantages such as corrosion and toxicity. Alcohols are currently purified from
fermentation broths by distillation but this requires significant amounts of energy. The
emergence of ionic liquids as replacement refrigerants and extractants are important
new applications of this versatile class of compounds. The enthalpy of mixing (or
excess enthalpy) is an excellent measure of the fundamental thermodynamics and
intermolecular interactions in IL/water and IL/organic systems. This is because it is a
measure of the temperature dependence of the solution nonideality and the
measurements are not dominated by the pure component properties (such as the pure
component vapor pressure when measuring vapor-liquid equilibrium). Calorimetry is a
direct and accurate technique to determine this thermodynamic property. The work in
this study was done using a Setaram C80 calorimeter with mixing cells. Excess

enthalpies have been measured for a series of imidazolium and ammonium-based
IL/water systems. In order to study the effect of alkyl chain length, we have also
investigated a series of IL/alcohol systems. Using this data we can predict the vapor
liquid equilibrium diagram and the activity coefficient at infinite dilution via the Non-
Random Two Liquid (NRTL) model.
COIL-4:213
Thermal Stability of Ionic Liquids in an Inert Environment
Yong Huang (1) , yhuang7@nd.edu, 182 Fitzpatrick Hall, Notre Dame IN 46556, United
States ; Jacob M Crosthwaite (1) ; Joan F Brennecke (1) . (1) Department of Chemical and
Biomolecular Engineering, University of Notre Dame, Notre Dame IN 46556, United
States
Thermal stability is an important property of ILs, especially if they are used for high
temperature applications. Some of these applications include use of ILs as solvents for
separations, as high temperature heat transfer fluids, and in geothermally driven
absorption refrigeration systems. This work focuses on thermal decomposition of
imidazolium, pyridinium and phosphonium ILs by temperature ramped and isothermal
thermogravimetric analysis (TGA) under N2 environment. The decomposition
mechanisms for these ILs were investigated by using chromatoprobe gas
chromatography/mass spectrometry (GC/MS) under helium environment. Dynamic and
isothermal decomposition or evaporation experiments of ILs were performed with a
Mettler Toledo TGA under N2 (inert environment). For dynamic experiments at a specific
ramp rate, one important descriptor of thermal stability is the onset temperature (Tonset).
Kinetic parameters were studied by using the Coats-Redfern integral method (Nature,
vol 201, iss 491 pg 68, 1964) or pseudo zero-order Arrhenius method. All isothermal
experiments were performed at temperature above 100 °C for 16 hours under nitrogen;
kinetic parameters were evaluated by pseudo zero-order Arrhenius mechanism or
Clausius-Clapeyron expression (J. Phys. Chem. B, Vol. 112, No. 33, 2008). Thermal
degradation analysis under helium was carried out on a series of imidazolium,
pyridinium and phosphonium ILs in GC/MS experiments at three different temperatures:
110 °C, 250°C and 350 °C. A principal mechanism of decomposition for imidazolium
and pyridinium ILs was nucleophilic substitution at nitrogen atoms or thermal
dealkylation of cations. For tetra-alkylphosphonium ILs, the two primary decomposition
pathways involved are: 1) nucleophilic substitution reaction at the α carbon where a
nucleophilic anion displaces a trialkylphosphine group and 2) β-elimination where the βproton
is abstracted by a base in concert with the expulsion of trialkylphosphine (Chem.
Mater., Vol. 14, No. 11, 2002).
COIL-4:214
Importance of Physico-Chemical Parameters in Ionic Liquid Based Catalysis

Catherine C. Santini (1) , santini@cpe.fr, 43 Boulevard du 11 Novembre 1918,
Villeurbanne F-69616, France ; Gorka Salas (1) ; Paul S. Campbell (1) ; Ajda Podgoršek (2) ;
Margarida F. Costa Gomes (2) . (1) LC2P2, Equipe Chimie Organométallique de Surface,
ESCPE, Université de Lyon, Institut de Chimie de Lyon, UMR 5265 CNRS-Université de
Lyon-ESCPE Lyon, Villeurbanne F-69616, France (2) Laboratoire de Thermodynamique
et Interactions Moléculaires, Clermont Université, UMR 6272 CNRS-Université Blaise
Pascal, Aubière 63171, France
The physical-chemical parameters in the reaction system for hydrogenation of 1,3cyclohexadiene
(CYD) in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide,
[C1C4Im][NTf2] and 1-butyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide,
[C1C1C4Im][NTf2] were determined. It was found that they influence the catalytic activity
of an Osborn-type catalyst [Rh(COD)(PPh3)2]NTf2 (COD=1,5-cyclooctadiene) and are
crucial in explaining the catalytic outcome. Firstly the solvation of CYD in the two
ILs was investigated by molecular simulations and ROESY NMR experiments. In both
ILs, CYD was found to be located in the lipophilic domains. Secondly, the role of mass
transport factors was studied in both ILs. For this, the viscosity of CYD-IL mixtures at
various molar ratios, R=CYD/IL, and the diffusion coefficients (by DOSY NMR) of CYD,
[C1C4Im] + and [NTf2] - were determined. Finally the ionicity of the media was determined
by a combination of the conductivity and the NMR measurements. We have ascertained
that to fully understand the kinetics of catalytic processes carried out in ILs, a
comprehensive study of all physical-chemical variables is necessary. Consequently,
when comparing literature data on catalytic activity in ILs the differences in physicalchemical
properties of the whole reaction system must be taken into account, and may
shed light on differences noted. In the case under study it has been found that mass
transport factors play a decisive role. 1-2 1) Wasserscheid, P.; Welton, T. Ionic Liquids in
Synthesis; Wiley VCH: Weinheim, Germany, 2008 2) P. S. Campbell, et al.
J.Phys.Chem.B 2010, 114, 8156-8165.
COIL-4:215
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Redox Behavior of Ruthenium Complexes in Ionic Liquids: Activation of Small
Molecules
Hirotaka Nagao (1) , h-nagao@sophia.ac.jp, 7-1, Kioicho, Chiyodaku Tokyo 102-8554,
Japan ; Shigeki Moriya (1) ; Akari Kajihara (1) ; Masahiro Yoshizawa-Fujita (1) ; Masahiro
Rikukawa (1) . (1) Materials and Life Sciences, Sophia University, Kioicho, Chiyodaku
Tokyo 102-8554, Japan
We have been investigating on redox behavior and reactions of ruthenium complexes
containing pyridyl-containing ligand(s) such as 2,2'-bipyridine (bpy), 2-pyridinecarboxylato
(pyca), 2,2':6',2”-terpyridine (trpy), and bispyridylalkylamine (bpa) in connection with
activation of small molecules on these metal complexes. Carbonylruthenium complexes
containing bpy and trpy ligands function as a catalyst for reduction reactions of carbon
dioxide in aqueous and organic solvents. 1,2 In this study, we investigated

electrochemical behavior of ruthenium complexes such [Ru(CO)L(trpy)] 2+ (L = bpy and
pap; phenylazopyridine) and [RuClXY(bpa)] n+ (X = Y = Cl: n = 0, X = NO; Y = Cl and
CH3O: n = 1) in ionic liquids, 1-ethyl-3-methylimidazolium and N-methyl-Npropylpyrrolidinium
bis(trifluoromethylsulfonyl)amide salts ([C2mim][N(Tf)2] and
[C3mpyr][N(Tf)2]) by cyclic voltammetry under Ar and CO2 atmosphere. By comparison
of CV profiles under Ar and CO2 atmosphere, catalytic ability of these ruthenium
complexes toward reduction of carbon dioxide were examined. The controlled-potential
electrolysis of these ruthenium complexes in the CO2-saturated ionic liquid and the
analysis of gas phase in gas chromatography measurements were carried out.
References: 1. H. Nagao, T. Mizukawa, and K. Tanaka, Inorg. Chem., 1994, 33, 3415.
2. H. Ishida, K. Fujiki, T. Ohba, K. Ohkubo, K. Tanaka, T. Terada, T. Tanaka, J. Chem.
Soc., Dalton Trans., 1990, 2155. Acknowledgment: This work was supported by
ENEOS Hydrogen Trust Fund.
COIL-4:216
Physicochemical and Acid-Base Properties of New Protic Ionic Liquids with 2-
Hydroxylethyl Groups
Xuedan SONG (1) , song@chem.kyushu-univ.jp, 6-10-1 Hakozaki, Higashi-ku, Fukuoka
Fukuoka 812-8581, Japan ; Ryo KANZAKI (2) ; Yasuhiro UMEBAYASHI (1) . (1)
Department of Chemistry, Faculty of Science, Kyushu University, Fukuoka Fukuoka
812-8581, Japan (2) Graduate School of Science and Engineering, Kagoshima
University, Kagoshima Kagoshima 890-0065, Japan
Protic ionic liquids (PILs) have been attracted attention as new proton transfer materials
for fuel cells, catalysts for organic syntheses and solvents for enzyme reactions. Solvent
physicochemical and acid-base properties of PILs play important role in these
applications. Therefore, a parameter ∆pKa, defined as the difference of pKa values
between the protonated cation (HB + ) and the conjugated acid of the anion (HA) in their
aqueous solutions, has been proposed by Angell et al. as the measure of acid-base
property of PILs. [1] However, it is needed to clarify the acid-base property of PILs from
the thermodynamic viewpoint. We thus proposed the autoprotolysis constant KS (=
[HA][B]/[HB + ][A – ]) for the autoprotolysis reaction, HB + + A - ⇌ HA + B, one of the
measures of the acid-base property on the basis of the direct pH measurement. [2] In
this contribution, we report the acid-base properties of a series of PILs composed of
ammonium cation with 2-hydroxyethyl groups [(C2H4OH)n(C2H5)(3-n)NH + ][X] (n = 0 ~ 3, X:
trifluoromethanesulfonate TFS – , bis(trifluoromethanesulfonyl)amide TFSA – and nitrate
NO3 – ). We found that a specific interaction between (C2H4OH)2(C2H5)NH + ···NO3 –
operates in [(C2H4OH)2(C2H5)NH + ][NO3 - ] to reduce the auto-protolysis constant pKS,
and that the HTFSA behaves as a stronger acid comparing with HTFS in ionic liquids
composed of (C2H4OH)2(C2H5)NH + . In addition, the cation dependence of the pKS and
physicochemical properties for [(C2H4OH)n(C2H5)(3-n)NH + ][TFS – ] were discussed. [1]
(a) M. Yoshizawa, W. Xu, C. A. Angell, J. Am. Chem. Soc. 2003, 125, 15411., (b) J.-P.
Belieres, C. A. Angell, J. Phys. Chem. B 2007, 111, 4926. [2] (a) R. Kanzaki, X. Song,
Y. Umebayashi, S. Ishiguro, Chem. Lett. 2010, 39, 578.; (b) R. Kanzaki, K. Uchida, X.

Song, Y. Umebayashi, S. Ishiguro, Anal. Sci. 2008, 24, 1347.; (c) R. Kanzaki, K.
Uchida, S. Hara, Y. Umebayashi, S. Ishiguro, S. Nomura, Chem. Lett. 2007, 36, 684.
COIL-4:217
Neutral Species from “Non-Protic” N-Heterocyclic Ionic Liquids
Oldamur Hollóczki (1) , holloczki@gmail.com, Szt. Gellért tér 4., Budapest Budapest H-
1111, Hungary ; László Nyulászi (1)(2) . (1) Materials Structure and Modeling Research
Group of the Hungarian Academy of Sciences, Budapest University of Technology and
Economics, Budapest H-1111, Hungary (2) Department of Inorganic and Analytical
Chemistry, Budapest University of Technology and Economics, Budapest H-1111,
Hungary
Ionic liquids (ILs) are built from oppositely charged particles, where the anions are
derivable from acids by deprotonation. ILs with easily availabile protons at the cationic
side are termed protic, and can produce neutral species (the deprotonated cation and
the acid) relatively easily. The availability of these neutral species can influence the
physical properties (e.g. evaporation), and also the chemical behavior, stability etc. of
the IL. Recently, we have demonstrated that 1,3-dialkyl-imidazolium salts with basic
anions (such as acetate) can form carbenes and acids in the gaseous phase, and this
influences the chemical properties including catalytic activity of these ILs as well.
Noteably, DFT calculated deprotonation energies of 1,2,3-trialkylimidazolium and 1alkylpyridinium
cations are only somewhat higher than that of 1,3-dialkylimidazolium
cation, furthermore the nucleophilic attack of the anion at the cation in N-heterocyclic
ILs may also result in neutral species. Accordingly, DFT calculations revealed that in
case of 1,2,3-trialkylimidazolium derivatives the proton transfer is a viable isomerisation
in the gas phase at elevated temperatures, resulting in diazapentafulvenes, in the
presence of sufficiently basic anions, such as the widely used acetate. In case of
pyridinium salts, however, the increase of anionic basicity results in the accessibility of
1,2- and 1,4-dihydropyridine derivatives by the facile attachment of the anion to the
cation, instead of proton transfer. The dominance of these isomers can only be
expected in the vapor, since in the bulk of the liquid the interaction with surrounding
charged particles stabilizes the ion pairs, thus, these neutral species are clearly present
in the liquid ILs in small concentrations. However, likewise for 1,3-dialkylimidazolium
salts, where we could demonstrate the organocatalytic activity due to the presence of
1,3-dialkyl-imidazol-2-ylidene, this small concentration can have effects on the physical,
and also the chemical properties of the IL, and these neutral species can facilitate
chemical reactions.
COIL-4:218
Use of Ionic Liquids Aggregates in Analytical Extraction Schemes
Veronica Pino (1) , veropino@ull.es, avda. Astrofisico Francisco Sanchez s/n, Facultad
de Quimica, La Laguna Canarias 38205, Spain ; Monica German-Hernandez (1) ; Armide

Martin-Perez (1) ; Ana M Afonso (1) . (1) Department of Analytical Chemistry, Nutrition and
Food Science, Universidad de La Laguna, La Laguna 38205, Spain
Ionic liquids (ILs) are a class of low melting point, ionic compounds which have a variety
of properties such as high thermal stabilities and low vapor pressures. Their unique
solvation properties, coupled to the fact that they can be structurally tailored for specific
applications, have resulted in an increasing study of ILs in many areas of fundamental
and applied chemistry. A new group of ILs able to form aggregates in aqueous solution
have been recently described. This behavior makes possible to include these ILs in the
category of compounds able to form organized media, like the surfactants. It is very
interesting to study these new ILs as they constitute a new area of surfactant
development, especially considering the limited number of traditional cationic
surfactants. Many of these ILs also possess low critical micelle concentration (CMC)
values, which permits the formation of organized media using small amounts. Aqueous
aggregates of ILs have been recently proposed as adequate extractants for organic
compounds bound to solid environmental or food matrixes. These ILs aggregates are
therefore acting as novel substitutes of organic solvents usually employed in
conventional extraction schemes. The IL-based extraction procedure can be
accelerated using microwaves or ultrasounds. Thus, the IL phase containing the
extracted analytes of interest can be subsequently injected in a high-performance liquid
chromatograph (HPLC). Recent investigations also propose the combination of IL
aggregates with gas-chromatography (GC) by means of solid-phase microextraction
(SPME). In this sense, the conventional extraction schemes in the analysis of organic
compounds contained in solid samples can be reduced to a stage of solubilization of the
samples in the ILs aggregates medium, followed by their separation using HPLC or
SPME-GC. It must be highlighted that it is not necessary to remove the IL medium prior
to HPLC or GC injection.
COIL-4:219
Asymmetric Induction Via Ion-Pairing Interactions
Valentin Wagner (1) , valentin.wagner@crt.cbi.uni-erlangen.de, Egerlandstr. 3, Erlangen
91058, Germany ; Karola Schneiders (1) ; Peter S Schulz (1) ; Peter Wasserscheid (1) . (1)
Department of Chemical Reaction Engineering, FAU Erlangen Nürnberg, Erlangen
91058, Germany
The properties of ionic liquids are dominated by their interionic interactions. Because of
the special nature of these interactions, IL properties differ from both, organic solvents
and high temperature molten salts. Our aim is to probe ion-pairing effects in ionic liquids
under the conditions of a chemical reaction using chiral induction among the two ions of
a binary ionic liquid as the probe. Based on this general concept we have demonstrated
that the hydrogenation of a prochiral keto-functionalized imidazolium salt over a
heterogeneous achiral catalyst (Ru/C) in presence of a enantiomeric pure, chiral
counter-ion, leads to significant asymmetric induction in the resulting cation. [1] The ee
found in the product cation depends on the polarity of the solvent, the ion structures and

the concentration of the ionic liquid. Using DOSY-NMR spectroscopy and conductivity
measurements the self-diffusion-coefficients of anions and cations were determined. It
could be shown, that the maximum chirality transfer and the lowest degree of
dissociation (which can be calculated from the self-diffusion-coefficient) of the relevant
ion pairs correlate very well. [2] An additional approach to measure ion-pair interactions,
the Dielectric relaxation spectroscopy (DRS) measurements were applied to one of our
systems. The results gave another clear proof for our hypothesis that chirality transfer in
ionic liquids is strongly linked to ion-pair interactions and formation of small ion clusters
of the IL. Furthermore we were able to show, that other chiral anions of both central [3]
and axial chirality also show asymmetric induction throughout the hydrogenation of
imidazoliumbased keto-functionalized cations. The inversion of the induction was also
achieved. [1] P. S. Schulz, N. Müller, A. Bösmann, P. Wasserscheid, Angew. Chem.
Int. Ed., 2007, 46, 1293. [2] K. Schneiders, A. Bösmann, P. S. Schulz, P. Wasserscheid,
Advanced Synthesis & Catalysis, 2009, 351(3), 432-440. [3] P. S. Schulz, K.
Schneiders, S.J. Sachnov, P. Wasserscheid, Tetrahedron: Asymmetry, 2010, 21(15),
1821-24.
COIL-4:220
Ionic Liquid Mediated Oxidation of Unsaturated Fatty Esters
Mathilde G Sørensen (1) , mags@kemi.dtu.dk, Kemitorvet byg. 207, Kgs. Lyngby 2800,
Denmark ; Anders Riisager (1) . (1) Department of Chemistry, Technical University of
Denmark, Kgs. Lyngby 2800, Denmark
In a world of limited resources and increasing pollution, it is a major challenge to find
alternative preferably renewable feedstock for sustainable production of fuels and
chemicals that currently are derived from finite fossil resources. Bio-oils are a group of
compounds that are attracting more and more interest in this context. They have proved
to be suitable for production of many different products like fuels or plasticizers, and
have also been forecast as a future platform chemical. Key advantages of bio-oil based
products, besides being based on renewable resources, include biodegradability and
low toxicity. Plant oils are particularly useful due to rapid biomass generation, but
industrial waste products like lard or tallow are also potential raw materials for
generation of useful products. Functionalization of the fatty acid moiety can alter the
properties or give rise to alternative applications. It is thus of great interest to find ways
to modify these kinds of compounds. In this work, catalytic oxidation of unsaturated
fatty acid derivatives was studied as a means of introducing a number of different
functionalities to the fatty acid moiety. In all experiments ionic liquids were used as the
solvent because they facilitate straightforward catalyst recycling. Furthermore, the ionic
liquid can be modified to adjust properties like solubility to simplify product separation.
Epoxidation with aqueous hydrogen peroxide proved to be very effective. Olefins were
in general readily epoxidized and provided essentially quantitative yield. Similar results
were also obtained upon recycling of the catalyst/ionic liquid. Importantly, no hydrolysis
of the ester bond was observed during the reactions – such hydrolysis is often a major
problem affecting fatty ester functionalization. With the combination of simple catalyst

ecycling and absence of hydrolysis, this system is of great interest for epoxidation of
olefins in general and for derivatized fatty acids in particular.
COIL-4:221
CO2 Solubility and Regeneration Studies Using Ionic Liquids as Additives in
Amine-Based CO2 Absorbent.
Jinkyu Im (1) , jinq@paran.com, Hoegi-dong, Dongdaemun-gu, Seoul, Republic of Korea
; Jelliarko Palgunadi (1) ; Youngeun Cheon (1) ; Minserk Cheong (1) ; Je Seung Lee (1) ; Hoon
Sik Kim (1) . (1) Department of Chemistry, Kyung Hee University, Seoul 130-701,
Republic of Korea
One of the global environmental problems of today is the increase of the greenhouse
gases concentrations in the atmosphere. This problem partly corresponds to the
increase of carbon dioxide (CO2) emission from the burning of fossil fuels for power
generations. To response this challenge, carbon capture and storage (CCS) using liquid
scrubber receives great attentions because there is potential for retrofit to existing
power plants without changing the existing process. Within this framework, a scrubber
system consisting of amine mixtures has been proposed to capture CO2 emitted in postcombustion
process with a consideration that the amine-based aqueous/non-aqueous
absorbents have been traditionally employed in natural gas sweetening. One of major
technical obstacles associated with the direct utilization of amine-based absorbent is the
high energy consumption for the absorbent regeneration. The present work is a study to
evaluate the role of ionic liquid (IL) in an amine-based scrubber for post-combustion
CO2 capture. A series of solutions containing 1-methylpiperazine in ethylene glycol as a
solvent with or without the addition of an IL were evaluated for CO2 removal. It was
found that a solution consisting of 1-methylpiperazine in ethylene glycol as a solvent
with small amount of piperazium-based ILs as an additive were able to capture CO2 with
a close capacity as the one without additive. Importantly, the IL has a role to improve
the recyclability of the absorbent indicated from the multiple CO2 absorption-desorption
experiments. Finally, optimum compositions were evaluated for the optimum CO2
capture.
COIL-4:222
Phosphonium Dicyanamide Ionogel Incorporating Bromophenol Blue Dye as a
Versatile Platform for Monitoring Ph in Solution
Vincenzo F Curto (1)(2) , vincenzo.curto2@mail.dcu.ie, Collins Avenue, Dublin Ireland
Dublin 9, Ireland ; Robert Byrne (1)(2) ; Dermot Diamond (1)(2) ; Fernando Benito Lopez (1)(2) .
(1) School of Chemical Sciences, NCSR: National Centre for Sensor Research, Dublin
Ireland Dublin 9, Ireland (2) School of Chemical Sciences, CLARITY: Centre for Sensor
Web Technologies, Dublin Ireland Dublin 9, Ireland

Online monitoring of pH levels in different environments such as bio-engineering and
chemistry is vital for effective control of many critical industrial processes[1]. The most
common chemical parameter monitored is pH, and there is an increasing interest in the
fabrication of robust, cheap and versatile pH sensing materials that can be easily
integrated within existing industrial technologies. Ideally these materials present low
fouling and do not require calibration, thus minimising manual attention over long
operational intervals. In this work we present an innovative material (ionogel) that
integrates pH-sensing capabilities for continuously measuring pH during chemical or
biological processes. The ionogel is a solid, flexible and easily to pattern material
generated using tetrabutylphosponium dicyanamide ionic liquid, hydrogel polymer (Nisopropylacrylamide
and N,N-methylene-bis(acrylamide)) and a pH sensitive dye
(Bromophenol Blue). Figure 1 shows the UV spectra of the ionogel-dye in an acidic and
a basic pH environment as well as the pictures of the ionogels. A substantial colour
variation is observed as the pH changes that can be monitored visually or optically[2].
We incorporated the photoresponsive dye during photo-polymerisation of the monomer
to improve stability, for example, by preventing leaching of the dye from the ionogel into
the sample phase. This strategy was not found to inhibit the sensitivity of the optical
response. UV spectra of the ionogel-dye, pictures of the ionogels at different
pH conditions and chemical structure of ionogel and dye [1] M. Blumentritt, et al.,
Sens.ActuatorsB,131(2008), 504-508. [2] F. Benito-Lopez, et al., BSN-2010,26-28
June,(2010),Singapore,291-296.
COIL-4:223
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Crown Ether Enhanced Exrtaction of Cesium into RTIL
K. Popov (1) , ki-popov@mtu-net.ru; A. Vendilo (2) ; D. Djigailo (3) ; E. Esipova (2) ; I.
Filimonov (2) ; V. Chistov (2) ; I. Pletnev (3) . (1) Department of Physical and Colloid
Chemistry, Moscow State University of Food Production, Moscow, Russian Federation
(2) Institute of Reagents and High Purity Substances (IREA), Moscow, Russian
Federation (3) Department of Chemistry, M.V.Lomonosov State University, Moscow,
Russian Federation
18-crown-6 (18C6), dibenzo-18-crown-6 (DB18C6), dibenzo-21-crown-7 (DB21C7) and
dibenzo-24-crown-8 (DB24C8) assisted extraction of Cesium from water into six
hydrophobic RTILs: trioctylmethylammonium salicylate ([TOMA][Sal]),
tetrahexylammonium dihexylsulfosuccinate ([THA][DHSS]), 1-butyl-3-methylimidazolium
hexafluorophosphate ([BMIM][PF6]), 1-butyl-3-methylimidazolium
bis[trifluoromethyl)sulphonyl]imide ([BMIM][N(Tf)2]), 1-hexyl-3-methylimidazolium
bis[trifluoromethyl)sulphonyl]imide ([HMIM][N(Tf)2]), and 1-(2-ethylhexyl)-3methylimidazolium
bis[trifluoromethyl)sulphonyl]imide ([EtHMIM][N(Tf)2]) is studied at
room temperature and the corresponding D values are measured within the pH range of
an aqueous phase from 1 to 6. It is demonstrated that the pH-dependence of crownether
assisted extraction from water into RTIL phase correlates well with the relative
distribution of a crown. The formation of crown ether complexes [Cs(18C6)] + and

[Cs(DB18C6)] + promotes cesium extraction into hydrophobic RTIL from water if the
complex stability in RTIL is higher then in water. For [BMIM][N(Tf)2], [HMIM][N(Tf)2],
[EtHMIM][N(Tf)2], [BMIM][PF6] and [TOMA][Sal] logK1 RTIL > logK1 water and cesium
content in RTIL increases due to 18C6 administration. For [THA][DHSS] logK1 RTIL <
logK1 water and crown ether decreases cesium content in RTIL. The logDCs 18C6 values
have the same order of magnitude for RTILs, 1,2-dichloroethane and other volatile
organic diluents, while the hazardous properties of the latter are much higher. It is noted
that the complex stability in RTIL increases as the RTIL ability to extract cesium without
18C6 (DCs) decreases. The stability constants correlate well with crown ether assisted
extraction degree of cesium from water into RTIL indicating an importance of complex
stability for the extraction process. This indicates clearly an importance of complex
stability contribution for hydrophobic RTILs in extraction processes. At the same time
this trend is strongly modulated by a relative solubility of the chelating agent, its
complex with a target cation and a metal nitrate in water and in a RTIL phase. It is found
that a more hydrophobic DB18C6 reveals better extraction of Cs + into [BMIM][NTf2],
[TOMA][Sal] and [THA][DHSS] then 18C6, while the stability constants of complex
formation are approximately the same.
COIL-4:224
Effect of Alkyl Chains of Cation and Anion on the Thermophysical Properties of
Propanenitrile imidazolium-Based Ionic Liquids
Cecilia Devi Wilfred (1) , cecili@petronas.com.my, Tronoh Perak 31750, Malaysia ;
Mohd Azmi Bustam (1) ; Zakaria Man (1) ; Abu Bakr Ziyada (1) . (1) Fundamental and Applied
Sciences, Universiti Teknologi PETRONAS, Tronoh Perak 31750, Malaysia
A new series of 1-alkyl-3-propanenitrileimidazolium-based ionic liquids (ILs)
incorporating dioctylsulfosuccinate [C2CN Cnim]DOSS , dodecylsulfate [C2CN
Cnim]DDS, benzene sulfonic acid [C2CN Cnim]SBA, benzene sulfonate [C2CN Cnim]BS
and trifluoromethanesulfonate [C2CN Cnim]TFMS have been prepared. The present
ionic liquids (ILs) are characterised using NMR, FTIR and elemental analysis and their
physical properties such as density, viscosity and refractive index have been performed
at a broad range of temperature (293.15 to 353.15) K and at atmospheric pressure
while their thermal stability were measured at heating rate 5 °C/min. The present ILs
show lower densities and higher viscosities compared to those of analogous nitrilefunctionalized
ILs with different anions. The differences in these two properties are due
to the presence of large anions (low ion mobility), long alkyl chain of the cations (Van
der Waals interactions) and hydrogen bonding of the functional groups. The refractive
index values of the present ILs are found to increase after the incorporation of nitrile
group and are in good agreement with that reported for other imidazolium-based nitrile
functionalized ILs The results show that thermal stability of the ILs with DOSS, DDS,
SBA, BS and TFMS anions were high in comparison with the corresponding ILs with
bromide anion. The coefficients of thermal expansion, lattice energy and molar
refraction were estimated from the experimental values of density and refractive index.

These ILs show a weak temperature dependency on the thermal expansion coefficient
and low lattice energy.
COIL-4:225
Design of Ionic Liquids for Dissolving Cellulose from a View Point of an Enzyme
Kazutaka Ohira (1) , b06t4013b@yahoo.co.jp, 4-101 Koyama-minami, Tottori City Tottori
Prefecture 680-8552, Japan ; Yoshikazu Abe (1) ; Toshiyuki Itoh (1) . (1) Chemistry and
Biotechnology, Tottori University, Tottori City Tottori Prefecture 680-8552, Japan
Recently cellulose has been attracted as an important renewable resource for
production of biocomposits and bio fuel alcohols. 1 However, since cellulose consists of
linear glucose polymer chains that form very tight hydrogen-bonded supramolecular
structure, cellulose resists against enzymatic degradation. Rogers and co-workers first
reported a breakthrough towards this issue using ionic liquid (IL) technology in 2002. 2
Since then, growing interest has been paid for developing a means that could modify
cellulose structure to easy digestive form by the enzymatic reaction using ionic liquids.
To develop novel ionic liquids that could dissolve cellulose and change its crystal form,
we attempted to design ionic liquids from a viewpoint of enzyme (cellulases) and found
that several types of ammonium ionic liquids that involve an amino acid as anion
sources showed good dissolving property against cellulose. We established that
[N221ME][Ala] worked as good dissolving agent for cellulose: 10 ~ 12 wt% of micro
crystalline cellulose (Avicel) was dissolved in the IL by just 10 minutes of stirring at
100°C. Furthermore, to our delight, it was found that the regenerated cellulose from this
solution was only Type II form. 1. Ohno, H.; Fukaya, Y. Chem. Lett. 2009, 38, 2. 2.
Swatloski, R. P.; Spear, S. K.; Holbrey, J. D.; Rogwers, R. D. J. Am. Chem. Soc. 2002,
124, 4974.
COIL-4:226
Thermodynamic Study of the Volumetric Properties of Binary or Ternary Excess
Molar Volumes for the Ionic Liquid Methyl Trioctylammonium Bis
(Trifluoromethylsulfonyl)Imide
Nirmala Deenadayalu (1) , deenadayalun@mweb.co.za, PO Box 1334, Steve Biko
Campus, Durban KwaZulu-Natal, South Africa ; Indra Bahadur (1) ; Tadeusz Hofman (2) .
(1) Department of Chemistry, DUT, Durban KwaZulu-Natal, South Africa (2) Division of
Physical Chemistry, Warsaw University of Technology, Warsaw, Poland
The experimental densities for the binary or ternary systems containing the ionic liquid
methyl trioctylammonium bis(trifluoromethylsulfonyl)imide ( [MOA] + [Tf2N] − ) were
determined at T = (298.15, 303.15, and 313.15) K. The binary systems were {methyl
trioctylammonium bis(trifluoromethylsulfonyl)imide [MOA] + [Tf2N] − + 2-propanol or 1butanol
or 2-butanol} and (1-butanol + ethyl acetate) or (2-butanol + ethyl acetate). The
ternary systems were {methyl trioctylammonium bis(trifluoromethylsulfonyl)imide + 2-

propanol or 1-butanol or 2-butanol + ethyl acetate}. The binary and ternary excess
molar volumes for the above systems were calculated from the experimental density
values for each temperature. The Redlich–Kister smoothing polynomial was fitted to the
binary excess molar volume data. The binary excess molar volume results showed both
negative and positive values over the entire composition range for all the temperatures.
The ternary excess molar volume data were successfully correlated by the Cibulka
equation.
COIL-4:227
Vapor-Liquid Equilibria of Binary Mixtures Including Ionic Liquids using
Headspace/Gas Chromatography
Anne-Laure Revelli (1) , arevelli@nd.edu, 310 Stinson-Remick Hall, Notre Dame
INDIANA 46556, United States ; Joan F, Brennecke (1) . (1) Department of Chemical and
Biomolecular Engineering, University of Notre Dame, Notre Dame INDIANA 46556,
United States
The use of ionic liquids (ILs) for separation processes is promising because of their
unique properties. Some organic mixtures forming azeotropes are very challenging to
separate. In order to find the most suitable ionic liquid for a specific separation problem,
systematic measurements of the different thermophysical properties such as vaporliquid
equilibria (VLE) data and activity coefficients are necessary to develop processes
and predictive thermodynamic models. The aim of this work is to investigate the
possible use of ILs as solvents for extractive distillation. In this way, VLE of binary
mixtures including organic compounds and various ionic liquids have been measured by
Headspace / Gas Chromatography. Activity coefficients γi of the organic compounds in
the ionic liquids have been determined from the experimental data and have been
correlated using activity coefficients models, including the Non-Random Two Liquid
(NRTL) and Universal Quasichemical Theory (UNIQUAC) equations.
COIL-4:228
Ionic Liquids as Reaction Media for Transfer Hydrogenation of Epoxides
Helle Søndergaard (1) , hsoe@kemi.dtu.dk, Kemitorvet 207, Lyngby 2800, Denmark ;
Anders Rissager (1) . (1) Department of Chemistry, Technical University of Denmark,
Lyngby 2800, Denmark
Catalytic hydrogen transfer (CTH) is defined as hydrogenation without the use of
gaseous hydrogen. CTH reactions can be catalyzed by either homogeneous or
heterogeneous catalysts. These low pressure reaction systems are thus much safer
than traditional hydrogenations because handling of hydrogen under high pressure is
avoided [1,2]. One problem with homogeneous catalysis is the final separation of
product from the catalyst containing medium. Ionic liquids (ILs) can provide easy phase
separation by selecting the right combination of cation and anion. In addition to phase

separation effects, the ionic liquid can also be functionalized to have a catalytic effect in
the form of an acidic or basic moiety [3,4]. The use of ILs as solvents for CTH is not a
new concept. Both alkenes [5] and ketones [6] have previously been hydrogenated in
different ILs. Epoxides, however, have only previously been hydrogenated using
hydrogen donors such as 2-propanol or ammonium formate in traditional solvents [7,8].
In this research we studied CTH of different epoxides in IL media. An example is the
conversion cyclooctene oxide to cyclooctanol, which was investigated in the presence of
different ILs and hydrogen donors. References [1] R. A. W. Johnstone, A. H. Wilby,
Chem. Rev., 85, 129 (1985) [2] C. Saluzzo, M. Lemaire, Adv. Synt. Catal., 344, 915
(2002) [3] K. R. Seddon, Nat. Mater., 2, 363 (2003) [4] D. Giunta, M. Solinas,
Encyclopedia of catalysis, ionic liquids in metal catalyzed reactions, John Wiley & Sons,
2002 [5] Z. Baán, Z. Finta et al, Tetrahedron Lett., 46, 6203 (2005) [6] M. Hut'ka, S.
Toma, Monatsch. Chem., 140. 1189 (2009) [7] M. Ricci, A. Slama, J. Mol. Catal., 89, L1
(1994) [8] J. P. Varghese et al., Synthetic Commun., 25, 2267 (1995)
COIL-4:229
Generation of Semiconductor Nanoparticles with Plasma Electrochemistry
Oliver Höfft (1) , o.hoefft@pe.tu-clausthal.de, Arnold-Sommerfeld-Str 6, Clausthal-
Zellerfeld 38678, Germany ; Norman Spitczok v. Brisinski (1) ; Angela Ulbrich (2) ; Stefan
Krischok (2) ; Frank Endres (1) . (1) Institute of Particle Technology, TU Clausthal,
Clausthal-Zellerfeld 38678, Germany (2) Institute of Micro- and Nanotechnologies and
Institute of Physics, TU Ilmenau, Ilmenau 98684, Germany
Due to their very low vapour pressure ionic liquids can be employed in vacuum
experiments as fluid substrates or solvents. Thus, ionic liquids are well suitable
electrolytes for plasma electrochemical processes, and stable plus homogeneous
plasmas are obtained. The plasma-electrochemical approach is hitherto the only
electrochemical route to the synthesis of free nanoparticles. We have reported that free,
isolated silver nanoparticles can be obtained in the ionic liquid [EMIm]TfO by applying a
plasma as a mechanically contact-free electrode [1]. Here we present our results using
argon plasma as electrode for the electrochemical synthesis of silicon and germanium
nanoparticles. We report about the challenge of these experiments because this method
is limited until now by the vapour pressure of the dissolved species. Possible
compounds like SiCl4 and SiBr4 for example have high vapour pressures and therefore
they are not suited for vacuum applications like the plasma process. We discuss the
plasma electrochemical reactions of two possible precursors, SiI4 and the germanium
dichloride-1,4-dioxane complex (GeCl2[C4H8O2]) in 1-ethyl-3-methylimidazolium
bis(trifluoromethylsulfonyl)amide ([EMIm]Tf2N) and 1-butyl-1-methylpyrrolidinium
bis(trifluoromethylsulfonyl)amide ([Py1,4]Tf2N), for the synthesis of semiconductor
nanoparticles. For SiI4 we have evidence for the production of non stoichiometric SixIy
compounds during the plasma process. This is supported by electrodeposition
experiments from the solution on Au(111). With the Germanium complex it was possible
to synthesize particles. Here particles smaller than 50 nm were observed. We will
present plasma experiments done at temperatures between 323 and 353 K. First results

show, besides a better solubility of the Germanium complex at elevated temperatures,
that the plasma process is faster compared to the room temperature experiments.
Additionally we will present X-ray photoelectron spectroscopy results of the pure and
plasma treated IL complex solutions. [1] S. A. Meiss, M. Rohnke, L. Kienle, S. Zein El
Abedin, F. Endres and J. Janek, ChemPhysChem., 2007, 8, 50.
COIL-4:230
Origin of Fluorescence Peak Shift in Ionic Liquids Having Imidazolium Cations
Seoncheol Cha (1) , sunchul@gmail.com, 1 Sinsu, Mapo Seoul, Republic of Korea ;
Doseok Kim (1) ; Tae Kyu Shim (1) . (1) Department of Physics, Sogang University, Seoul,
Republic of Korea
The shape of fluorescence spectrum of the organic molecules is generally independent
of the excitation wavelength (as called as Kasha's rule), and it is because the internal
conversion in the excited state is usually much faster than the fluorescence decay
lifetime. By contrast, the emission spectra of pure ionic liquids do not obey Kasha's rule;
instead the fluorescence peak from [BMIM][BF4] redshifts following the increase in the
wavelength of the excitation beam. There have been several proposals to explain the
anomalous fluorescence of ionic liquids based on special properties of some ionic
liquids such as molecular aggregates. In order to check this possibility, fluorescence
from ionic liquid-water mixture was investigated. The fluorescence peak shift was the
same for the mixtures at different concentrations, suggesting the fluorescence peak shift
does not come from the structure or the intermolecular arrangement of ionic liquids. 1methylimidazole
is a molecule consisting of an imidazolium ring, and is the precursor for
the synthesis of imidazolium-based ionic liquids. Material properties of 1methylimidazole
are very different from imidazolium-based ionic liquids. However, the
fluorescence from 1-methylimidazole also red-shifted with the increase in the excitation
wavelength as in [BMIM][BF4]. We suggest that this anomalous fluorescence behavior
of ionic liquids originates from the molecular excitation at the absorption-tail;
fluorescence is seen to redshift for excitation at longer wavelength as only the subset of
the ensembles of the molecules having lower electronic energy levels can be excited.
COIL-4:231
Liquid Crystalline Properties of Phosphonium Type Zwitterion/Alkali Metal Salt
Mixtures
Satomi Taguchi (1) , 50009641217@st.tuat.ac.jp, 2-24-26 Naka-cho, Koganei Tokyo
184-8588, Japan ; Takahiro Ichikawa (1) ; Takashi Kato (2) ; Hiroyuki Ohno (1) . (1)
Department of Biotechnology, Tokyo University of Agriculture and Technology, Nakacho,
Koganei Tokyo 184-8588, Japan (2) Department of Chemistry and Biotechnology,
The University of Tokyo, Hongo, Bunkyo-ku Tokyo 113-8656, Japan

Liquid crystalline structure was found in the mixture of phosphonium type zwitterions
(sulfobutyl-tri-n-hexylphosphonium betaine: ZI) and alkali metal salts. Thermal
properties of ZI/alkali metal salts mixtures were examined with differential scanning
calorimetry (DSC). The mixture of ZI and lithium salts (LiCl, LiPF6, LiBF4) showed only
glass transition temperature. However, the DSC trace of the mixture of ZI with
equimolar amount of bis(trifluoromethane sulfonyl)imide salts (LiTf2N, NaTf2N, KTf2N)
showed both glass transition temperature and clearing temperature. Polarizing optical
microscope (POM) observation for there ZI/Li salt mixtures revealed that there was no
characteristic texture for liquid crystalline phase. The POM image indicated that ZI/Li
salt mixture formed cubic structure. The X-ray diffraction (XRD) pattern of ZI/LiTf2N
mixture at 110 °C shows three intense peaks at 3.56°, 4.08°, and 4.46°, related to the
spacing of 24.8, 21.6, and 19.8 Å, recpectively. The reciprocal spacing ratio of three
peaks were 2 : √5: √6, which can be assigned to the (200), (210), and (211) reflections,
respectively for the cubic phase with Pm3n symmetry. Those results suggested that ZI
and Tf2N salts mixture formed micelle cubic structure.
COIL-4:232
Electrochemical Oxidation of Glucose in Ionic Liquids with Gold Nano-Particle
Modified Electrode
Mitsuru Abe (1) , ring-of-wisdom@hotmail.co.jp, 2-24-16, naka-cho, koganei Tokyo 184-
0012, Japan ; Yukinobu Fukaya (1) ; Hiroyuki Ohno (1) . (1) biotechnology, Tokyo University
of Agriculture and Technology, koganei Tokyo 184-0012, Japan
Some ionic liquids (ILs) dissolve and extract cellulose from biomass under mild
condition. They are also considered to be effective to hydrolyze cellulose into sugar by
the addition of a small amount of water. In spite that glucose-type bio-fuel cell has
already been developed with aqueous electrolyte solution. To improve operation
condition and durability of these cells, we aimed to design these cells with ILs. We
conducted the electrochemical oxidation of glucose in some polar ILs. Water is required
to hydrolyze cellulose into glucose. However, water addition makes polar ILs
considerably lower the cellulose solubility. We have to set up, therefore, a glucose
oxidation electrode in the presence of minimum amount of water, 10 wt% or less. In this
study, we have used gold nano-particles (AuNP) as a catalyst for glucose oxidation.
AuNP was prepared with citric acid reduction method, and the average diameter of the
nano-particles was 15 nm. The AuNP solution was cast on the surface of gold
electrodes and dried to prepare AuNP modified electrodes. First, we confirmed the
glucose oxidation activity of the electrodes in 50 mM phosphate buffer (pH7.0). The
electrode showed the catalytic activity, and the oxidation current was observed from -
0.3 V vs. Ag|Ag+. Specific voltammograms for the glucose oxidation with AuNP were
obtained. Then, a polar ionic liquid, 1,3-dimethylimidazolium methylphosphonate which
has a good ability to solubilize cellulose, was mixed with pH7.0 phosphate buffer.
Regardless of the amount of water, the current for glucose oxidation was not detected in
the mixuture. The lack of the catalytic activity may be caused by the adsorption of the
imidazolium rings to the electrode surface. Then, alkyl ammonium carbonate type IL,

which has little affinity with Au, was used. With the addition of sodium hydroxide, AuNP
showed the glucose oxidation in the IL containing 10 wt% water.
COIL-4:233
Ionic Liquid- Functionalized Molybdenium Disulfide Nanoparticles as Novel
Stabilizing Surfactants for Ionic Liquid/Oil Microemulsions
Anja Stojanovic (1) , anja.stojanovic@chemie.uni-halle.de, von Danckelmann Platz 4,
Halle (Saale), Germany ; Wolfgang H Binder (1) . (1) Department of Macromolecules
Chemistry, Martin-Luther University Halle-Wittenberg, Faculty of Natural Sciences II,
Institute of Chemistry, Halle (Saale) 06120, Germany
Due to several outstanding properties of ionic liquids their possible applications in
tribology have recently gained an increasing attention within the scientific community 1 .
Especially the use of ionic liquid-based microemulsions as potential novel lubricant
systems has been the focus of extensive research. However, up to now, only little is
known about the preparation, properties and performance of ionic liquid containing
microemulsions. 1, 2 Here we report novel ionic liquid- functionalized molybdenium
disulfide nanoparticles as potential stabilizing surfactans for IL-based microemulsions.
In the first step, several novel tetraethylene glycol-based ionic liquids bearing
imidazolium cation and appropriate chelating moieties were synthesized and
characterized via 1 H, 13 C NMR and ESI-TOF/MS. In the next step, obtained ILs were
covalently grafted onto the molybdenium disulfide to gain functionalized nanoparticles.
Prepared nanoparticles were analysed via TEM, XRD as well as with MALDI-TOF/MS.
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Figure 1. Ionic liquid- functionalized molybdenium disulfide nanoparticles
Acknowledgment: The authors are grateful to MINILUBES Network-European
Commission Research FP7 for financial support. References: (1) Minami, I.
Molecules. 2010, 14, 2286-2305. (2) a) Gao, Y., Wang, S., Zheng, L., Han, S., Zhang,
X., Lu, D., Yu, L., Ji, Y., Zhang, G., J. Colloid Interface Sci. 2006, 301, 612-616; b)
Pramanik, R., Sarkar, S., Ghatak, C., Rao, V. G., Sarkar, N., J. Phys. Chem. B, 2011,
doi: dx.doi.org/10.1021/jp110896w
COIL-4:234
Synthesis of Graphene Ionic Liquid Electrode for Electrochemical Determination
of Ascorbic Acid, Dopamine and Uric Acid
Ting-Kang Hsu (1) , sunchialiang@gmail.com, 259 Wen-Hwa 1st Road, Kwei-Shan, Tao-
Yuan Taiwan 333, Taiwan Republic of China ; Chun-Yu Chu (1) ; Chia-Liang Sun (1) . (1)
Department of Chemical and Materials Engineering, Chang Gung University, Tao-Yuan
333, Taiwan Republic of China
Ionic liquids (ILs) have been known for almost one century and their reactivity has been
reviewed. [1] More recently, the electrochemical biosensors based on carbon ionic liquid

electrodes (CILEs) have been reported. [2] On the other hand, graphene has recently
received tremendous attention. [3] Graphene and its composite materials also exhibit a
significant potential for biosensors. [4] However, there is little research to study
graphene ionic liquid electrode (GILE) in electrochemical biosensors. Therefore, in this
study GILE-modified glassy carbon (GC) electrode has been prepared for simultaneous
determination of ascorbic acid (AA), dopamine (DA), and uric acid (UA). In Figure 1, it is
found that GILE/GC electrode outperforms the graphene/GC. It suggests that GILE has
great potential as a platform for the routine analysis of AA, DA, and UA. Figure
1. Cyclic voltammograms of graphene/GC and GILE/GC electrodes in 0.66 mM AA +
0.33 mM DA + 0.33 mM UA. References [1] Hapiot, P.; Lagrost, C. Chem. Rev. 2008,
108, 2238. [2] Fukushima, T.; Kosaka, A.; Ishimura, Y.; Yamamoto, T.; Takigawa, T.;
Ishii, N.; Aida, T. Science, 2003, 300, 315. [3] Novoselov, K. S.; Geim, A. K.; Morozov,
S. V.; Jiang, D.; Zhang, Y.; Dubonos, S. V.; Grigorieva, I. V.; Firsov, A. A. Science,
2004, 306, 666. [4] Sun, C. L.; Lee, H. H.; Yang, J. M.; Wu, C.C. Biosens. Bioelectron.
2011 (in press). DOI: 10.1016/j.bios.2011.01.023
COIL-4:235
Good's Buffer Inspired Ionic Liquids
Huy N Ha (1) , Huy.Ha@monash.edu, Wellington Road, Clayton VIC 3800, Australia ;
Doug R MacFarlane (1) . (1) School of Chemistry, Monash University, Clayton VIC 3800,
Australia
Zwitterionic Good's buffers 1 are prevalent in biochemistry, due to their
applicable pKa range, as a means to control media close to physiological pH.
Surprisingly, the moiety of Good's buffer highly resembles a subset of structures widely
used in the ionic liquid field, largely those found in the morpholinium family. To date,
work by Poole et al. who first explored Good's buffer based ILs, in this case as anions,
where incorporated with ammonium and phosphonium based cations as solvents for
gas chromotography, 2-4 has so far not seen much application in other areas. Here we
have further explored the use of Good's buffers as possible IL precursors. Zwitterions of
this sort are known to have larger melting points than ionic liquids, usually in excess of
200 °C; therefore reducing the melting point of these chemicals by forming ILs may be
largely beneficial in their fields of application. For example, autoclave sterilization
leading to unwanted precipitation during sterilization of biological media. An ionic liquid
form of the Good's buffer also increases solubility of the buffer which is often desirable
but difficult with the pure zwitterion. We show that Good's buffers can be made into
suitable biocompatible ionic liquids, to address some of the issues limiting their
application. Buffer IL mixtures of the type described in our recent paper 5 based on these
compounds will also be discussed.
COIL-4:236
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Novel Cation Class for ILs and IL Fluoride Solvates: Synthesis and
Physicochemical Properties
Kelvin Walst (1) , kelvin.walst@pg.canterbury.ac.nz, Ilam Rd, Ilam, Christchurch
Canterbury 8041; Owen J Curnow (1) . (1) Department of Chemistry, University of
Canterbury, Christchurch 8041, New Zealand
A novel class of IL cation has been developed: These have been prepared with a range
of counter anions, and the physicochemical, electrochemical and thermal properties
have been investigated. This novel class of ILs have been observed to have properties
that are broadly similar to other cation classes, but with subtle differences due the
aprotic and delocalized nature of the cation. Alcohol (ethanol, isopropanol) solvates of
fluoride anions have been seen to stabilize salts containing the fluoride anion via strong
hydrogen bonds, where usually the naked fluoride IL is unstable. Mono- and di-alcohol
solvate ILs have been easily formed, depending on conditions of removal of excess
alcohol and the cation used.
COIL-4:237
Group Contribution-Based Model for Estimating the Melting Point of Ionic Liquids
Claudia C Aguirre (1) , caguirr9@uc.cl, Casila 170, Antofagasta Antofagasta ii region,
Chile ; Luis A. Cisternas (1) ; Jose O Valderrama (2) . (1) Department of Chemical
Engineering, Universidad de Antofagasta, Antofagasta Antofagasta ii region, Chile (2)
Mechanical Engineering, University of La Serena, La Serena La Serena iv region, Chile
Based on experimental data collected from the literature a group contribution method is
proposed for the estimation of melting point of imidazolium, pyridinium, pyrrolidinium,
ammonium, phosphonium and piperidinium-based ionic liquids with common anions.
Interest in ionic liquids has significantly increased in recent years due to their unique
properties which can be tuned to make them applicable to a wide range of applications.
To assist the design and selection of ionic liquids for particular applications knowledge
of their physical properties is essential. Experimentally determined physical property
data for ILs is limited in the literature. Hence, predictive models could expand the range
of data for synthesised ILs and also properties of ILs which have yet to be synthesised
could be estimated. The melting point is an important property of ILs since it
represents the lower temperature of the liquid gap to use them as solvent or other
applications. The factors that primarily control the melting point of a compound are:
intermolecular forces, molecular symmetry and the conformational degrees of freedom
of a molecule. For ionic liquids, charge, size and charge distribution in the respective
ions, also influence the melting point. The proposed group contribution method
considers the contributions of ionic groups and methylene groups as additive
parameters and two nonadditive characteristic geometric parameters of cations such as
symmetry and flexibility. A total of 293 data points for 136 ILs were used in this study.
The average relative error and the average absolute error of the proposed model are

7.8 K and 22.6 K respectively. It is concluded that the proposal is useful for the
prediction of the melting points for a wide range of ionic liquids.
COIL-4:238
Polymer/Sulfur-Based Ionic Liquid Hybrid Electrolytes for Lithium Batteries
Aaron S Fisher (1) , asf@umd.edu, 1201 Chemical and Nuclear Engineering Builiding,
College Park MD 20742, United States ; Mian B Khalid (2) ; Matthew Widstrom (3) ; Peter
Kofinas (2) . (1) Department of Chemical and Biomolecular Engineering, University of
Maryland, College Park MD 20742, United States (2) Fischell Department of
Bioengineering, University of Maryland, College Park MD 20742, United States (3)
Department of Materials Science and Engineering, University of Maryland, College Park
MD 20742, United States
Flexible thin film batteries have many attractive properties that would lead to enhanced
performance for the next generation of lithium ion batteries. Systems have been limited
by their performance benchmarks, which can be overcome with the addition of ionic
liquids (IL). IL chemistries based upon tri-ethyl sulfonium have been explored to
maintain the wide electrochemical stability (high cathodic stability) displayed by the
polymer systems while increasing ionic conductivity. The synthesized ILs have been
blended with a lithium salt in lithium conducting polymer matrices to produce solid
electrolytes. Such shape-conforming materials could be easily wound up into coils or
processed as coatings or sheets, thus providing large area devices with integrated
electronics. These materials would be inherently safer replacing the current combustible
liquid electrolyte systems with a non-flammable polymer system. Electrochemical
characterization of the polymer electrolytes was conducted by potentiodynamic,
potentiostatic and galvanostatic measurements as well as by impedance spectroscopy.
At 0 °C the synthesized electrolytes have demonstrated conductivity >10 -4 S/cm, while
at 40 °C the synthesized electrolytes have demonstrated conductivity >10 -2 S/cm.
Cathodic stability, which ultimately impacts the power of a given cell has been reversibly
demonstrated to 5 V vs. lithium. Given the widely accepted performance benchmarks
needed for a commercial electrolyte these values are of great scientific interest, which
will allow commercial access to higher power cathodes that have been currently
unusable due to limitations in carbonate based electrolytes.
COIL-4:239
The Behaviour of Radicals in Ionic Liquids: The Strange Case of 2,2-Diphenyl-1-
Picrylhydrazyl (Dpph)
Alasdair W Taylor (1) , Alasdair.Taylor@nottingham.ac.uk, University Park, Nottingham
Nottinghamshire NG7 2RD, United Kingdom ; Simon Puttick (1) ; Peter Licence (1) ; E.
Stephen Davies (1) . (1) School of Chemistry, University of Nottingham, Nottingham NG7
2RD, United Kingdom

The role of ionic liquids as solvents in radical reactions has been suggested to be far
from innocent. To investigate the behaviour of radical species, the stable radical, 2,2diphenyl-1-picrylhydrazyl,
dpph, has been studied using electorn spin resonance (ESR)
spectroscopy and electrochemistry in a range of ionic liquids. The solution ESR
spectrum of dpph in conventional, molecular solvents is typically symmetrical and
exhibits a 1:2:3:2:1 quintet, indicative of spin-spin coupling of the single unpaired
electron to two 14 N nuclei. However, the spectrum is altered dramatically in simple, nonfunctionalised
ionic liquids, e.g. for [C4C1Im][Tf2N] (left hand Figure), only three lines are
visible. Our analysis indicates that the change in shape of the ESR spectrum is related
to intermolecular interactions of dpph with the ionic liquid. 2 The cyclic voltammogram of
dpph has two prominent reversible redox couples corresponding to its one-electron
oxidation and reduction (see right hand Figure). The potential difference between the
two couples, ∆E½, can be related to the Lewis basicity of the solvent. 3 In ionic liquids,
∆E½ is anion dependent and shows that even anions considered weakly coordinating,
e.g. [Tf2N] - , are as Lewis basic as solvents such as DMSO whereas other anions, e.g.
[EtOSO3] - , are even more Lewis basic. 2 1. Puttick et al., in preparation 2.
Abou-Elenien, J. Electroanal. Chem., 1993, 345, 303-321 3. Taylor et al., in preparation
http://www.nottingham.ac.uk/ionicliquids/
COIL-4:240
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Thiol-Ene Coupling Reactions as a Method to Prepare Functionalized Ionic
Liquids.
Kaila M Mattson (1) , kmm708@jaguar1.usouthal.edu, 307 N University Blvd., Mobile AL
36688; Arsalan Mirjafari (1) ; Richard A O[apos]Brien (1) ; Kevin N West (2) ; James H Davis,
Jr. (1)(2) ; Jonathan L McDonald (1) ; Maelynn La (1) ; Samuel M Murray (2) . (1) Department of
Chemistry, University of South Alabama, Mobile Alabama 36688, United States (2)
Department of Chemical and Biomolecular Engineering, University of South Alabama,
Mobile Alabama 36688, United States
Typically, ionic liquids (ILs) containing long aliphatic appendages are either highly
viscous liquids or solids at room temperature. Our group has previously shown sidechain
unsaturation to be a viable technique for overcoming this process limitation and
depressing IL melting points. We are now utilizing this dramatic structure/property
relationship to drive to design of new functionalized ILs. Thiol-ene chemistry has
proven to be a versatile and useful synthetic tool to prepare an array of organic
molecules, including biomaterials. We investigated the thiol-ene reaction with different
ene-functionalized ILs by reacting them photochemically with alkylthiols, yielding
structurally diverse ILs in a single step. In addition, we employed differential scanning
calorimetry to study the effects of both long and branched substituents upon IL melting
points. Several ILs were selected as ene substrates for the study. Imidazolium-based
cations with either N-allyl or (N-vinyl, N'-allyl) precursors were chosen to assess the
effect, if any, of having the alkene moiety connected directly to the center of the cationic
charge versus being separated from it by one carbon unit. In addition, two different

anions were employed to discern any control over the course of the thiol-ene reaction.
The synthetic methodology as well as the impact of these structural modifications upon
IL melting points will be discussed.
COIL-4:241
Conformational Changes of [Bmim][NO3] with Relation to the Phase Transitions
Naohiro Hatano (1) , em49026@nda.ac.jp, 1-10-20 Hashirimizu, Yokosuka Kanagawa
239-8686, Japan ; Takahiro Takekiyo (1) ; Hiroshi Abe (2) ; Yukihiro Yoshimura (1) . (1)
Department of Applied Chemistry, National Defense Academy, Yokosuka Kanagawa
239-8686, Japan (2) Department of Materials Science and Engineering, National
Defense Academy, Yokosuka Kanagawa 239-8686, Japan
Conformational behavior of room temperature ionic liquids (RTILs) has been studied to
clarify the relationship between the molecular orientation and complicated phase
transition behavior of RTILs [1]. Recently, Strechan et al.[2] reported the temperatureinduced
phase transition of 1-butyl-3-methylimidazolium nitrate ([bmim][NO3]) using an
adiabatic calorimetry method. They found that pure [bmim][NO3] has four crystalline
phases in the temperature range from 272 to 310 K, though the detailed information of
transformed phases of [bmim][NO3] is not clear. In this study, we have investigated the
temperature-induced conformational change of [bmim] + cation in pure [bmim][NO3] from
223 K to 370 K using a JASCO NR-1800 Raman spectrophotometer. The [bmim] +
cation is known to have the trans-trans(tt) and gauche-trans(gt) conformers for the
NCCC and CCCC angles of butyl chain in the liquid state [3]. Here, we show that the
phase transitions in [bmim][NO3] have relation to the conformational changes. More
interestingly, we have found that a new conformational state other than tt and gt
conformers exist in the lower temperature region below ~250 K. References [1] T.
Endo et al., J. Phys. Chem. B, 114, 407 (2010), [2] A.A.Strechan et al., Thermochim.
Acta, 474, 25 (2008), [3] R. Ozawa et al., Chem. Lett., 32, 948 (2003).
COIL-4:242
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Synthesis of Ionic Liquids Consisting of FDA Approved Compounds
Asako Narita (1) , anarita@as.ua.edu, PO/Box 870336, Tuscaloosa AL 35487, United
States ; Parker D McCrary (1) ; John R Canada (1) ; Robin D Rogers (1) . (1) Center for Green
Manufacturing and Department of Chemistry, The University of Alabama, Tuscaloosa
AL 35487, United States
Non toxic Ionic liquids (ILs) are needed for sensitive applications such as use as active
pharmaceutical ingredients, 1 as solvents for pharmaceutical synthesis, 2 and for
diagnosis. 3 However, the toxicity of ILs depends on their structure and the biocompatibility
of many ILs needs to be dekonstarted and approved. One approach we
have undertaken to guide the choice of IL ions has been to study the formation of ILs

using US Food and Drug Administration (FDA) approved chemicals for both anions and
cations. Here we report ILs prepared from compounds that could be anionic or cationic
from the GRAS (Generally Recognized as Safe) and EAFUS (Everything added to Food
in the United States) lists. Seventeen liquids or amorphous glass salts have been
obtained so far. When amines and di- or tri-carboxylic acids are mixed in 1:1 ratios,
acidic ILs were obtained. Such acidic ILs can form oligomeric anions and exhibit pH
buffering due to their multiple protonation sites. The ILs consisting of FDA approved
compounds are expected to be low toxicity materials or solvents, however, further
testing may be necessary. 1. W. Hough et al., Bull. Chem. Soc. Jpn., 2007, 80, 2262. 2.
V. Kumar, et al., Bioorg. Med. Chem. Lett., 2008, 18, 5640. 3. K. Naka, et al., Polym.
Adv. Technol., 2008, 19, 1241.
COIL-4:243
Enzymatic Synthesis of Caffeic Acid Phenethyl Ester Analogues from
Underutilized Natural Resource in Ionic Liquid
Atsushi Kurata (1) , kurata090401@nara.kindai.ac.jp, 3327-204 Nakamachi, Nara City
Nara 631-8505, Japan ; Shintaro Takemoto (1) ; Yuki Kitamura (1) ; Tokio Fujita (1) ; Kazuya
Iwai (2) ; Noriaki Kishimoto (1) . (1) Department of Applied Biological Chemistry, Kinki
University, 3327-204 Nakamachi, Nara City Nara 631-8505, Japan (2) Department of
R&D Center, UCC Ueshima Coffee Co. Ltd., 3-1-4 Zushi, Takatsuki-shi Osaka 569-
0036, Japan
A novel consecutive enzymatic conversion was developed for production of caffeic acid
phenethyl ester analogues from unused coffee beans. The procedure was comprised of
chlorogenate hydrolase and Novozyme435 with [BMIM][NTf2] as the solvent. The
analogues exhibited strong antiproliferative activities toward various human tumor cells.
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COIL-4:244
Liquid-Liquid Phase Diagrams of Hydrophobic Ionic Liquids with Water
Filipa M Maia (1) , deq08005@fe.up.pt, Rua Dr. Roberto Frias, s/n, Porto Porto 4200-
465, Portugal ; Oscar Rodríguez (1) ; Eugénia A. Macedo (1) . (1) LSRE/LCM – Laboratory
of Separation and Reaction Engineering, University of Porto - Faculty of Engineering,
Porto 4200, Portugal
Ionic liquids (ILs) have several different properties that make them attractive for
industrial use. These properties include extremely low vapour pressure, good
conductivity and high thermal stability, among others. In this work, the main focus is the
ability of hydrophobic ILs to form two liquid phases when in contact with water. Such ILs
and their phase diagrams are of interest for separation processes of aqueous solutions
by liquid extraction. The ILs studied are 1-decyl-3-methylimidazolium tetrafluoroborate
[C10mim][BF4], 1-methyl-1-propylpyrrolidinium bis(trifluoromethylsulfonyl)imide

[C3mpyrr][Tf2N] and 1-methyl-1-propylpiperidinium bis(trifluoromethylsulfonyl)imide
[C3mpip][Tf2N]. There are three different types of cations present and two different
anions. In addition, the phase diagram of [C10mim][BF4] is compared to those of
[C6mim][BF4] and [C8mim][BF4], which had already been determined and published [1].
For the determination of phase diagrams, the composition of each phase at equilibrium
was determined at different temperatures using a gravimetric method. Samples from
each phase were weighed, after which all water was evaporated and samples were
weighed again. Tie-lines were determined for temperatures ranging from 5 ºC up to 70
ºC or to the upper critical solution temperature (UCST) of the system. ILs with the
bis(trifluoromethylsulfonyl)imide anion are more hydrophobic than those with the
tetrafluoroborate anion. In systems where the Tf2N anion is present, very small amounts
of water can be found in the IL-rich phase, while the opposite happens for the water-rich
phase. The intake of water by the IL-rich phase is slightly smaller in the system with
[C3mpip][Tf2N] than in the system with [C3mpyrr][Tf2N]. The same happens with the
intake of IL by the water-rich phase. The UCST of these two systems was not reached.
However, the UCST of the system with [C10mim][BF4] was found to be between 52 and
55 ºC. [1] FM Maia, O Rodríguez, EA Macedo, Fluid Phase Equilib. 296 (2010) 184-
191.
COIL-4:245
Supported Ionic Liquid Nanoparticles (SILnPs) as a Heterogeneous Acid Catalyst
for the Dehydration of Fructose to 5-Hydroxymethylfurfural
João A.P. Coutinho (1) , jcoutinho@ua.pt, University of Aveiro, Aveiro Aveiro, Portugal ;
Kalpesh B. Sidhpuria (1) ; Ana L Daniel-da-Silva (1) ; Tito Trindade (1) . (1) Department of
Chemistry, University of Aveiro, CICECO, Aveiro 3810-193, Portugal
Abundant biomass resources are promising alternatives for the sustainable supply of
valuable chemical intermediates and liquid fuel. Acid catalyzed dehydration of sugars to
5-hydroxymethylfurfural (HMF) is one of the most important approaches to transform
biomass to useful chemicals and therefore, numerous studies on the dehydration of
hexose to HMF have been taken place over many homogeneous and heterogeneous
catalysts. However, still new efforts towards an efficient and easy-to-use process for the
preparation of HMF are ongoing. In the above context, supported ionic liquid
nanoparticles (SILnPs) have been prepared by immobilization of ionic liquid, 1-(triethoxy
silyl-propyl)-3-methyl-imidazolium hydrogen sulfate (IL-HSO4) on the surface of
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silica nanoparticles and investigated for the dehydration of fructose to HMF. .
The simultaneous effects of different reaction parameters on % HMF yield were
investigated using experimental design and found that reaction temperature is the key
parameter in fructose dehydration. The SILnPs catalysts developed in this study
showed improved activity than other previously reported zeolites and strong acid ion
exchange resin catalysts. They have been efficiently and very easily recycled over
seven times without any significant loss in fructose conversion (99.9%) and HMF yield
(63.0%) at the optimized reaction conditions.

COIL-4:246
Chemical Recycling Monomers of Polycarbonate by Using Ionic Liquids
Shwu-Jer Chiu (1) , sjchiu@mail.mcut.edu.tw, 84, GungJuan Rd., Taishan, New Taipei
24301, Taiwan Republic of China ; Tzu-Husan Hsu (1) . (1) Department of Chemical
Engineering, Ming Chi University of Technology,, New Taipei 24301, Taiwan Republic
of China
Chemical recycling monomers of polycarbonate (PC), bisphenol A (BPA) and dimethyl
carbonate (DMC), in the presence of methanol was investigated by using ionic liquids
as a solvent and catalyst. The depolymerization of PC was carried out in an autoclave
under autogeneous pressure. A number of ionic liquids were employed to screen the
activity for depolymerization of PC, as well as the percentage of monomers recovery,
and the effects of reaction temperature, reaction time, and weight ratio of ionic
liquid:methanol:PC were also examined. The solid residue was characterized as
unreacted PC by FTIR and SEM if it was exited at the end of reaction. The composition
and concentration of liquid products was analyzed by GC/MS and GC, respectively. It
was found in the case of depolymerization temperature 100 o C, time 60 min, and weight
ratio of ionic liquid:methanol:PC equal 1:1:2, the conversion of PC depolymerization in
the ionic liquid 1-Hethyl-3-methylimidazole chloride, [Hmim]Cl, the conversion of PC
depolymerization was 100% and showed a good result of recovering monomers BPA
and DMC. The effect of number of cycles using ionic liquid on the conversion of PC
depolymerization and percentage of monomers recovery were also considered in this
study.
COIL-4:247
Development of CO2 Removal Technology Under Extremely Dilute Condition
Using Ionic Liquids
Takashi Makino (1) , m-kanakubo@aist.go.jp, 4-2-1 Migataka, Miyagino-ky Senjau,
Miyagi 983-8551, Japan ; Mitsuhiro Kanakubo (1) ; Tatsuya Umecky (1) ; Akira Suzuki (1) ;
Masato Sakurai (2) . (1) National Institute of Advanced Industrial Science and Technology
(AIST), Japan (2) Japan Aerospace Exploration Agency, Japan
Ionic liquids have attracted much attention as physical and/or chemical absorbents to
separate acidic gases because they are less flammable, nearly involatile, chemically
and thermally stable, and show excellent solubility. Although many researchers have
studied solubility of single pure gases in ionic liquids, there have been a very limited
data for binary and multi-component gas mixtures, in particular, at dilute concentrations.
In the present work, we have made a challenge to eliminate CO2 at extremely dilute
concentration, 4000 ppm, in N2 by using hybrid ionic liquid mixtures composed of
physical and chemical absorbents. The CO2 uptakes in the hybrid mixtures with different
concentrations were investigated as a function of time at different temperatures; CO2
was found to be removed more effectively at lower temperatures. We have also

examined that the hybrid mixtures saturated with CO2 can be regenerated without loss
of the absorbent by degassing treatment under vacuum. Based on the above results,
the possible air purification technology by the pressure swing absorption, leading to
reduction of intensive thermal regeneration energy, will be discussed for the future
application in some specific environments such as “aerospace”, where the vacuum
treatment can be readily performed without a lot of additional power.
COIL-4:248
P-V-T Relations for Ammonium-Based Ionic Liquid + Carbon Dioxide Binary
Systems
Takashi Makino (1) , makino.t@aist.go.jp, 4-2-1 Nigatake, Miyagino-ku, Sendai Miyagi
983-8551, Japan ; Mitsuhiro Kanakubo (1) ; Tatsuya Umecky (1) ; Akira Suzuki (1) . (1)
Research Center for Compact Chemical System, National Institute of Advanced
Industrial Science and Technology, Sendai Miyagi 983-8551, Japan
Volumetric properties of ionic liquids, especially in equilibrium with gas components, are
important for both related technologies and fundamental physicalchemistry.
Nevertheless, a few studies have been carried out on the volumetric properties for gas +
ionic liquid systems under two-phase equilibrium conditions. This paper reports p-V-T
relations for ionic liquid + carbon dioxide systems. We focused on the molar
concentration of carbon dioxide in ammonium-based ionic liquids with the
bis[trifluoromethanesulfonyl]amide anion. These ionic liquids have a cation containing
ether or carbonyl groups. The purpose of this study was to discuss the effect of such
functional groups on the molar concentration and molar ratio of carbon dioxide in ionic
liquid phase. In general, the ammonium-based ionic liquid shows smaller carbon dioxide
solubility than the imidazolium-based. However, the present data indicate that the molar
concentration and molar ratio of some ammonium ionic liquids are comparable with
those of imidazolium ones. Further data and discussion would be shown in the
presentation. The experiments of this study followed the development of two
experimental setups. One apparatus was used to measure the volumetric change of
ionic liquid phase by the dissolution of gases. The molar amount of gas dissolved in
ionic liquid phase was separately obtained with the other apparatus by reading the
pressure drop. Both the information enabled us to acquire p-V-T relations at given
temperatures and pressures. The expanded uncertainties of the molar concentration
and molar ratio were 0.07 mol dm -3 and 0.006, respectively. It has been confirmed that
the solubility data for 1-butyl-3-methylimidazolium bis[trifluoromethanesulfonyl]amide
agree well with those reported in literature.
COIL-4:249
CO2 Absorption Properties of Glyme-Li Salt Complex Solutions
Daisuke Kodama (1) , dkodama@chem.ce.nihon-u.ac.jp, 1 Nakagawara, Tokusada,
Tamura-machi, Koriyama Fukushima 963-8642, Japan ; Mitsuhiro Kanakubo (2) ; Satoshi

Hashimoto (1) ; Takashi Makino (2) ; Tatsuya Umecky (2) ; Akira Suzuki (2) . (1) College of
Engineering, Department of Chemical Biology and Applied Chemistry, Nihon University,
Koriyama Fukushima 963-8642, Japan (2) National Institute of Advanced Industrial
Science and Technology (AIST), Sendai Miyagi 983-8551, Japan
Room-temperature ionic liquids (RT-ILs) generally have negligibly small vapor pressure,
high thermal and chemical stability, and can have higher solubilities of acidic gases
such as CO2, NOx and SOx than those of normal gases, N2, H2, and O2. These attractive
properties could lead the way to clean gas separation technologies that eliminate
emissions of the liquid absorbent into the atmosphere. We have proposed an effective
CO2 separation process from gas mixtures by physical absorption using ionic liquids. In
the present study, the solubilities and saturated liquid densities of CO2 in glyme-Li salt
complex solutions, which show similar properties as RT-ILs, have been measured at
high pressures and at 313.15 K without any analysis of phase compositions. The
solubilities of CO2 in glyme-Li salt complex solutions slightly decreased by salting-out
effect compared with those in pure glymes, as shown in Fig. 1. On the other hand, the
amount concentrations of CO2 and glyme-Li salt complex solutions have not changed in
the present systems. Furthermore, the density, viscosity, and electrical conductivity of
glyme-Li salt complex solutions were measured at atmospheric pressure.
COIL-4:250
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Experimental and Theoretical Study of Kinetics of 1-Butyl-3-Methylimidazolium
Bromide Synthesis
Yauheni U. Paulechka (1) , paulechka@bsu.by, Leningradskaya 14, Minsk - 220030,
Belarus ; Dzmitry S. Firaha (1) ; Gennady J. Kabo (1) . (1) Chemistry Faculty and Reseach
Institute for Physical Chemical Problems, Belarusian State University, Minsk 220030,
Belarus
Quaternization of 1-methylimidazole (MeIm) by 1-halobutanes is a key stage in
synthesis of 1-butyl-3-methylimidazolium ionic liquids (ILs). In this work we studied
kinetics of the reaction of MeIm with 1-bromobutane (BuBr) in acetonitrile media in a
wide range of concentrations, temperatures and degrees of conversion. It was found
that in diluted solutions the studied reaction follows the expected SN2 kinetics. However,
at higher concentrations of the reagents, deviation from the simple SN2 rate law was
observed. This deviation was caused by the concentration dependence of activity
coefficients for the reagents and the transition state. The activity coefficients were
calculated using the COSMO-SAC model as well as the Sketchard-Hildebrand (SH)
equation. Both the approaches were found to provide good description of the
experimental data in the range of concentrations 0–1.8 mol·dm -3 for MeIm and 0–4.7
mol·dm -3 for BuBr. The values of the activation energy of the studied reaction calculated
from the obtained kinetic data using both COSMO-SAC and SH equation were very
close and agreed with the literature values for similar systems.

COIL-4:251
Some Organic Reactions in Pyrrolidinium Ionic Liquids
Kwok-Yin Wong (1) , bckywong@polyu.edu.hk, Dept of ABCT, HK PolyU, Hunghom
Kowloon, Hong Kong Special Administrative Region of China; Wing-Leung Wong (1) ;
Kam-Piu Ho (1) . (1) Applied Bio & Chem Tech, Hong Kong Polytechnic University,
Hunghom, Kowloon, Hong Kong Special Administrative Region of China
Ionic liquids have been promoted as green solvents and electrolytes as they are nonvolatile
and recyclable, and possess tunable polarity and miscibility with various organic
and inorganic compounds. Although ionic liquids based on imidazolium salts have been
extensively used, they are unstable upon prolonged electrolysis or in the presence of
strong oxidizing agents. In our laboratory, we have been investigating pyrrolidiniumbased
ionic liquids for various organic transformation reactions including cycloaddition
of carbon dioxide to epoxides, epoxidation of alkenes by peracids, and hydration of
alkynes to ketones. The pyrrolidinium ionic liquids possess superior stability over the
imidazolinium counterparts and the results will be discussed in this presentation.
COIL-4:252
Simulation of the Solution Structure and Transport Properties of Anionic [PtCl6] 2-
and [PtCl4] 2- Metal Complexes in 1-Alkyl-3-Methylimidazolium Ionic Liquids
Gerhard A Venter (1)(2) , gerhard.venter@uct.ac.za, PD Hahn Building, Rondebosch
Western Cape 7701, South Africa . (1) Department of Chemistry, University of Cape
Town, Rondebosch Western Cape 7701, South Africa (2) Scientific Computing
Research Unit, University of Cape Town, Rondebosch Western Cape 7701, South
Africa
Understanding the solution structure and concomitant transport properties of heavy
metal ions and transition metal complexes in room temperature ionic liquids (RTILs) has
implication in studying the processes of extraction and/or separation, and muliphase
catalysis. In this work, the focus is on octahedral and square planar anionic complexes
of hexachloroplatinate(IV) and tetrachloroplatinate(II). These chlorinated species are
important in platinum group metal (PGM) separation, where they are the dominant
species encountered in extraction methods. These complexes have also been used as
precatalysts and/or catalytically active species in oxidation of methane to methanol.
Using classical molecular dynamics simulations of >100ns the dynamical structure and
transport properties of these species, through pair and spatial distribution functions and
calculated translational and rotational diffusion constants, are compared in room
temperature ionic liquids of 1-alkyl-3-methylimidazolium chloride, with C4 (butyl), C6
(hexyl) and C8 (octyl) alkyls. The dynamical behavior of the ionic liquid solvent is known
the be very slow, and it is found that long simulation times are required to present a
sufficiently converged set of properties of the solute. The transferability of nonpolarizable
force field parameters for the metal complexes, derived for aqueous-type

simulations, to ionic liquids are evaluated and discussed. The coordination in solution
between the ionic liquid cation (predominantly through the acidic C2 proton on the
imidazolium ring) and the metal complexes is also elaborated on.
COIL-4:253
2D and 3D Superlattices of Gold Nanodisks Obtained By Sputtering Deposition
onto Nitrile Functionalized Ionic Liquid
Pedro Migowski (1) , pmigowski@gmail.com, Av. Bento Gonçalves, Porto Alegre RS
91501-970, Brazil ; Heberton Wender (2) ; Adriano F Feil (2) ; Luciana F de Oliveira (1) ;
Martin H G Prechtl (1) ; Giovanna Machado (3) ; Sérgio R Teixeira (2) ; Jairton Dupont (1) . (1)
Instituto de Química, Universidade Federal do Rio Grande do Sul, Porto Alegre Rio
Grande do Sul 91501-970, Brazil (2) Instituto de Física, Universidade Federal do Rio
Grande do Sul, Porto Alegre Rio Grande do Sul 91501-970, Brazil (3) Nanotecnologia,
CETENE, Recife PE 50.740-540, Brazil
This work reports the production of 2D and 3D superlattices of gold nanodisks (NDs)
obtained by sputter deposition of Au onto a nitrile functionalized ionic liquid (IL), namely
1-(butyronitrile)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [(BCN)MI.N(Tf)2].
The unexpected formation of Au NDs was strongly corroborated by several
characterization techniques, including transmission electron microscopy (TEM), small
angle X-ray scattering (SAXS), TEM tomography and scanning force microscopy (SFM).
It was observed that the formation of Au NDs as well as their size distributions depends
on the sputtering deposition conditions. As the sputtering discharge voltage increased,
the population of NDs decreased and a population of smaller nanospheres (NSs)
appears. Moreover, no Au NDs were observed when discharge voltages higher than
340 V where used. The formation of nanodisks could be related to a strong interaction
between the sputtered Au atoms and the functionalized IL surface, leading to a
preferential lateral growth of the gold nuclei. Furthermore, as the sputtering discharge
voltage increases more energetic Au atoms are ejected from the Au target, thus having
sufficient energy to penetrate deeply on the IL surface. Therefore, the energy of the
sputtered atoms seems to be governing the nanoparticles growth. Highly energetic
sputtered Au atoms will interact loosely with the outmost nitrile groups, and the Au
nanoparticles growth occurs in a chemical environment that favours the formation of Au
NSs. These findings open up a new way to design experiments to produce NPs with
unusual shapes and sizes. Moreover, the simple change in surface composition of the
functionalized ILs might yield new and unexpected anisotropic NPs whose synthesis is
not possible with classical colloidal methods.
COIL-4:254
Solvent-Free, Microwave Synthesis of Ionic Liquid Crystal Compounds Based on
Imidazole

Julien FOUCHET (1) , Julien.Fouchet@ipcms.u-strasbg.fr, 23 rue du Loess, BP-43,
Strasbourg 67034, France . (1) IPCMS/DMO, IPCMS/DMO, University of Strasbourg,
Strasbourg 67034, France
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}div.Section1 { page: Section1; } Ionic liquids are attracting increasing interest for their
applications as solvents in organic synthesis, catalysis and electrochemistry. Ionic
liquids based on an imidazolium core are especially useful in that we can adjust their
properties (melting point, viscosity, polarity, …) by changing the structure and the nature
of both the cation and anion. These compounds are non volatile, non-flammable, and
both thermally and chemically stable. Liquid crystals combine the properties of an
isotropic liquid (mobility) and a crystalline solid (order in position and direction). Almost
all such mesomorphic compounds are based on two antagonistic units: a rigid and/or
hydrophilic part and a flexible and/or hydrophobic part. The combination of ionic liquid
and liquid crystalline properties could provide a vast range of interesting new materials.
For this, the imidazolium unit is again an excellent platform that can be designed to
promote liquid crystalline phases and can be easily prepared with a large variety of
anions. Extending some preliminary work, we report a solvent-free, microwavepromoted
N-arylation (Ullman-type coupling) of imidazole as means of expanding the
aromatic core and obtaining unsymmetrical imidazolium liquid crystals. Various
compounds showing ionic liquid or liquid crystal behaviour have been obtained.
Introduction of substituted aromatic and heterocyclic groups is planned in order to
improve electronic properties and to obtain room temperature ionic liquid crystals.
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COIL-4:255
Characterization of the Effect of Atmospheric Water on the Hydrogen Bond on
Butyl Methyl Imidazolium Chloride ([BMIM] + Cl - ) by Terahertz Spectroscopy
Heidy Visbal (1) , heidy@kri-inc.jp, Kyoto Research Park, 134, Chudoji Minami machi,
Shimogyou ku, Kyoto Kyoto 600-8813, Japan ; Atsushi Mizusawa (2) ; Hideki Kawazaki (1) ;
Toshimi Fukui (1) . (1) Nano-hybrid Research Laboratory, KRI, Inc, Kyoto Kyoto 600-8813,
Japan (2) Nano-Structured Materials Research Laboratory, KRI, Inc., Kyoto Kyoto 600-
8813, Japan
In this work we characterize the effects of water content on the interaction between
anion-cation of [BMIM] + Cl - by terahertz spectroscopy in the 0.1 THz to 3 THz range.
Density functional theory (DFT) method was used to calculate the structure of ionic
liquid and discuss the non-bond interaction in the ion pair. The [BMIM] + Cl - was heated
at 80� in vacuum (~10 -1 torr) for 24 hs and was transferred to a dry box (dew point < -
90�). The sample was prepared between two quartz plates and sealed with kapton
tape to avoid the contact with atmospheric water. The terahertz spectrum was

measured at this point and after removing the kapton seal at 0 and 30 min. The
DFT results showed that the THz spectra in this region did not originate from the
intramolecular vibrations of the imidazolium cations. The terahertz spectrum showed a
sharp peak around 1.8 THz for the kapton-sealed sample. This peak shifted to a low
wavenumber when kapton tape was removed and atmospheric water contacted by the
orifice of the sample holder. This effect can be explained due to the ion-ion separation
becomes larger and weaker. The shoulder peak around 1.6 THz was enhanced after
contact with atmospheric water. It should be attributed to new interactions with water
molecules. We concluded that the interion vibrations are affected by the atmospheric
water contents in the ILs.
COIL-4:256
Physi- and Chemisorption of Ionic Liquids onto Silica
Ralf Lungwitz (1) , ralf.lungwitz@s2000.tu-chemnitz.de, Strasse der Nationen 62,
Chemnitz 09111, Germany ; Stefan Spange (1) ; Thomas Linder (2) ; Jörg Sundermeyer (2) .
(1) Department of Polymer Chemistry, Chemnitz University of Technology, Chemnitz
09111, Germany (2) Department of Inorganic Chemistry, Phillips-University Marburg,
Marburg 35032, Germany
The interaction of Ionic Liquids (IL) with solid surfaces play an important role in many
catalytic processes e.g. procedures using supported Ionic Liquid phase catalysts. To
combine the chemistry of ILs with the advantages of heterogeneous catalysis, the ILs
have been physi- and chemisorbed onto the silicatic support. The main goal of
this work is the targeted physi- and chemisorption of ILs onto silica. Nmethylimidazolium
chloride shows a strong anion mediated physisorption, when
adsorbed onto Aerosil ® 300. 1 The reaction of basic IL-precursors (ylides, carbenes,
carboxylates) with silica was performed in order to achieve chemisorption of Ionic
Liquids. Thereby, the formed cation build up hydrogen bonds to the simultaneous
generated surface silanolate anions. 2 [1] R. Lungwitz, S. Spange, J. Phys.
Chem. C, 2008, 112, 19443. [2] R. Lungwitz, T. Linder, J. Sundermeyer, I. Tkatchenko,
S. Spange, Chem. Commun., 2010, 46, 5903.
COIL-4:257
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Relation Between H-Bond Acidity and Basicity in Ionic Liquids
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Heiko Niedermeyer (1) , heiko.niedermeyer06@imperial.ac.uk, Chemistry, South
Kensington Campus, London London SW7 2AZ, United Kingdom ; Tom Welton (1) ;
Patricia A. Hunt (1) . (1) Department of Chemistry, Imperial College London, London SW7
2AZ, United Kingdom

It is well known that the H-bond acidity of ionic liquids is mainly controlled by the cation,
while the H-bond basicity depends mainly on the anion. If measured by solvatochromic
probes in the Kamlet-Taft parameter scheme, these two properties however are not
entirely independent. As can be seen in the figure, high β values, indicating strong Hbond
basicity, tend to lower the apparent H-bond acidity of the cation in the ionic liquid.
However the opposite does not seem to be the case, as the H-bond basicity is almost
entirely independent of the α value of the corresponding cation. Possible
explanations for this are analyzed computationally, experimentally and using simple
chemical equilibria and the possibility of multiple sites of interaction at anion and cation
is studied.
COIL-4:258
Properties of Ionic Liquids Based on Oxofluoroanions (PO2F2 − , SO3F − , VOF4 − ,
WOF5 − , and MoOF5 − )
Kazuhiko Matsumoto (1) , k-matsumoto@energy.kyoto-u.ac.jp, Yoshida Sakyo-ku, Kyoto
Kyoto 606-8501, Japan ; Takeshi Enomoto (1) ; Takatsugu Kanatani (1) ; Rika Hagiwara (1) .
(1) Graduate School of Energy Science, Kyoto University, Kyoto Kyoto 606-8501, Japan
Ionic liquids based on fluorocomplex anions are widely used in electrochemistry and
synthetic chemistry. Oxofluoroanions are also interesting candidates as counter anions
in ionic liquids. In the present study, physical, chemical, and electrochemical properties
of ionic liquids based on some oxofluoroanions are reported. The PO2F2 − and SO3F−
anions have sizes between the two popular anions, BF4 − (Td) and PF6 − (Oh), with lower
symmetry (C2v and C3v). Both [EMIm][PO2F2] and [EMIm][SO3F] (EMIm + : 1-ethyl-3methylimidazolium)
are room temperature ionic liquids and have ionic conductivities of
12 and 11 mS cm –1 , respectively. A solvatochromic method suggests that the donor
properties of a series of fluoro- and oxofluorocomplex anions have the order of PF6 − <
BF4 − < N(SO2CF3)2 − < SO3CF3 − < SO3F − < PO2F2 − . Electrochemical windows measured
on a vitreous carbon electrode for [EMIm][PO2F2] and [EMIm][SO3F] are 4.2 V and 4.3
V, respectively. Oxofluoroanions of transition metals (VOF4 − , WOF5 − , and MoOF5 − ) are
also combined with some alkylimidazolium, pyridinium, and pyrrolidinium cations. The
VOF4 − anions form a polymeric unit in the solid state, leading to the high melting point
(75 o C for [EMIm][VOF4]). [EMIm][MoOF5] and [EMIm][WOF5] are room temperature
ionic liquids with viscosities of 86 and 105 cP. The electrochemical windows of
[EMIm][MoOF5] and [EMIm][WOF5] are narrower than those of [EMIm][PO2F2] and
[EMIm][SO3F] because of the lower stability of WOF5 − and MoOF5 − against reduction.
COIL-4:259
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Effectiveness of Hydrated Ionic Liquid Composed Of Choline Cation and
Dihydrogen Phosphate Anion as a Medium for Biomolecules

Kyoko FUJITA (1) , kyokof@cc.tuat.ac.jp, 2-24-16 Nakacho, Koganei Tokyo 184-8588,
Japan ; Hiroyuki OHNO (1) . (1) Department of Biotechnology, Tokyo University of
Agriculture and Technology, 2-24-16 Nakacho, Koganei Tokyo 184-8588, Japan
Ionic liquids (ILs) containing small amount of water have attracted attention because of
potential possibility as a new solvent for biomolecules [1]. Solubility of proteins in
general ILs is quite low. In this report, we describe the solubility and activity of some
proteins and biomolecules in hydrated dihydrogen phosphate (Hy[ch][dhp]). The
Hy[ch][dhp] was prepared by mixing [ch][dhp] with different amount of water to
preliminarily examine the physico-chemical properties. Considering viscosity, melting
point and other properties, we fixed the amount of water to be 30 wt%. In this mixture,
about five water molecules were hydrated directly to one ion pair. The Hy[ch][dhp]
dissolved some biomolecules including metaroproteins such as cytochrome c,
peroxidase, ascorbate oxidase, azurin, pseudoazurin and fructose dehydrogenase
without any chemical modification. These biomoleules were confirmed to maintaine
higher ordered structure around the active site after dissolution in the Hy[ch][dhp] [2].
The activity of some biomolecuels have been analyzed as a function of storage time in
the Hy[ch][dhp] [3]. References 1 K. Fujita, D.R. MacFarlane and M. Forsyth, Chem.
Commun., 2005, 4804. 2 K. Fujita and H. Ohno, Biopolymers, 2010, 93, 1093. 3 K.
Fujita, N. Nakamura, K. Igarashi, M. Samejima, H. Ohno, Green Chemistry, 2009, 11,
351.
COIL-4:260
Physiochemical Properties of Ionic Liquid-Water Mixtures
Simon Peter Gallagher (1) , simon.gallagher24@mail.dcu.ie, Dublin City University,
Glasnevin, Dublin Dublin Dublin 9, Ireland ; Robert Byrne (1) ; Dermot Diamond (1) . (1)
National Centre for Sensor Research, Dublin City University, Dublin Dublin Dublin 9,
Ireland
In order for Ionic Liquids (ILs) to be utilized to their full potential, it is necessary to have
a complete understanding of their physical properties, including phase transitions
temperatures 1 . We have previously reported into the extent of structuring of ILs using
photochromic molecular probes, and investigated the appropriate IL water content to
yield hydrated IL systems for analysis of polarity and to create environments suitable for
effective enzyme activity 1,2,3 . In this study we investigated interactions in hydrated ILs
containing variable hydrophobic and hydrophilic regions through optical and thermal
analysis. The enthalpies and phase transitions of the systems were compared, between
the temperature range -50°C to +30°C for the ILs with varying degrees of hydration.
Reichardt's dye was used as a molecular probe to monitor changes in interactions in the
ILs as a function of temperature. Comparisons were made between ILs and for ILs with
varying degrees of hydration. Spectroscopic studies were performed using Perkin Elmer
UV-Visible Spectrometer and phase transitions monitored using Perkin Elmer
Differential Scanning Calorimeter. The ILs examined are;
Trihexyltetradecylphosphonium Chloride [P6,6,6,14 Cl], Tributyltetradecylphosphonium

[P4,4,4,14 Cl], 1-Ethyl-methyl-3-imidazolium-ethyl Sulfate [Emim][EtSO4] and
Trihexlytetradecylphosphonium [P6,6,6,14 DCA]. 1. Robert Byrne, Simon Coleman,
Simon Gallagher, and Dermot Diamond. Designer Molecular Probes for Phosphonium
Ionic Liquids. Physical Chemistry Chemical Physics, 2010. 2. Kyoko Fujita, Douglas R.
MacFarlane, Maria Forsyth, Masahiro Yoshizawa-Fujita, Kenichi Murata,† Nobuhumi
Nakamura, and Hiroyuki Ohno*,Solubility and Stability of Cytochrome c in Hydrated
Ionic Liquids: Effect of Oxo Acid Residues and Kosmotropicity, 2007. 3.Sergei V.
Dzyuba and Richard A. Bartsch, Expanding the polarity range of ionic liquids,
Tetrehedron Letters, 2002.
COIL-4:261
Neutron Diffraction Studies on Emim[FeCl4]. A Magnetic Ionic Liquid with Long-
Range Magnetic Ordering
Imanol de Pedro (1) , depedrovm@unican.es, Avda Los Castros s/n, Santander
Cantabria 39005, Spain ; Abel Garcia Saiz (1) ; Jesus A. Blanco (2) ; Maria T. Fernandez
Diaz (3) ; Jesus Rodriguez Fernandez (1) . (1) Departament of Magnetic materials CITIMAC,
Facultad de Ciencias, Universidad de Cantabria, Santander Cantabria 39005, Spain (2)
Departament of Physics, Universidad de Oviedo, Oviedo Asturias 33007, Spain (3)
Institut Laue-Langevin, Grenoble Cedex BP 156X, F-38042, France
Ionic liquids with anions containing transition metal complexes (i.e. magnetic ionic
liquids or MILs) are the earliest developed RTILs [1] These new materials are
considered to open up a wide range of applications in relation with their magnetic
properties and electrochromic switching such as transport and separation of materials
[2], magnetic fluids based on nanoparticles [3], acting as an absorbent liquid when
applying a magnetic field, catalysis process, or as effective extractants for the
desulfurization (SOx) from fuel oils [4]. Up to now, the few magnetic studies performed
in RTMILs showed paramagnetic behaviour, with only small deviations from the Curie
law at low temperatures. However, we have found, for the first time, a long-range
magnetic ordering of a RTMIL. The physical properties of 1-ethyl-3-methylimidazolium
tetrachloroferrate Emim[FeCl4] clearly show a long-range antiferromagnetic ordering
when it is frozen (polycrystalline state at 280 K) with a Néel temperature TN ∼ 3.8 K [5].
We present the study of this material using both high resolution and variable
temperature neutron powder diffraction experiments confirming the three-dimensional
magnetic ordering and giving further insight in the origin of the magnetic behaviour at
low temperatures. In addition, a solid–solid transition below Tt= 210 K has been
detected indicating polymorphism behaviour. [1] S. Hayashi, et al., Chem. Lett. 33
(2004) 1590. [2] M. Okuno, et al., Appl. Phys. Letter. 89 (2006) 132506. [3] F.C. Oliveira,
et al., J. Phys. Chem. 113 (2009) 8566. [4] Nan Hee Ko et al., Energy & Fuels (2008)
22, 1687. [5] de Pedro I, et al., J. Phys: Condens. Matter, (2010) 22 296006.
COIL-4:262
Structures and Dynamics of Cyclohexyl-Substituted Imidazolium Ionic Liquids

Toshihiko Mandai (1) , monday1004@graduate.chiba-u.jp, 1-33 Yayoi-cho, Inage-ku,
Chiba-shi, Chiba-shi Chiba 263-8522, Japan ; Mamoru Imanari (2) ; Hyuma Masu (2) ; Keiko
Nishikawa (1) . (1) Department of Nano Science, Graduate School of Advanced
Integration Science, Chiba University, Chiba-shi Chiba 263-8522, Japan (2) Chemical
Analysis Center, Chiba University, Chiba-shi Chiba 263-8522, Japan
We have synthesized and characterized a series of cyclohexyl-substituted imidazolium
based ionic liquids incorporating a bis(trifluoromethanesulfonyl)amide and a tosylate
anions. To reveal the characteristic features afforded by a flexible and bulky
cyclohexyl substituent, the physicochemical properties including densities, shear
viscosities, and thermal properties, were measured and compared with the respective nalkyl-imidazolium
ionic liquids. The cyclohexyl-imidazolium ionic liquids showed higher
densities, higher shear viscosities, and higher glass transition temperatures than their
acyclic counterparts. Using 1 H and 13 C nuclear magnetic resonance spectra, we also
studied the conformational dynamics of these species. Activation energies for the
segmental motion of each carbon were estimated from the linear slope of the Arrhenius
plot for the correlation time. Values of the activation energies suggest that the
cyclohexane ring has lower flexibility than the respective n-alkyl group. This conclusion
is consistent with the macroscopic observations. In the presentation on the day, we will
also report and discuss the crystal structures of cyclohexyl-substituted imidazolium
tosylate salts.
COIL-4:263
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Effect of Anion Structure to Thermal Properties on Alkali Metal
(Fluorosulfonyl)(Trifluoromethylsulfonyl)Amides
Keigo Kubota (1) , keigo-kubota@aist.go.jp, 1-8-31, Midorigaoka, Ikeda Osaka 563-
8577, Japan ; Hajime Matsumoto (1) . (1) Research Institute for Ubiquitous Energy
Devices, Advanced Industrial Science and Technology (AIST), Osaka 1-8-31
Midorigaoka, Ikeda 563-8577, Japan
Alkali metal salts containing low coordinating anions are important compounds not only
for raw materials of ionic liquids but for industrial applications such as supporting
electrolytes of lithium ion batteries. Among them, we have focused on alkali metal
containing perfluorosulfonylamide anions such as [(FSO2)2N] - ([C0C0] - ) and
[(CF3SO2)2N] - ([C1C1] - ) and studied their thermal properties which are fundamental and
important information for their applications. Furthermore, this study will be available to
discuss about structure dependences. Physicochemical properties, especially thermal
properties of ionic liquids might be greatly affected by structures of cations and anions.
Though effects of cation structures are extensively studied due to easy designing of
cation structures, those of anion structures are not widely due to lack of variety of
anions. Comparison of thermal properties of alkali metal perfluorosurufonylamides are
considered to contribute to the discussion about their anion structures such as
symmetry. Recently, we have reported thermal properties of alkali metal salts

containing asymmetric (fluorosulfonyl)(trifluoromethylsulfonyl)amide
([(FSO2)(CF3SO2)N] - , ([C0C1] - ) [1]. For ionic liquids, compounds of the asymmetric anion
have lower melting points (Tm) than those of symmetric anion such as [C0C0] - and
[C1C1] - [2]. We have reported that these alkali metal salts have Tm at 100-150�. In the
result of detailed investigation, it was found that M[C0C1]s have unique phase behavior.
For Li[C0C1] and Cs[C0C1], liquid phases after melting were crystallized very slowly. For
Rb[C0C1] and Cs[C0C1], Tms are changeable due to crystal polymorphism. It is
considered that the features are caused by asymmetric structure and FSO2 side chain
of [C0C1] - . Referenecs [1] K. Kubota, T. Nohira, R. Hagiwara, H. Matsumoto, Chem.
Lett., 39, 1303, (2010). [2] H. Matsumoto, N. Terasawa, T. Umecky, S. Tsuzuki, H.
Sakaebe, K. Asaka, K. Tatsumi, Chem. Lett,. 37, 1020, (2008). Acknowledgement
This work was supported by R&D project for Li batteries (Li-EAD) by NEDO.
COIL-4:264
Merging the Chemistry of Electron-Rich Olefins (ERO) With Imidazolium Ionic
Liquids
J. Clyburne (1) , jason.clyburne@smu.ca, 923 Robie Street, Halifax Nova Scotia
B3H3C3, Canada ; C. Walsby (2) ; C. Sherren (1) ; C. Mu (2) ; I. McKenzie (2) ; B. McCollum (2) ;
J-C Brodovitch (2) ; T. Storr (2) ; K.R. Seddon (3) . (1) Department of Chemistry, Saint
Mary[apos]s University, Halifax NS, Canada (2) Department of Chemistry, Simon Fraser
University, Burnaby BC, Canada (3) School of Chemistry and Chemical Engineering,
Queen’s University Belfast, Belfast Northern Ireland, United Kingdom
Ionic liquids (ILs) have attracted attention because of their potential applications in
various industrial settings. This report will survey some chemistry of simple molecular
species with structurally simple reagents in ionic media. The chemistry of N-heterocyclic
carbenes is intimately associated with chemistry observed in imidazolium based ionic
liquids. Likewise, the chemistry of Electron-Rich Olefins (ERO) was important in the
early understanding of NHCs, and EROs possess chemistry that is unique among
alkenes. The link and relevance of EROs and IL chemistry has been ignored even
though there is some evidence indicating its role. Here we report that the ionic liquid 1ethyl-3-methylimidazolium
tetrachloroaluminate(III) reacts with lithium to produce a
persistent radical, which can be considered a hydrogen-atom adduct of an electron-rich
olefin (ERO). Reaction of tetrakis(dimethylamino)ethene, a bona fide ERO, with
muonium, produces a structurally similar radical. These results demonstrate the
importance of ERO chemistry to applications of ionic liquids, particularly where charge
carrying in basic conditions is important, such as in photocells.
COIL-4:265
Ionic Liquids as Effective Absorbents for Carbon Dioxide Capture

Stefan Baj (1) , stefan.baj@polsl.pl, Zamkowa 1, Zabrze; Slaskie 41-803, Poland . (1)
Institute for Chemical Processing of Coal, Institute for Chemical Processing of Coal,
Zabrze; Slaskie 41-803, Poland
The new methods for reducing the emissions of CO2 from the industrial gases are now
of a great importance. Recently, room-temperature ionic liquids (RTILs), possessing
negligible vapour pressures, high thermal stability, a large liquid range, having the ability
to dissolve many organic and inorganic substances, and being readily recyclable, have
been described as a promising alternative media for CO2-selective separation. Current
technologies for CO2 removal are based on aqueous amine solutions. However RTILamine
solutions can offer some advantages, e.g. lower energy consumption in the
process. Additionally, ionic liquids are nonvolatile and CO2 can be desorbed after the
process without loss of solvent and easily recycled. In the present work the solutions of
ionic liquids containing 12,5 weight % of monoethanolamine (MEA) or diethanolamine
(DEA) were investigated. The wide range of the room-temperature ionic liquids both
hydrophilic and hydrophobic was examined. The effects of the agitation speed,
temperature and concentration of amines in ionic liquids on the CO2 absorption process
were determined. Moreover, the solubility of amines in ionic liquids and the solubility of
corresponding carbamate salts were examined. On the basis of these studies the
systems in which carbamate salt forms a separated liquid phase and the systems where
carbamate participated in a solid state were chosen. Participation of the carbamate in a
separate phase permits to drive the capture reaction to the formation of more amounts
of carbamate. Easy removal of the carbamate phase from the mixture after absorption
of CO2 and the possibility of recycling of ionic liquid without of its loss make this method
useful for practical applications. Additionally, in two phase systems desorption energy
can be reduce.
COIL-4:266
HPILC: Dynamic Analysis of Cellulose Hydrolysis in Ionic Liquids
Kosuke Kuroda Kuroda (1) , 50010641205@st.tuat.ac.jp, 2-24-16 Nakacho, Koganei,
Tokyo Tokyo, Japan ; Yukinobu Fukaya (1) ; Hiroyuki Ohno (1) . (1) Department of
Biotechnology, Tokyo University of Agriculture and Technology, Tokyo Tokyo 184-8588,
Japan
We have already reported an HPLC system for the analysis of cellulose using ionic
liquids (ILs) as eluents, called high performance ionic liquid chromatography (HPILC) 1) .
HPILC has been developed to analyze scarcely soluble polymers. In this study, HPILC
has been applied for the direct analysis of hydrolysis of cellulose using 1-ethyl-3methylimidazolium
methylphosphonate (IL-1) as an eluent. The mixtures composed of
cellulose and glucose as models of hydrolyzed cellulose were preliminarily analyzed
with HPILC. The peaks were found independently and ratio of their peak area clearly
related to their mixing ratio. The cellulose was depolymerized in IL-1 with ultrasonication
not to disturb the component of the solution. The peaks for microcrystalline cellulose
and bacterial cellulose shifted depending on the sonication time. As a reference,

hydrolyzed cellulose in an aqueous phase with immobilized cellulase was also
analyzed. The peak for initial cellulose was lowered and shifted to a lower molecular
weight side. At the same time, the peaks for oligo-saccharides were detected. We then
performed hydrolyzed the celluloses with solid-acid in 1-allyl-3-methylimidazolium
chloride (IL-2), which has high thermal stability. Cellulose was confirmed to be
hydrolyzed with solid-acid in IL-2. All the data indicated that the HPILC system was
effective for the dynamic study for cellulose hydrolysis. 1) Y. Fukaya, A. Tsukamoto, K.
Kuroda, H. Ohno, Chem. Commun. 2011, 47, 1994.
COIL-4:267
Electrodeposition of Aluminium from An [NTf2]-Based Ionic Liquids: Unravelling
Complex Mechanisms from Complex Solutions
Jean-Pierre M Veder (1) , Jean-Pierre.Veder@csiro.au, Gate 1, Normanby Road, Clayton
Victoria 3168, Australia ; Theo Rodopoulos (1) ; Mike Horne (1) ; Thomas Ruether (2) ; Alan
Bond (3) . (1) Process Science and Engineering, CSIRO, Clayton Victoria 3168, Australia
(2) Energy Technology, CSIRO, Clayton Victoria 3168, Australia (3) School of
Chemistry, Monash University, Clayton Victoria 3168, Australia
Ionic liquids (ILs) are appealing media for the electrodeposition of metals that cannot
otherwise be deposited in aqueous systems. Unlike molecular solvents commonly
employed in electrodeposition processes, ILs are reactive media that deliver complex
coordination chemistry and have interesting metal solution properties. Hence
understanding the metal chemistry that underpins the electrodeposition process is
critical to improving the technology. Electrochemical studies (i.e. cyclic voltammetry,
chronoamperometry, etc.) on various ILs loaded with metal salt precursors demonstrate
that the mechanisms associated with the metal reduction and oxidation processes are
complex in nature and are seldom easy to comprehend. Nevertheless, it is apparent
that there is a wealth of knowledge that can be extracted from such techniques. It is
therefore appealing to utilize electrode substrates with ideal electrode behaviour such
as boron-doped diamond (BDD). BDD electrodes are ultrawide band-gap
semiconductors that are well suited for mechanistic studies of metal electrodeposition
because they do not overcomplicate the electrochemistry by the addition of unwanted
background electrode processes. This paper presents comparative results on the use
of boron-doped diamond (BDD) against other carbon-based electrodes (i.e. glassy
carbon (GC)) as well as two metallic electrodes (i.e. gold and platinum) for studying
interesting metal redox processes in ILs. The use of BDD is demonstrated as a superior
electrode substrate because it is free from surface functionalities on the hydrogenterminated
surface, is absent of alloying interactions with metal deposits, does not
contain any significant parasitic background reactions and is stable over the large
potential window of the IL. Such favourable electrode characteristics have enabled us to
probe and interpret the complex mechanism of aluminium electrodeposition in an [NTf2]based
IL.
COIL-4:268

Thiol-Yne Coupling Reactions as a Tool to Prepare Structurally Diverse Ionic
Liquids
Arsalan Mirjafari (1) , mirjafari@usouthal.edu, 307 N University Blvd., Mobile Alabama
36688, United States ; Richard A O[apos]Brien (1) ; Kevin N West (2) ; James H Davis,
Jr. (1)(2) ; Samuel M Murray (2) . (1) Department of Chemistry, University of South Alabama,
Mobile Alabama 36688, United States (2) Department of Chemical and Biomolecular
Engineering, University of South Alabama, Mobile Alabama 36688, United States
Presently ionic liquids (ILs) containing long aliphatic appendages are either highly
viscous liquids or solids at room temperature. Our group has previously shown sidechain
unsaturation to be a viable method for overcoming this process limitation and
depressing IL melting points. Thiol-yne chemistry has proven to be a versatile and
useful synthetic tool to prepare an array of organic molecules, including dendrimers. We
investigated thiol-yne chemistry with different yne-functionalized ILs by reacting them
photochemically with alkylthiols, yielding structurally diverse ILs in a single step. In
addition, we utilized differential scanning calorimetry to study the effects of both long
and branched substituents upon IL melting points. Imidazolium and quaternary
ammonium-based cations were selected as yn substrates for the study. Incorporation of
alkyl substituents in a vicinal position in these systems provided a unique tool to study
the structure-property relationship of ILs with thioether linkages and a variety of alkyl
appendages on the melting points. The synthetic methodology as well as the impact of
these structural modifications upon IL melting points will be discussed.
COIL-4:269
Pure Cellulose Nanoparticles from Trimethylsilyl Cellulose Synthesized In Ionic
Liquids
Marc Kostag (1) , Marc.Kostag@uni-jena.de, Humboldtstraße 10, Jena Thuringia 07743,
Germany ; Tim Liebert (1) ; Thomas Heinze (1) . (1) Faculty of Chemical and Earth
Sciences, Institute of Organic Chemistry and Macromolecular Chemistry, Center of
Excellence for Polysaccharide Research, Jena 07743, Germany
Silylethers of cellulose are interesting derivatives of the biopolymer because they exhibit
thermoplastic behavior at higher functionalization, may be applied as intermediate in
subsequent reactions and have a high tendency to form defined supramolecular
structures. Trimethylsilylation can be carried out by applying ionic liquids (ILs) such as
1-ethyl-3-methylimidazolium acetate, as reaction medium. Pure trimethylsilyl cellulose
(TMSC) can be efficiently synthesized with 1,1,1,3,3,3-hexamethyldisilazane (HMDS)
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yielding products with degrees of substitution (DS) up to 2.89. During the
synthesis of highly functionalized derivatives precipitation of the TMSC occurred, which
simplifies the recycling of the IL. The tendency of TMSC toward the formation of
supermolecular structures was exploited for the formation of pure cellulose
nanospheres by a simple dialysis process. FTIR spectroscopy confirmed the complete

emoval of the TMS functions during this process. Scanning electron microscopy,
dynamic light scattering, atomic force microscopy, and particle size distribution analysis
showed that cellulose particles with a size of 100 to 200 nm are accessible in this
simple manner.
COIL-4:270
High Pressure Phase Equilibria of Ionic Liquids and Carbon Dioxide Systems
Marina S Manic (1) , marina.manic@dq.fct.unl.pt, Quinta de Torre, Caparica 2829-516,
Portugal ; António J Queimada (2) ; Eugénia A Macedo (2) ; Manuel Nunes da Ponte (1) ;
Vesna Najdanovic-Visak (1) . (1) REQUIMTE/FCT/UNL, Caparica 2829-516, Portugal (2)
LSRE/LCM/FEUP, Porto 4200-465, Portugal
The CO2 solubility in eight different ILs, namely 1-butyl-3-methylimidazolium
bis(trifluoromethylsulfonyl)imide, [C4mim][NTf2], 1-decyl-3-methyl-imidazolium
bis(trifluoromethylsulfonyl)imide, [C10mim][NTf2], 1-butyl-1-methyl-pyrrolidinium
bis(trifluoromethylsulfonyl)imide, [bmpyr][NTf2], butyl-trimethyl-ammonium
bis(trifluoromethylsulfonyl)imide, [N4111][NTf2], methyltrioctyl-ammonium bis(trifluoromethylsulfonyl)imide,
[N1888][NTf2] and trihexyl-tetradecylphosphonium bis(trifluoromethylsulfonyl)imide,
[P66614][NTf2], trihexyltetradecylphosphonium bromide, [P66614][Br
and trihexyltetradecylphosphonium chloride, [P66614][Cl] was measured using a highpressure
sapphire cell, in the pressure range of (8 – 20) MPa and at two temperatures,
313 K and 323 K. The gas solubility was determined at each fixed temperature and
pressure. The variety of ILs chosen for this study gives an opportunity to discuss the
influence of the cation, as well as the anion on vapor-liquid equilibrium of ILs-CO2
systems. Despite the fact that experimental data already provides some information
about the systems and helps to understand their behavior, development of prediction
tools are very important due to the plenty of potential applications of ionic liquid
systems. The solubility data obtained in this work were used to evaluate the application
of the Cubic Plus Association equation of state (CPA EoS) to estimate the behavior of
the ILs-CO2 systems. A systematic study about how to obtain the pure component
parameters and the effect of considering or not both CO2 and ionic liquids as
associating components was performed. Acknowledgment: M.S. Manic is grateful to
Fundação para a Ciência e Tecnologia, Portugal, for the doctoral fellowships
SFRH/BD/45323/2008.
COIL-4:271
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Quantitative Analysis of A DNA Duplex Stability in a Hydrated Ionic Liquid
Naoki Sugimoto (1)(2) , sugimoto@konan-u.ac.jp, 7-1-20, Minatojima-minamimachi,
Chuo-ku, Kobe Hyogo 650-0047, Japan ; Hisae Tateishi-Karimata (1) . (1) Frontier
Institute for Biomolecular Engineering Research (FIBER), Konan University, Kobe

Hyogo 650-0047, Japan (2) Faculty of Frontiers of Innovative Research in Science and
Technology (FIRST), Konan University, Kobe Hyogo 650-0047, Japan
DNA has enormous potential for applications to advanced “green” materials such as
biosensors, biodevices, and biocircuits. For DNA materials to become practically
applicable, finding a medium in which DNA keeps unique abilities and is stable for long
time periods at room temperature is an important bottleneck. Room-temperature ionic
liquids (ILs) have generated tremendous interest as non-volatile media that provide
favorable environments for a wide range of chemical reactions and a variety of
bioapplications. Choline dihydrogenphosphate (choline dhp) with 20 wt% dissolved
water is one of the hydrated ILs, which has been demonstrated to be a good solvent for
proteins and DNAs for ensuring long-term stability. It is considered that the hydrated IL
is useful as a medium developing “green” DNA materials because the hydrated IL can
keep the activity of biomolecules for long time. However, its detail effect on the DNAs
remains unclear. Here, we have investigated quantitatively the behavior of DNA in
hydrated ILs. We examined stability of non-self-complementary DNA duplexes by
ultraviolet (UV) melting. The melting temperature (Tm) values of two DNA duplexes with
different sequences, ODN1 (A-T rich sequence) and ODN2 (G-C rich sequence), were
measured in solutions containing several molars choline dhp or NaCl. NaCl was used
as the reference because NaCl solution is a standard to measure DNA stability. Choline
dhp induced a drastic change in the duplex stabilities depending on their sequences
compared with the NaCl-containing solution. We also investigated the thermodynamic
parameters. The stability change of the DNA duplexes caused by choline dhp was
because the enthalpic contribution exceeded the entropic contribution. Our results
showed that it is possible to develop “green” DNA materials by applying a unique
interaction between ILs and DNAs.
COIL-4:272
Physical Properties of Three Commercial Imidazolium-Based Ionic Liquids: Effect
of The Anion
Emilio J. González (1) , emiliojgg@fe.up.pt, Faculty of Engineering, Rua Dr. Roberto
Frias s/n, Porto 4200-465, Portugal ; Eugenia A. Macedo (1) ; Raquel González (2) ; Sandra
Corderí (2) ; Ángeles Domínguez (2) . (1) LSRE Laboratory of Separation and Reaction
Engineering, Associate Laboratory LSRE/LCM, Department of Chemical Engineering,
University of Porto, Porto 4200-465, Portugal (2) Advanced Separation Processes
Group, Department of chemical engineering, University of Vigo, Vigo Pontevedra
36310, Spain
The ionic liquids (ILs) are relatively new compounds and experimental data on physical
properties of pure ILs are scarce. Nevertheless, this information is very necessary not
only for process and product design but also for the contribution to the databank of
thermodynamic properties. In this work, a systematic study of physical properties
(density, viscosity, and refractive index) of three commercial imidazolium-based ILs was
carried out as a function of the temperature. The ILs investigated were 1-hexyl-3-

methylimidazolium bis(trifluoromethylsulfonyl)imide, [HMim][NTf2], 1-hexyl-3methylimidazolium
trifluoromethylsulfonate, [HMim][TFO], and 1-hexyl-3methylimidazolium
dicyanamide, [HMim][N(CN)2]. The density, refractive index, and
viscosity were measured using an Anton Paar DSA-5000 digital vibrating tube
densimeter, an automatic refractometer ABBEMAT-WR Dr. Kernchen and an automatic
viscosimeter Lauda PVS1, respectively. These physical properties for [HMim][NTf2] and
[HMim][N(CN)2] were experimentally measured from (293.15 to 343.15) K and
atmospheric pressure, while for [HMim][TFO] it was measured from (303.15 to 343.15)
K and atmospheric pressure due to the melting point value, which is at 298 K. From the
experimental data, the effect of temperature and anion in the physical properties was
analyzed. A linear equation was used to express the correlation with the temperature for
density and refractive index, while dynamic viscosity values were fitted using Vogel-
Fulcher-Tamman (VFT) equation. As expected, all the measured properties decrease
when temperature is increased for the three studied ILs. The density of the studied ILs
containing the [HMim] + cation increases with molecular mass of the associated anion,
while for the refractive index the trend is the opposite. Regarding the viscosity, it can be
concluded that larger molecular weight of the anion do not correspond to larger viscosity
values.
COIL-4:273
Ionic Liquids as Solvents for Ruthenium-Catalyzed C-H Activation Reactions
Tobias Biletzki (1) , tobias.biletzki@freenet.de, August-Bebel-Straße 2, Jena Thuringia
07743, Germany . (1) Department of Chemical and Earth Sciences, Institute for
Inorganic and Analytical Chemistry, Jena Thuringia 07743, Germany
Biletzki, T., Imhof, W. Institute of Inorganic and Analytical Chemistry, Friedrich-Schiller-
University Jena, August-Bebel-Str. 2, 07743 Jena The catalytic four component
reaction of a, b-unsaturated aldehydes, primary amines, carbon monoxide and ethylene
(or terminal alkenes in general) produces chiral 2,3-dihydropyrrolones as the main
product in non-polar solvents and 2,3-disubstituded pyrroles as sideproducts. The
reaction is catalyzed by Ru3(CO)12 and the initial metal induced C-H activation/CO
insertion reaction sequence triggers a highly selective reaction cascade leading to the
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observed heterocyclic compounds. [1, 2, 3] Chemoselectivity of the reaction is
highly influenced by the relative permittivity of the solvent. [4] Optimization of the reaction
conditions in [C4mim][BTA] showed that the reaction works under milder conditions with
regard to reaction time and partial pressures of the gaseous substrates than when
performed in classical organic solvents. In some cases the ionic liquid phase containing
the ruthenium catalyst species might even be reused for up to three subsequent runs
after extracting the products. [5] [1] Berger, D., Imhof, W., J. Chem. Soc., Chem.
Commun. 1999, 1457-1458. [2] Berger, D., Imhof, W., Tetrahedron 2000, 56, 2015-
2023. [3] Dönnecke, D., Imhof, W., Tetrahedron 2003, 59, 8499-8507. [4] Gillies, G.,
Dönnecke, D., Imhof, W., Monatsh. Chem. 2007, 138, 683. [5] Biletzki, T., Stark, A.,
Imhof, W., Monatsh. Chem. 2010, 141, 413-418.

COIL-4:274
Design and Control of LCST-type Phase Transition of Ionic Liquid/Water Mixture
Yuki Kohno (1) , 50009831201@st.tuat.ac.jp, Naka-cho, Koganei Tokyo 184-8588,
Japan ; Shohei Saita (1) ; Hiroyuki Ohno (1) . (1) Department of Biotechnology, Tokyo
Univesity of Agriculture and Technology, Naka-cho, Koganei Tokyo 184-8588, Japan
Ionic liquids (ILs) containing phosphonium cations and amino acid anions with
trifluoromethanesulfonyl group on the amino group were clearly phase-separated with
water at room temperature, but homogeneously miscible upon cooling. 1) This became
immiscible again upon heating. This reversible phase transition, called lower critical
solution temperature (LCST), of the IL/water mixtures has not been reported previously.
However, there was no discussion on the required factors for IL/water mixture to show
the LCST-type phase behavior. In the present study, we studied the phase behavior of
several ILs after mixing with water, and analyzed necessary factors for IL/water mixture
to show LCST-type phase behavior. The miscibility of ILs with water has been analyzed
using 4 different phosphonium or ammonium cations, coupled with 12 different anions.
The miscibility of the ILs and water depended strongly on both the cation and anion
species, and a few IL/water mixtures showed LCST-type phase transition. The phase
separation temperature (Tc) of the ILs was controlled by both ion species and initial
amount of the added water. Since the water content in the IL-rich phase varied with
temperature, we studied the temperature dependence of the water content in the IL-rich
phase after phase separation. The number of water molecules per ion pair in the IL rich
phase (mwater) was found to depend strongly on the temperature. Upon heating, the
value of mwater for the IL-rich phase decreased considerably above the Tc. These results
clearly show that the LCST-type phase transition of IL/water mixtures involves an
exponential decrease of water content in the IL-rich phase. Since the mwater value was a
function of ion species, the Tc value can be controlled accurately by mixing some ILs
with different hydrophobicity. 1) K. Fukumoto, H. Ohno, Angew. Chem. Int. Ed., 2007,
46,1852.
COIL-4:275
Easy Preparation of Ion Conductive Ionic Liquids
Yuki Tsuji (1) , 50010831206@st.tuat.ac.jp, 2-24-16 Naka-cho, Koganei Tokyo 184-8588,
Japan ; Tomonobu Mizumo (1) ; Hiroyuki Ohno (1) . (1) Department of Biotechnology, Tokyo
University of Agriculture and Technology, Tokyo 2-24-16 Naka-cho, Koganei 184-8588,
Japan
We prepared benzimidazolate-based ionic liquids (ILs) by the neutralization of tetra-nbutylphosphonium
hydroxide ([P4444][OH]) and neutral benzimidazole (BzIm). 1 H−NMR
measurement revealed that the proton peaks attributed to the benzimidazolate anion
([BzIm]) shifted 0.3-0.6 ppm to the higher magnetic field side than those for neutral
BzIm. The shift strongly suggests the formation of [P4444][BzIm] salt. TG/DTA analysis

showed that the Td of neutral BzIm was 207 °C, whereas that for [P4444][BzIm] salt was
317°C. Furthermore, there was no decomposition signal for pristine BzIm in the TG/DTA
chart of the salt. These data all verify the formation of [P4444][BzIm] salt. Then, mixing
ratio was changed to realize either hydroxide ion conductor or proton conductor
(BzIm/[P4444][OH] with different amount of BzIm (x%, x=16.7-80%)). The [P4444][OH] rich
mixtures are expected as hydroxide ion conductive materials. On the other hand, BzIm
rich mixtures are expected as proton conductive materials. This system could easily be
controlled to prepare anion/cation conductive materials by just changing the mixing
ratio. The mixture with x= 16.7% showed the highest ionic conductivity, 3.57×10 −3 S
cm −1 at 60°C. This high ionic conductivity is suggested to the results of low glass
transition temperature (−67.1°C) and low viscosity (23 cP at 60°C). The mixtures with
x=54.5 and 60% showed excellent thermal stability showing one step thermogravimetric
loss at 315 and 311°C, respectively. By the chronoamperometric measurement with an
electrochemical cell equipped with platinum electrodes under hydrogen atmosphere,
this mixture was confirmed to show steady-state current suggesting the proton
conduction in the matrix.
COIL-4:276
Understanding Melting Point of Protic Ionic Liquids and Molten Salts at Molecular
Level
Koichi Fumino (1) , koichi.fumino@uni-rostock.de, Dr.-Lorenz-Weg 1, Rostock
Mecklenburg-Vorpommern 18051, Germany ; Ralf Ludwig (1) . (1) Institute of Chemistry,
Physical Chemistry, University of Rostock, Rostock 18051, Germany
Ionic liquids (ILs) are salts with uncommonly low melting point and are formed by a
combination of specific cations and anions leading to distinctive properties and a variety
of applications.[1,2] The working temperature range of any liquid is set by the melting
and boiling or decomposition point. In particular, the melting point (Tm) varies
substantially among different ILs. Until now no interpretation at the molecular level is
provided for these fundamental physical properties. Krossing et al. developed a simple
predictive framework to calculate Tm for ILs based on lattice and solvation free
energies.[3] They showed that ILs are liquid under standard ambient conditions
because the liquid state is thermodynamically favourable due to the large size and
conformational flexibility of the ions involved. That leads to small lattice enthalpies and
large entropy changes favouring the liquid state. Unfortunately, their method does not
give any correlation with experimentally obtained Tm for protic ionic liquids (PILs) as
shown by Markusson et al.[4] It is the purpose of this work to provide a moelcular
understanding for the exceptional Tm of ammonium ion-based PILs or molten salts. We
can show that Tm characteristically depends on the number of H-bond acceptors and
methyl groups at the various ammonium ions. The presence and extension of hydrogen
bonding in PILs is studied by far infrared and THz spectroscopy and supported by DFT
calculations on PIL aggregates. [1] P. Wasserscheid, T. Welton, Ionic Liquids in
Synthesis, 2nd Ed., VCH-Wiley, Weinheim, 2007. [2] H. Weingaertner, Angew. Chem.,
2008, 120, 664-682; Angew .Chem. Int. Ed., 2008, 47, 654-670. [3] I. Krossing, J. M.

Slattery, C. Dauguenet, P. J. Dyson, A. Oleinikova, H. Weingaertner, J. Am. Chem. Soc.
2006, 128, 13427-13434. [4] H.Markusson, J.-P. Belieres, P. Johansson, C. A. Angell,
P. Jacobsson, J. Phys. Chem. A, 2007, 111, 8717-8723.
COIL-4:277
Investigations on the Activity Profile of Immobilized Grubbs Metathesis Catalysts
in a Supported Ionic Liquid Phase (SILP) System
Judith Scholz (1) , Judith.Scholz@crt.cbi.uni-erlangen.de, Egerlandstrasse 3, Erlangen
Bavaria 91058, Germany ; Marco Haumann (2) ; Peter Wasserscheid (1) . (1) Department of
Chemical Reaction Engineering, Friedrich-Alexander-University of Erlangen-
Nuremberg, Erlangen 91058, Germany (2) Department of Chemical Reaction
Engineering, Friedrich-Alexander-University Busan Campus, Busan 618-230, Republic
of Korea
Due to their tuneable solubility properties ionic liquids (ILs) turned out to be well-suited
for biphasic IL-organic transition metal catalysis [1,2]. However, traditional biphasic ILorganic
systems require large amounts of IL which make them often economically
unattractive. Moreover, due to their high viscosity, mass transfer limitations can occur.
Application of the SILP-concept offers the possibility to circumvent these drawbacks [3].
The surface of a high-area porous support material is coated with a thin film of IL in
which the homogeneous catalyst is dissolved. Mass transport limitations can be avoided
and investment costs can be minimized. These SILP-systems can then be handled like
heterogeneous catalysts and applied in a continuous flow process with fixed-bed
reactors. Since the advent of well-defined homogeneous ruthenium carbene
complexes olefin metathesis has become a remarkable topic in synthetic organic
chemistry [4]. Nonetheless, in contrast to their successful use in organic synthesis, the
application of Grubbs-type catalysts on the commodity industrial scale is problematic
due to stability issues. Hence, unravelling the fundamentals of metathesis catalyst
deactivation is of major importance. Despite the significance of mechanistic elucidation
to catalyst optimization, relatively few studies have been performed to understand the
activity profiles of ruthenium-based metathesis systems in detail and under steady-state
condition [5]. For the observation of such catalyst activity profiles, experiments in a
continuous gas-phase fixed-bed reactor were carried out. Grubbs-type catalysts were
immobilized via the SILP-concept. The influence of the alkene feed on the activity and
stability of Grubbs metathesis catalysts is presented. [1] T. Welton, Chem.Rev. 1999,
2071. [2] P. Wasserscheid, W. Keim, Angew. Chem. Int. Ed. 2000, 39, 3772. [3] A.
Riisager, R. Fehrmann, M. Haumann, P. Wasserscheid, Eur. J. Inorg. Chem. 2006, 695.
[4] R.H. Grubbs, Tetrahedron 2004, 60, 7117. [5] M. Ulman, R.H. Grubbs, J. Org.
Chem. 1999, 64, 7202.
COIL-4:278
Absorption Properties of Innovative Task-Specific Azolium-Based Rtils: Dual
Affinity Towards Hydrofluoroethers and Water

Verena Adamer (1) , verena.adamer@uibk.ac.at, Innrain 52, Innsbruck A-6020, Austria ;
Ulrich J. Griesser (1) ; Herwig Schottenberger (1) . (1) Faculty of Chemistry and Pharmacy,
University of Innsbruck, Innsbruck A-6020, Austria
Hydrofluoroethers (HFEs) are suggested as replacements for the ecologically harmful
freons. Like other fluorocarbons, they interact weakly with water and many organic
solvents. HFEs are technically used as anhydrous cleaning agents, dielectric heat
transfer fluids and for vapor degreasing or dewatering. They allow for “spot-free”
cleaning of electronic parts and are employed as finishing agents for the “chemical
mechanical polishing” of wafers with aqueous slurries. To recover these expensive and
volatile solvents from exhaust air, room temperature ionic liquids (RTILs) with a high
affinity to HFEs are intriguing alternatives to conventional, energy-consuming
condensate traps. The present work introduces newly developed RTILs, which can
absorb large quantities of HFEs such as HFE-7100 (mixture of isomeric methyl
nonafluorobutyl ethers). They also absorb small amounts of water, which is remarkable
in view of the extreme polarity difference between HFEs and water. This unique dual
affinity is attributable to distinct hydrophilic and “fluorophilic” substituents of the
quaternized azolium moieties. The absorption abilities of a series of novel ILs for water
and HFE vapor were compared to commercial reference RTILs (1-butyl-2,3dimethylimidazolium
and 1-ethyl-3-methylimidazolium triflimide). The new RTILs and the
reference ILs form two phases with water and behave similarly with respect to moisture
absorptivity. One of the new ILs (1-(2-hydroxyethyl)-3-(1H,1H,2H,2Hperfluorodecyl)imidazolium
triflimide) is able to take up more than 3% (w/w) water at a
relative humidity of 98%. However, the tailored ILs exhibit superior HFE uptake (2 to 12
times of its own mass in saturated HFE vapor). Presaturation with water clearly
decreases the uptake capacity of the ILs for HFE. Karl Fischer titrations revealed that
the water content decreased in the moisture-saturated ILs after exposure to the HFE
atmosphere. These results show the potential of the new RTILs for technical
applications, e.g., as scrubbing liquids for HFE-containing exhaust air, but also as
working fluids in liquid absorption chillers.
COIL-4:279
Dialkyl Phosphate-Related Ionic Liquids as Solute–Solvent Interaction Probes
Carmen Froschauer (1) , csaf7911@uibk.ac.at, Innrain 52a, Innsbruck Tirol 6020,
Austria ; Michael Hummel (2) ; Gerhard Laus (1) ; Herwig Schottenberger (1) ; Herbert Sixta (2) ;
Hedda K. Weber (3) ; Klaus Wurst (1) ; Gerhard Zuckerstätter (3) . (1) Faculty of Chemistry
and Pharmacy, University of Innsbruck, Innsbruck 6020, Austria (2) Department of
Forest Products Technology, Helsinki University of Technology, Espoo 02150, Finland
(3) Competence Centre of Wood Composites and Wood Chemistry K-Plus, Linz 4021,
Austria
Cellulose, the most abundant polymer on the planet, is soluble in a range of ionic liquids
(ILs) which are capable to break the hydrogen bonds between the carbohydrate
chains.[1] The concept of probing solute-solvent interactions in cellulose solutions, e.g.

y 7 Li-NMR of molten lithium salts, has been applied a decade ago.[2] Hydrophobic
interactions have been probed by 31 P-NMR of cellulose derivatives.[3] In addition, the
hydrogen bond acceptor properties of ILs and their effect on cellulose solubility have
been correlated by 1 H-NMR in model solutions. [1] Recently, we introduced O,Sdimethylthiophosphate-based
ILs as fractionation media of (ligno)cellulosic materials.[1]
In continuation of our interest in this subject, we now present ILs based on the new
O,Se-dimethylselenophosphate anion. Sodium O,Se-dimethylselenophosphate can be
synthesized according to described procedures[1] and subsequently used to convert
alkylimidazolium chlorides into the corresponding O,Se-dimethylselenophosphate salts.
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Fig. 1 Molecular structure of the new 1-butyl-2,3-dimethylimidazolium O,Sedimethylselenophosphate.
It seemed attractive to utilize the presence of several active
nuclei in the new ILs for multinuclear ( 13 C, 31 P, 77 Se) NMR studies. The results are
correlated with the solvation behaviour for cellulose. References: [1] Froschauer, C.;
Himmer, K.; Wurst, K.; Laus, G.; Schottenberger, H. Z.Kristallogr. NCS 255 2010 569-
570 and references cited therein. [2] Brendler, E.; Fischer, S.; Leipner, H. Cellulose
2001, 8, 283. [3] King, A.W.T.; Kilpeläinen, I.; Heikkinen, S. Järvi, P.; Argyropoulos,
D.S. Biomacromolecules 2009, 10, 458.
COIL-4:280
Thermodynamic Properties of 1-Butyl-3-Methylpyridinium Tetrafluoroborate at
High Temperatures and Pressures
Ismail Kul (1) , ikul@widener.edu, One University Place, Chester PA 19013, United
States ; Javid Safarov (2)(3) ; Waleed A. El-Awady (3)(4) ; Egon Hassel (2) ; Astan
Shahverdiyev (3) . (1) Department of Chemistry & Biochemistry, Widener University,
Chester PA 19013, United States (2) Institute of Technical Thermodynamics, University
of Rostock, Rostock D-18059, Germany (3) Department of Heat and Refrigeration
Techniques, Azerbaijan Technical University,, Rostock D-18059, Germany (4)
Mechanical Power Engineering Department, Mansoura Univeristy, Baku AZ1073,
Azerbaijan
Ionic liquids (ILs) are salts that are liquid at room temperature, non-flammable, thermally
stable, and have no detectable vapor pressures. ILs are characterized as promising
solvents for clean processes and green chemistry. These liquids are promising ideal
systems which can be used for different purposes in chemical catalysis, separation
processes and electrochemistry. We have intensively investigated the thermophysical
properties of various ILs during the last decade because of need of these applications.
In this work, we studied the (p,ρ,T) properties of 1-butyl-4-methylpyridinium
tetrafluoroborate [B4mpy][BF4] at T=(283.15 to 393.15) K and at pressures p = (0.101 to
100) MPa, using a new modernized high pressure – high temperature Anton-Paar DMA
HPM vibrating tube densimeter. Densities of [B4mpy][BF4] at ambient pressure and at
temperatures T=(283.15 to 363.15) K were also measured using Anton-Paar DMA 5000
vibrating tube densimeter for comparison with the existing literature data. The density
measurements is predicted to be equivalent to the reproducibility of the density

measurements, i.e. ∆ρ/ρ = ±(0.01 to 0.08) %. The measured densities as a function of
pressure and temperature were fitted to an empirical equation of state, which fits the
experimental results of density of [B4mpy][BF4] within ±0.0096 % percent,
corresponding to 0.142 kg m -3 standard with a maximal deviation of 0.57 kg m -3 . This
equation was used for the calculation of thermal properties of the ionic liquid (IL), such
as isothermal compressibility, isobaric thermal expansibility, differences in isobaric and
isochoric heat capacities, thermal pressure coefficient and internal pressure as a
function of pressure and temperature. Internal pressure and the temperature coefficient
of internal pressure data were used to make conclusions on the molecular
characteristics of the IL.
COIL-4:281
Biobutanol Recovery Using Non-Fluorinated Task Specific Ionic Liquids (TSILS)
Lesly Y. Garcia-Chavez (1) , l.y.garcia-chavez@tue.nl, Den Dolech 2 Helix Building
STO1.27, Eindhoven North Brabant P.O. Box 513, 5600 MB, The Netherlands;
Christian M. Garsia (1) ; Boelo Schuur (1) ; André B. de Haan (1) . (1) Department of Chemical
Engineering and Chemistry, Eindhoven University of Technology, Eindhoven North
Brabant P.O. Box 513, 5600 MB, The Netherlands
Biofuels have received major attention as an alternative to fossil fuels. Although ethanol
is currently one of the most known biofuel; butanol high energy density is an advantage
over ethanol. A very interesting option for butanol production is the fermentation
process. However an energy efficient butanol separation process is required mainly
because of the low concentrations of butanol in the fermentation broth. Liquid-liquid
extraction (LLE) seems to be an alternative to the conventional distillation process. To
achieve an efficient LLE a solvent with high distribution coefficient and selectivity for
butanol is required. In an approach to improve the solvent properties, we tested a range
of hydrophobic ionic liquids (IL). We found trihexyl(tetradecyl) phosphonium bis 2,4,4trimethylpenthylphosphinate
(Cyphos 104), methyltrioctyl ammonium decanotate
(MTOA Dec) and tetrakis(decyl)ammonium 1-metyl-1-cyclohexanoate (TDA MCH) to be
very promising Task Specific Ionic Liquids (TSIL) for the extraction of butanol. The
advantage of these TSIL over commonly used BF4 - and PF6 - containing ILs is their
stability ( BF4 - and PF6 - anions degrade in the presence of water to form the hazardous
HF) and compared to more stable fluorous hydrophobic anions like N(CF3SO2)2 - (NTf2)
or [(C2F5)3PF3] - (FAP), TSIL showed a stronger affinity for butanol. Cyphos 104, MTOA
Dec and TDA MCH show distribution coefficients up to 9, 11 and 8 about 4 times better
than IL reported thus far. In addition, selectivities of 56, 37 and 121 respectively were
found. A conceptual design study for LLE using TSILs was simulated in ASPEN-Plus
and compare to the conventional process in terms of energy requirement. We found that
up to 60% energy saving can be achieved using LLE with TSILs
COIL-4:282
Phospholipase D Catalyzed Reactions in Ionic Liquids

Andrea Mele (1)(2) , andrea.mele@polimi.it, Via L. Mancinelli, 7, Milano Italy 20131, Italy ;
Paola D[apos]Arrigo (1)(2) ; Chiara Signo[apos] (1)(2) ; Cinzia Chiappe (3) . (1) Dipartimento di
Chimica, Materiali ed Ingegneria Chimica “G. Natta”, Politecnico di Milano, Milano, Italy
(2) The Protein Factory, Politecnico di Milano and Università dell’Insubria, Milano, Italy
(3) Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Pisa, Italy
Phospholipids (PLs) are important components in medicinal, diagnostic,
biotechnological, cosmetic, industrial and research applications. 1 Their involvement in
the formation of natural membranes and self-organisation in water has stimulated a
large body of studies on their physical properties. 2 These investigations rely on the
availability of material derived from natural sources largely modified by semisynthesis or
from compounds obtained by total synthesis. 3 Total synthesis of PLs is complex and
expensive. Nevertheless, all sites of PLs can be modified with biocatalytic methods
using phospholipases. 4 Phospholipase D (PLD) (EC 3.1.4.4) has been used to obtain
the modification of the polar head of the molecules: PLD catalyses in vivo the hydrolysis
of phospholipids to phosphatidic acid. However, in the presence of an alcohol PLD
catalyze the in vitro transphosphatidylation to a group of phospholipids of interest. The
transphosphatidylation is carried out in water-organic solvent and the extent of the
competing hydrolytic reaction depends on the source of the enzyme and nature of the
nucleophile. 5 The use of ionic liquids (ILs) in phospholipids chemistry had not been yet
investigated. We have tested the stability and the activity of a phospholipase D from
Streptomyces sp. in various commercial ionic liquids. In this communication we
illustrate the encouraging preliminary results of the use of ionic liquids as cosolvents in
transesterification reactions with different alcohols. The best results have been obtained
in the synthesis of phosphatidylserine leading to an almost quantitative suppression of
unwanted hydrolytic side reaction. 1. Uhumwangho, M.U.; Okor, R.S. J. Biomed. Sc.
2005, 4, 1, 9-21. 2. Sandermann, Jr. Biochimica et Biophysica Acta 1978, 515, 3, 209-
237 3. Eibl, H. Chem. Phys. Lipids 1980, 26, 405-429. 4. D'Arrigo, P.; Servi, S. Trends
in Biotechnology, 1997, 15, 90-96. 5. Carrea, G.; D'Arrigo, P.; Piergianni, V.;
Roncaglio, S.; Secundo, S.; Servi, S. Biochimica Biophysica Acta, 1995, 1255, 273-279.
COIL-4:283
Molecular Dynamics Simulation: A Powerful Tool for Engineering Ionic Liquids
Thorsten Koeddermann (1) , koeddermann@scai.fraunhofer.de, Schloß Birlinghoven,
Sankt Augustin NRW 53754, Germany ; Marco Huelsmann (1) ; Dirk Reith (1) . (1)
Computational Chemical Engineering, Fraunhofer Institute SCAI, Sankt Augustin 53754,
Germany
Nowadays, molecular dynamics simulations are widely used to support the development
process for new materials. The key to a quantitative property prediction is the accuracy
of the simulation's foundation, the force field. A force field describes the intra- and
intermolecular interactions by a semi-empirical equation and its associated parameters.
Manual adjustment and optimization of these parameters is, at best, extremely time
consuming. Hence, an automated parameterization scheme is essential in our pursuit to

create tailor-made models for specific investigations in a timely fashion. This has been
realized and implemented into a Gradient-based Optimization Workflow (GROW) [1] for
the automated development of molecular models. In this presentation, we will show
how our developed simulation procedure technically works and we will present
simulations of different ionic liquids calculating properties like densities, self diffusion
coefficients, viscosities and enthalpies of vaporisation of pure liquids and of IL/solvent
mixtures.
COIL-4:284
Criticality and Vapor-Liquid Phase Behavior of Ionic Liquids from Monte Carlo
Simulations
Edward J. Maginn (1) , ed@nd.edu, 182 Fitzpatrick Hall, Notre Dame Indiana 46556,
United States ; Neeraj Rai (1) . (1) Department of Chemical and Biomolecular
Engineering, University of Notre Dame, Notre Dame Indiana 46556, United States
Although our understanding of the vapor–liquid phase behavior of non–ionic compounds
has matured, progress in the field of ionic liquids is hindered primarily due to their
complex molecular structure and the presence of long-range Coulombic interactions.
Thermal stability limitations virtually eliminate direct experimental determination of
vapor–liquid coexistence curves (VLCCs), and sampling difficulties have prevented the
use of realistic intermolecular potentials (atomistic force fields) to determine VLCCs of
ionic liquids via molecular simulations. These difficulties led authors of a recent review
article to state that determination of the normal boiling points and critical temperatures
of ionic liquids is a “forbidden territory”. Furthermore, the aggregation state of ions in the
saturated vapor phase remains an open question, although at low temperature and high
vacuum, the dominant species are single ion pairs. Here we describe the first set of
vapor–liquid phase diagrams determined in silico for a family of imidazolium based ionic
liquids. The calculations employ an accurate atomistic force field that has been
validated against condensed phase properties. We show that the critical temperature,
density, and enthalpy of vaporization decrease with increasing length of the alkyl chain
on the cation, while the saturation pressure increases with increasing chain length.
These trends are in direct opposition to what is observed with simple alkanes and
alcohols, but is consistent with experimental trends. Moreover, we show that the
saturated vapor phase consists mainly of single ion–pairs at low temperatures and
pressures, but as temperature and pressure increase, larger neutral aggregates appear.
For these ionic liquids the Guggenheim and Eötovos empirical relations provide good
estimates of the critical temperature when used with low temperature surface tension
and density data, but a recently developed group contribution method is not suitable for
this purpose.
COIL-4:285
Influence of Hydrogen Bonding on the Properties of Ionic Liquids Shown for
Melting Points, Viscosities and Enthalpies of Vaporization

Ralf Ludwig (1) , ralf.ludwig@uni-rostock.de, Dr.-Lorenz-Weg 1, Rostock 18059,
Germany ; Koichi Fumino (1) ; Tim Peppel (2) ; Monica Geppert-Rybczynska (1) ; Jochen K.
Lehmann (1) ; Dzmitry H. Zaitsau (1) ; Sergey P. Verevkin (1) ; Martin Köckerling (2) . (1)
Institute of Chemistry, Physical and Theoretical Chemistry, University of Rostock,
Rostock D-18059, Germany (2) Institute of Chemistry, Inorganic Chemistry, University
of Rostock, Rostock D-18059, Germany
Potential applications of ionic liquids depend on the properties of this class of liquid
material.[1,2] To a large extent the structure and properties of these Coulomb systems
are determined by the intermolecular interactions between anions and cations. In
particular the subtle balance between Coulomb forces, hydrogen bonds and dispersion
forces is of great importance for the understanding of ionic liquids.[3,4] The purpose of
the present paper is to answer three questions: Do hydrogen bonds exist in these
Coulomb fluids? To what extent do hydrogen bonds contribute to the overall interaction
between anions and cations? And finally, are hydrogen bonds important for the physical
properties of ionic liquids? All these questions are addressed by using a suitable
combination of experimental and theoretical methods including synthesis of new
imidazolium ionic liquids, far infrared spectroscopy, terahertz spectroscopy, single
crystal diffraction, DFT calculations, viscometry and quartz-crystal-microbalance
measurements. The key statement is that although ionic liquids consist solely of anions
and cations and Coulomb forces are the dominating interaction, also local interaction
such as hydrogen bonding has significant influence on the structure and properties of
ionic liquids. This is demonstrated for the case of melting points, viscosities and
enthalpies of vaporization. As a consequence, a variety of important properties can be
tuned towards a larger working temperature range, finally expanding the range of
potential applications. 1. Ionic Liquids in Synthesis, 2nd Ed.., Eds.: P. Wasserscheid, T.
Welton, VCH-Wiley, Weinheim, 2008. 2. H. Weingärtner, Angew. Chem. Int. Ed. 2008,
47, 654 - 670. 3. K. Fumino, A.Wulf, R. Ludwig, Angew. Chem. Int. Ed. 2010, 49, 449 –
453. 4. C. Roth, T. Peppel, K. Fumino, M. Köckerling, R. Ludwig; Angew. Chem. Int.
Ed. 2010, 49, 10221 – 10224.
COIL-4:286
Snow White (∆Hvap) and the Seven Dwarfs (approaches): Express Highway to
Vaporization Enthalpy
Sergey P. Verevkin (1) , sergey.verevkin@uni-rostock.de, Dr-Lorenz-Weg 1, Rostock
Mecklenburg Vorpommern 18059, Germany . (1) Chemical Department, University of
Rostock, Rostock 18059, Germany
Snow White (Vaporization Enthalpy of an Ionic Liquid) is a princess living with her
Stepmother (IL-community). Stepmother forced Snow White to work as a scullery maid
(due to negligible vapor pressure and the large vaporization enthalpy) and would daily
ask her Magic Mirror "who is the fairest one of all" (or “is the vapor pressure low
enough”). For many years the mirror would always answer that the Stepmother was,
pleasing her. In 2006 the Magic Mirror informs the Stepmother that Snow White is now

the fairest in the land (or “the ILs have measurable vapor pressure at elevated
temperatures!!”). The jealous Stepmother orders to take Snow White into the woods and
to kill her (in order to justify a numerous applications of IL). Snow White fled into the
woods and met there seven dwarfs (seven methods have been developed for
determination of vaporization enthalpies: [1]-transpiration method, [2]-quartz-crystal
microbalance, [3]-static method, [4]-combustion calorimetry, [5]-TGA, [6]-DSC, [7]-first
principles calculations). Snow White begins a new life with the dwarfs while they mine
for jewels and at night sing, play music and dance (and putting efforts for reliable
measurements of vapor pressure and vaporization enthalpy of ILs). Meanwhile, the
Stepmother discovers that Snow White is still alive and she tricks Snow White into biting
into the poisoned apple (thermal decomposition of ILs during investigation) that sends
her into a deep sleep (irreproducible measurements), which can only be broken by
love's first kiss. After some time, a Prince (Thermochemical Lab, Rostock), kisses her
(overcoming all experimental obstacles), which breaks the spell and awakens her
(giving consistent results for the set of 25 new vaporization enthalpy data). "...and they
lived happily ever after."
COIL-4:287
Simulations of Solvation in Ionic Liquids Using a Simplified Model
Mark Maroncelli (1) , maroncelli@psu.edu, 104 Chemistry Building, University Park PA
16802, United States ; Durba Roy (1) . (1) Department of Chemistry, The Pennsylvania
State University, University Park PA 16802, United States
We have recently developed a reduced representation of a typical room-temperature
ionic liquid consisting of a 3-site cation and a single-site anion whose interaction
parameters were chosen to reproduce the properties of the prototypical liquid 1-butyl-3methylimidazolium
hexafluorophosphate. The computational economy of this model
enables simulation of large systems over the hundreds of nanoseconds time scale
necessary to simulate solute-based dynamics of the sort measured in our laboratory. To
date we have used it to simulate equilibrium and dynamic characteristics of solvation of
both idealized and realistic solutes. We find that the electrostatic solvation energies of
ionic and dipolar solutes can be understood in terms of simple continuum models and
the solute / solvent size ratio. The solvation response to a dipole perturbation closely
resembles the response measured using solutes such as coumarin 153, including the
stretched-exponential character of the diffusive portion of the response. Linear response
predictions are remarkably accurate, except when small ions are examined. In most
cases translational motions of ions rather than cation rotations are the primary
determinants of both the long- and short-time dynamics. We have also used simulations
to explore the connection between the solvation response and the dielectric relaxation
and charge-charge dynamics of neat model solvent. Neither simple continuum
descriptions nor more sophisticated models incorporating the wavevector dependence
of the charge-charge dynamics of the pure solvent provide accurate predictions for the
solvation response even in the most favorable of cases. Finally, we have examined
friction on translational and rotational motion of solutes. As expected, charged solutes

experience much greater friction in ionic liquids than do equivalent neutral solutes. The
frictional effect of electrostatic interactions is best viewed as an indirect effect of
electrostriction increasing the “mechanical” friction produced by the short-range
repulsive forces rather than as a result of “dielectric friction”.
COIL-4:288
Structure Inducing Ionic Liquids- Enhancement of Alpha Helicity in the Abeta(1-40 )
Peptide from Alzheimer's Disease
Nolene Byrne (1) , nolene.byrne@deakin.edu.au, GTP building, Geelong Victoria 3217,
Australia ; Natalie Debeljuh (1) ; Colin Barrow (1) . (1) Institute for Technology Research and
Innovation, Deakin University, Geelong Victoria 3217, Australia
Protein folding is a research topic that generates intense research efforts worldwide.
The importance of understanding protein misfolding has direct implications in
understanding the origins of human disease that stem from protein misfolding. These
diseases include Alzhiemers disease, Parkinson disease, and type II diabetes. Ionic
liquids as solvents for protein folding offer a new avenue to study protein – solvent
interactions which led to the stabilization of various folding intermediates, which are
critically important in understanding the folding/misfolding and formation of amyloid
fibrils. We have studied the impact of ionic liquid solvents on the structure of the
Abeta1-40 peptide. We have selected this peptide due to its role in the pathogenesis of
Alzheimer's disease. We find that ionic liquid solvents were able to induce a
conformational change in the structure of the Abeta1-40 peptide. This conformational
change has direct impact on the Alzhiemers peptide to self assembly into amyloid fibrils.
We present our current findings and provide insights into the structure inducing
properties of ionic liquids.
COIL-4:289
Synthesis and Characterisation of a New Class of Ionic Liquid Cations
Kelvin J. Walst (1) , kevin.walst@canterbury.ac.nz, Private Bag 4800, Christchurch 8040,
New Zealand ; Owen J. Curnow (1) ; Ruomeng Wang (1) ; Ruhamah Yunis (1) . (1)
Department of Chemistry, University of Canterbury, Christchurch 8040, New Zealand
A new class of readily-synthesised, highly-versatile and stable cations will be presented.
This includes five symmetry types to date, protic and aprotic cations, and a facile route
to non-ammonium chiral cations based on amino acids. A variety of anions have been
utilised, including fluoride, and structure-property relationships have been investigated
using DSC, TGA, viscosity, miscibility and conductivity studies.
COIL-4:290

Hydrogen Bonding and Local Structures of Ionic Liquids/H2O, Alcohols Interfaces
Studied by Nonlinear Vibrational Spectroscopy and MD Simulation
Yukio Ouchi (1) , ohuchi@mat.chem.nagoya-u.ac.jp, Furo-cho, Chikusa-ku, Nagoya Aichi
464-8602, Japan ; Takashi Iwahashi (1) ; Yasunari Sakai (1) ; Doseok Kim (2) ; Tatsuya
Ishiyama (3) ; Akihiro Morita (3) . (1) Department of Chemistry, Nagoya University, Nagoya
Aichi 464-8602, Japan (2) Department of Physics, Sogang University, Seoul 121-742,
Republic of Korea (3) Department of Chemistry, Tohoku University, Sendai Miyagi 980-
8578, Japan
"Buried interface" is one of the unexplored physico-chemical subjects to be investigated.
In this paper, we have carried out a series of experiments with use of interface selective
IR-Vis sum-frequency generation (IV-SFG) vibrational spectroscopy together with
molecular dynamic simulations for RTIL/H2O, alcohols interfaces. We have found a
couple of novel ordered structures at Liq/Liq interfaces. [Cnmim]PF6 /alcohol interface
forms preferentially oriented alkyl chain structure due to the fact that the OH group of
the alcohol strongly and preferentially interacts with PF6 anions. [Cnmim]TFSA/H2O
interface induces polar orientations of anions and specific hydrogen bonding network in
H2O phase. Figure 1 shows a typical example of SF spectral changes of the
H2O/[Cnmim]TFSA interfaces. When [Cnmim]TFSA contacts with water to form a Liq/Liq
interface, the SF signal of SO2-ss (~1140 cm −1 ) suddenly disappeared for n = 4. On the
contrary, the SF signal of SO2-ss became very broad for n = 8. These results
indicate that the TFSA anion orients randomly at the water/[C4mim]TFSA interface and
the TFSA anion for n = 8 polar orients with its SO2 group pointing toward the water
phase. The peak broadening is caused by inhomogeneous interaction of hydrogen
bonding of water. Octyl-chain of the cation supports the polar orientation of the cation
and the anion at the interface. Heterogeneous and complex systems of such interfaces
can explain various functions occurring at the interfaces.
COIL-4:291
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Molecular Insight into Ionic Liquid Behavior in Double Layer Capacitors and in
Electrolytes for Lithium Batteries
Oleg Borodin (1)(2) , olegutah@gmail.com, 2800 Powder Mill Rd., Adelphi MD 20783,
United States ; Jenel Vatamanu (2) ; Grant Smith (2) . (1) Electrochemistry Branch, Army
Research Laboratory, Adelphi MD, United States (2) Department of Materials Science &
Eng., University of Utah, Adelphi MD, United States
Ionic liquids at electrified interfaces exhibit a complicated response to the applied
electric field. We will present molecular dynamics (MD) simulations on N-methyl-Npropylpyrrolidinium
bis-fluorosulfonyl imide (pyr13FSI) and pyr13TFSI room temperature
ionic liquids confined between graphite electrodes as a function of applied potential. The
electric double layer (EDL) structure and differential capacitance (DC) of pyr13FSI as a
function of applied potential will be compared with the results for pyr13TFSI. While both

ILs show camel shape behavior of differential capacitance vs. applied potential, we
observed that the smaller size of the FSI anion compared to TFSI resulted in a 30%
higher DC observed on the negative electrode for pyr13FSI compared to pyr13TFSI
shown in Figure 1 instead of expected differences on the positive electrode. The larger
DC observed on the negative electrode for pyr13FSI compared to pyr13TFSI was
associated with two structural features of the EDL: a) a closer approach of FSI
compared to TFSI to the electrode surface and b) a faster rate (vs. potential) of anion
desorption from the electrode surface with decreasing potential electrode for FSI
compared to TFSI. Additionally, the limiting behavior of DC at large applied potentials
will be discussed together with the electrode charging kinetics. Lithium
transport and coordination structure in ILs extracted from MD simulations will be
discussed in the second part of the talk.
COIL-4:292
Biomass Functionalization Meets Micellar Catalysis:Novel Synthetic Strategies in
Ionic Liquids
Katharina Bica (1) , kbica@ioc.tuwien.ac.at, Getreidemarkt 9/163, Vienna Vienna 1060,
Austria ; Anna K Ressmann (1) ; Philipp Gritsch (1) ; Peter Gaertner (1) . (1) Institute of
Applied Synthetic Chemistry, Vienna University of Technology, Vienna Vienna 1060,
Austria
Although the growing interest in ionic liquids as alternative solvents was mostly caused
by the possibility to avoid large volumes of volatile solvents, a number of critical aspects
of ionic liquids make them an interesting media for synthesis and catalysis that can give
rise to distinct chemistry of their own compared to traditional molecular solvents. 1 The
isolation of active ingredients from biomass is mainly performed using extraction
processes; however this is always associated with the dangers of combustible solvents,
human risk and often limited efficiency. 2 Facing these issues, we present our
investigations towards the direct isolation of the active ingredients such as Shikimic
acid, the major precursor for the antiviral drug Tamiflu ® , from biomass. We will not only
discuss ionic liquids as alternative extraction media, but present novel synthetic
strategies for the manufacturing of Tamiflu ® and other drug precursors, including
biomass functionalization and catalysis in ionic liquid-aqueous biphasic media. 1
Ionic Liquids in Synthesis; Wasserscheid, P., Welton, T., Eds.; Wiley-VCH: Weinheim,
Germany, 2008; Vols. 1-2. 2 Swatloski, R. P.; Spear, S. K.; Holbrey, J. D.; Rogers, R.
D. J. Am. Chem. Soc. 2002, 124, 4974.
COIL-4:293
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Utilization of Novel Switchable Ionic Liquids for the Fractionation of
Lignocellulosic Materials

Ikenna Anugwom (1) , ianugwom@abo.fi, Piispankatu 8, Turku Turku 20500, Finland ;
Pasi Virtanen (1) ; Päivi Mäki-Arvela (1) ; Jyri-Pekka Mikkola (2) . (1) Laboratory of Industrial
Chemistry and Reaction Engineering, Åbo Akademi University, Åbo Abo 20500, Finland
(2) Technical Chemistry, Department of Chemistry, Chemical-Biological Center, Umeå
University, Umeå 90187, Sweden
Ionic Liquids are promising solvents for biomass. The main obstacle using conventional
ILs is recycling. Switchable Ionic Liquids (SILs) facilitate easy recycling and are made
from affordable chemicals, (glycerol) and industrial flue gases (SO2 and CO2) as
triggers, together with 1,8-diazabicyclo-[5.4.0]-undec-7-ene. The new SILs were
characterized by NMR, FTIR, TGA and DSC. Native hardwood (Betula) chips (3x3 cm)
with moisture content of 32 wt-% were treated with SILs for 5 days at 100°C under
normal pressure without stirring. The SIL to wood weight ratio was 5:1. The contents of
cellulose, hemicelluloses and lignin of the treated material were determined. Treatment
of birch with SIL1 (CO2) and SIL2 (SO2), demonstrated a 29 wt-% and 94 wt-%
reduction in the hemicelluloses content of the un-dissolved fraction compared to native
birch, respectively. With SIL2 lignin was removed nearly quantitatively, together with
extractives and pectins. SEM images of native and SIL treated birch chips are shown in
Fig. 1. The un-dissolved material was efficiently fibrillated. The recovered precipitate
from spent SIL1 after wood chip treatment contained about 40 wt-% hemicelluloses.
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The spent SIL1 was reused for four consecutive experiments without significant
loss of performance. These results indicate that these novel SILs offer unique,
affordable and easy to handle solvent system for the dissolution of native wood.
Dissolution was performed at lower temperatures compared to e.g. sulfate pulping, thus
facilitating lower energy consumption.
COIL-4:294
New Developments in the Processability of Wood with Ionic Liquids
Alistair W. T. King (1) , alistair.king@helsinki.fi, Faculty of Science, P.O. Box 55 (A.I.
Virtasen Aukio 1), HELSINKI Etelä Suomen Lääni FIN-00014 University of Helsinki,
Finland ; Lasse Kyllönen (1) ; Pirkko Karhunen (1) ; Jorma Matikainen (1) ; Ilkka Kilpeläinen (1) .
(1) Department of Chemistry, University of Helsinki, HELSINKI 00700, Finland
Certain ionic liquids are promoted as potential media for the fractionation of lignin from
polysaccharide in intact woody material. These processes should grant access to
sulphur-free lignin, for the potential production of future specialities and commodities. In
addition, fibrous pulp should be recovered, which is of similar quality and processability
for substitution into existing value chains. Initial processing concepts have relied upon
the ability of certain ionic liquids to dissolve cellulosic pulp 1 and potentially wood. 2
These processes have met with mixed success, but steady improvements are being
made. 3 From our recent studies, we would like to contribute our understanding of
lignocellulose solubility/fractionation in ionic liquids. Our conclusions will be derived from
simple NMR studies into the solubility of wood into a range of media. Additionally, we

would like to present a new concept for wood processing in ionic liquid media. This is
the effect of fibrillation of wood chips, without dissolution of the cellulosic component,
from certain refined ionic liquid structures. References: 1 R. P. Swatloski, S. K. Spear,
J. D. Holbrey, R. D. Rogers, J. Am. Chem. Soc., 2002, 124, 4974. 2 D. A. Fort, R. C.
Remsing, R. P. Swatloski, P. Moyna, G. Moyna, R. D. Rogers, Green Chem., 2007, 9,
63; I. Kilpeläinen, H. B. Xie, A. W. T. King, M. Granström, S. Heikkinen, D. S.
Argyropoulos, J. Agric. Food Chem., 2007, 55, 9142. 3 N. Sun, X. Jiang, M. L. Maxim,
A. Metlen, R. D. Rogers, ChemSusChem, 2011, 4, 65; T. Leskinen, A. W. T. King, I.
Kilpeläinen, D. S. Argyropoulos, submitted to Ind. Eng. Chem. Res. 2011.
COIL-4:295
Looking at the Reactivity of 1-Ethyl-3-Methylimidazolium Acetate with CO2 and
Biomass from Crystal Structures: Will Chemistry Explain the Controversies?
Gabriela Gurau (1) , gurau001@as.ua.edu, BOX 870336, Tuscaloosa AL 35487, United
States ; Héctor Rodríguez (2) ; Steven P. Kelley (1) ; Robin D. Rogers (1) . (1) Department of
Chemistry and Center for Green Manufacturing, The University of Alabama, Tuscaloosa
AL 35487, United States (2) Department of Chemical Engineering, University of
Santiago de Compostela, Santiago de Compostela E-15782, Spain
In the quest for understanding how solubility and reactivity in/of ionic liquids (ILs) can be
controlled through the specific combination of particular cations and anions, we
investigated the potential for nominally stable ionic liquids, such as 1-ethyl-3methylimidazolium
acetate ([C2mim][OAc]), to be activated by proper choice of anion via
direct 'in situ' N-heterocyclic carbene (NHC) formation to uniquely combine favorable IL
properties (thermal/chemical stability, etc.) with NHC reactivity. We have recently
reported the 'carbene-in-a-bottle' concept, where, through anion selection, the standing
carbene concentration present in equilibrium in ILs can be modified to provide both
reactive carbene moieties and solvent for a variety of applications. 1 Guided by these
initial results, we decided to explore the potential reactivity of [Cnmim][OAc] ILs with
other substances via the same mechanism. Despite several reports on solubility data of
CO2 in these ILs indicating no reaction between CO2 and the IL, we were curious why
this should be true given our findings of an apparent standing carbene concentration in
[C2mim][OAc] and therefore studied the interaction of CO2 more fully. Here we will
present our results demonstrating direct reaction of CO2 with the imidazolium ring in
[C2mim][OAc]; a result which may help explain certain recent solubility results. These
results are critical for better understanding ILs in general, as well as the possibilities
(and limitations) of these appealing acetate imidazolium ILs, which are being actively
investigated in cutting-edge research fields. 1. Rodríguez, H.; Gurau, G.; Holbrey, J.
D.; Rogers, R. D. Chem. Commun., 2011, 47, 3222.
COIL-4:296
Amino Acid Based Ionic Liquids as Templates for the Synthesis of Metal
Nanoparticles

Ambrose A Melvin (1) , ashwinmelvin08@gmail.com, Homi Bhabha road, Colaba,
Mumbai Maharastra 600004, India ; Santhosh k Haram (2) ; Deepa Khushalani (1) . (1)
Department of Chemical Sciences, Tata Institute of Fundamental Research, Mumbai
Maharastra 600004, India (2) Department of Chemistry, University of Pune, Pune
Maharastra 411007, India
Natural amino acids have proved to be an outstanding class of ligands 1 and capping
agents, especially in the case of metal nanoparticles (MNPs). On the other hand ionic
liquids (ILs) have shown great versatility as intriguing solvents and/or reagents in a wide
variety of chemical reactions. As a result, presented here is the use of amino acid based
ionic liquids (AAILs) for the synthesis of MNPs. It should be noted that these AAILs act
as a self reducing and capping agent for the formation of a wide variety of MNPs. This
novel property of AAILs puts them ahead of other non aqueous and biocompatible
solvents as it provides a facile one-step route to metal nanostructures. The MNPs that
have been formed are Ag, Au, Pt and Pd. The size of these nanostructures ranges from
2 - 40 nm. The AAILs employed were glycine, lysine and cysteine based ILs (the cation
was tetrabutylphosphonium ion). Extensive characterization was carried out using FT-
NMR, FTIR, UV, SERS, TGA, DSC and HRTEM, the results of which will be presented
along a purported mechanism of formation of the MNPs. References 1) Chen etal,
J. Am. Chem. Soc. 2007, 129,13879. 2)J. Dupont, J. BrazilChem. Soc. 2004, 15, 341.
3) J. Krämer et al,Organometall.2008, 27, 976.
COIL-4:297
Ionogels : Confined Ionic Liquids as New Drug Delivery Sytem
Lydie Viau (1) , lydie.viau@univ-montp2.fr, Place Eugène Bataillon, Montpellier
Languedoc-Roussillon, France ; Corine Tourné-Péteilh (1) ; Jean-Marie Devoisselle (1) ;
André Vioux (1) . (1) Institut Charles Gerhardt, Montpellier, France
Ionogels are materials obtained by immobilization of ionic liquids (ILs) on inorganic
(silica, alumina) or organic (polymers, carbon nanotubes) supports for applications such
as solid electrolytes, catalysis. 1 The use of supported ILs for biological applications is
more limited. Formulation of drugs is an industrial great challenge indeed numerous
efforts are developed to build up new drug delivery systems. In this field, mesoporous
templated silica materials appear as potential drug delivery systems due to their uniform
porous structure, high surface area, tunable pore sizes and good biocompatibility. Up to
now, drugs were mainly physically adsorbed into the channels of mesoporous silica.
Nevertheless, this loading method requires several steps to achieve the final drug
loaded and functionalized material. The synthesis of ionogels by silica sol-gel
processing in ILs has been reported by our group. Here, we proposed a novel approach
to encapsulate ibuprofen in porous functionalized silica by a one-step sol-gel procedure.
We therefore synthesized a new ionic liquid based on ibuprofenate drug and
imidazolium type cation. Ionogels confining this new IL were synthesized and the ability
of these materials to act as a new drug delivery system was tested. 2 . We have
demonstrated an important influence of the nature of the silica on the drug release thus

allowing a control of the kinetic.These ionogels constituted a new class of drug delivery
system, with high drug content molecularly dispersed as a new IL form. They are easily
shaped and do not need any further process to achieve a final pharmaceutical form. (1)
Le Bideau, J. ; Viau, L. ; Vioux, A. Chem. Soc. Rev., 2011, 40, 907-925. (2) Neouze,
M.-A. ; Le Bideau, J. ; Gaveau,P. ; Bellayer S. ; Vioux, A. Chem. Mater., 2006, 18, 3931.
(3) Viau,L. ; Tourné-Péteilh, C. ; Devoisselle, J.-M. ; Vioux, A. Chem. Commun. 2010,
46, 228-230.
COIL-4:298
Ionic Liquids: Multifonctionnal Agents in Polymer Science
Sébastien Livi (1) , sebastien.livi@gmail.com, 416 Bard hall, Ithaca NY 14850, United
States ; Jannick Duchet-Rumeau (1) ; Jean-François Gérard (1) . (1) Ingénierie des
Matériaux Polymères IMP, Université de Lyon, Villeurbanne 69100, France
In materials science, the goal is to create new materials with significantly improved
physical properties from designing matter structuration at naoscale. For many years,
several approaches have been described for designing new structures from organic
molecules, polymers, or organic-inorganic hybrids. Ionic liquids (ILs) which are organic
salts with a melting point below 100°C are attracting much attention of academic and
industrial research in many fields of chemistry and industry due to their excellent
thermal stability, inflammability, low vapor pressure and high ionic conductivity. Over the
last years, ILs have been popularly used as solvents for organic synthesis, as catalysis,
in electrochemical applications and also as media for polymerization processes. But ILs
can also represent supramolecular polymeric structures with a high degree of selforganization
since the IL structure involves three-dimensional networks of anions and
cations bound by weak interactions. In this work, ILs were used as new building blocks
to get a nanoscale structuration within a polymer matrix. Three routes were tested to
process nanostructured materials (Figure 1) i) from a phase separation with a
fluorinated matrix, ii) from intercalation within the lamellar fillers and iii) from the
solubility in carbon dioxide. Nanostructured films with dramatic mechanical properties,
nanocomposites with a tailored dispersion state and microcellular foams were
elaborated from ionic liquids. To find the more relevant combination of cation and anion
to design the more efficient IL to get these structurations, different organic salts have
been synthetized. Thus, the influence of the chemical nature of cation, phosphonium vs
imidazolium vs pyridinium and the nature of the counteranion, halide anions, iodide (I - )
or bromide (Br - ) vs fluoride anions, i.e. hexafluorophosphate (PF6 - ) has been described.
COIL-4:299
Aluminophosphate Zeolite Synthesis in Ionic Liquids
Jennifer L Anthony (1) , anthonyj@ksu.edu, 1005 Durland Hall, Manhattan KS 66506,
United States ; Xin Sun (1) ; Sean Tomlinson (1) ; John Schlup (1) . (1) Department of
Chemical Engineering, Kansas State University, Manhattan KS 66506, United States

Zeolitic molecular sieves have extensive applications in catalysis and separations.
These stable, crystalline materials with nanometer-sized pores can have a wide range
of chemical compositions, such as silicates, phosphate metal oxides, or all-carbon
molecular sieves. Subsequently, there has been extensive research on the synthesis of
new frameworks as well as trying understanding their crystallization mechanism.
Crystalline molecular sieves traditionally are prepared using a hydrothermal synthesis
method. A typical zeolite synthesis would consist of a mixture of water, a source of the
framework atoms, a mineralizing agent (e.g. OH - or F - ), and a structure-directing agent
(SDA). Recently, it has been shown that aluminophosphate molecular sieves can be
prepared ionothermally. In ionothermal synthesis, an ionic liquid serves as the solvent
and often the structure directing agent as well. Our group has focused on the
ionothermal synthesis of porous, crystalline aluminophosphates and silicates with the
emphasis on determining how the ionic liquid properties influence the final materials. In
particular, we are investigating the interactions between the ionic liquid solvent and the
molecular sieve precursors prior to the synthetic reaction through solubility and
spectroscopic measurements. In this presentation, we will discuss the effects of reaction
composition and conditions on structures of the porous aluminophosphate molecular
sieves (AlPOs) and compare to those using traditional hydrothermal techniques. We
also will discuss the influence of the ionic liquid structure on the resulting materials and
will present our results from investigating the influence of the ionic liquid structure on the
solubility of the precursors and the ionic liquid-precursor complexes seen by
spectroscopy.
COIL-4:300
New Materials for Dye-Sensitized Solar Cells
Jenny Pringle (1) , Jenny.Pringle@monash.edu, Wellington Road, Clayton VIC 3800,
Australia ; Vanessa Armel (2) ; Maria Forsyth (1) ; Doug MacFarlane (2) . (1) Department of
Materials Engineering, Monash University, Clayton VIC 3800, Australia (2) School of
Chemistry, Monash University, Clayton VIC 3800, Australia
The future of dye-sensitized solar cells (DSSCs) as a commercially viable alternative to
traditional silicon-based solar cells is dependent on the development of cheaper, lighter
weight, flexible devices utilizing plastic substrates. For the widespread use of these
solar cells an extended device lifetime is also critical and hence the use of solid state
electrolytes, which eliminate leakage problems, is also highly advantageous. Here we
report the synthesis of conducting polymer-on-conducting plastic (ITO-PEN) cathodes,
the synthesis of which is potentially amenable to large scale reel-to-reel processing
techniques. The cell efficiencies obtained are equivalent to those obtained using the
traditional platinised FTO glass electrodes (>8% using an acetonitrile-based electrolyte).
We also report the use of a new type of solid state electrolyte, based on Organic Ionic
Plastic Crystals. These materials are structurally analogous to ionic liquids, but the salts
display melting points above room temperature and can exhibit plastic crystalline
behaviour. Organic ionic plastic crystals are unique solid-state electrolytes in terms of
both their mechanical and transport properties; they combine the advantages of fast ion

conduction with electrochemical and thermal stability and non-volatility, even above
their melting point. Thus, these are excellent matrix materials for DSSC electrolytes,
and efficiencies of over 5 % at 1 sun have been achieved.
COIL-4:301
Properties of Ionic Liquid-Water Mixtures as Electrolytes for Mg-Air Batteries
Jan Novak (1) , j.novak@bham.ac.uk, Edgbaston, Birmingham West Midlands B15 2TT,
United Kingdom ; Timothy Khoo (2) ; Paul Bayley (2) ; Melanie Britton (1) ; Patrick Howlett (2) ;
Maria Forsyth (2) . (1) University of Birmingham, Birmingham, United Kingdom (2) Deakin
University, Melbourne, Australia
Phosphonium-based ionic liquids (IL) have shown promise as candidates for
electrolytes in Mg-air batteries. However, the high viscosity of the ILs, compounded by
the addition of necessary metal salts, results in low ionic conductivity, hence poor
battery performance. One solution for this is the introduction of diluents which reduce
viscosity and increase conductivity. It has been shown that the chemical structure of the
organic diluents affect the transport properties of the charge-carrying ions in the
electrolytes. In our research we have studied the effect of water addition on the physical
properties of the ionic liquid trihexyl(tetradecyl)phosphonium chloride ([P6,6,6,14][Cl]).
Variable-temperature measurements of viscosity, conductivity and diffusion coefficients
using nuclear magnetic resonance were employed to characterise the physical
properties of the electrolyte mixtures. We have shown that the addition of water to the IL
results in a decrease in viscosity and a corresponding increase in ionic conductivity
(Figure 1 (a)). Interestingly, the addition of metal salts to the IL-water mixtures resulted
in an increase in conductivity at lower water contents (∼0 % and 2 %) but a decrease at
higher water contents (6 % and 8 %) (Figure 1 (b)). Figure 1 Conductivity of [P6,
6, 6, 14][Cl] with varying water content. (a) Shows the temperature dependence and (b)
shows the effect of addition of LiCl at 313 K.
COIL-4:302
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Electrical Properties of Semiconducting Polymers Electrochemically Doped with
Ionic Liquids
Bryan D Paulsen (1) , pauls445@umn.edu, 421 Washington Ave. SE, Minneapolis MN
55455, United States ; C. Daniel Frisbie (1) . (1) Department of Chemical Engineering &
Materials Science, University of Minnesota, Minneapolis MN 55455, United States
We report the thorough investigation of the electrochemistry and conductivity of the
benchmark semiconducting polymer poly(3-hexylthiophene) (P3HT) gated with the ionic
liquid bis(trifluoromethylsulfonyl)imide tris(pentafluoroethyl)trifluorophosphate (EMI
FAP). The use of EMI FAP allowed for the stable and reversible oxidation of P3HT far
beyond what is obtainable with traditional organic electrolytes. Dynamic charge

densities were obtained from cyclic voltammograms providing a wide energy view of the
electrochemical density of states in P3HT, while simultaneous conductivity
measurements revealed a finite potential window of high conductivity. Variable
temperature measurements of the charge density dependent mobility were investigated
through out the entire window of finite conductivity, revealing the nature of charge
carriers in conjugated polymers at very high charge carrier density. Electrochemistry
and conductivity measurements were extended to P3HT gated with a series of ionic
liquids consisting of 1-ethyl-3-methylimidazolium, 1-butyl-1-methylpyrrolidinium, and
trihexyl(tetradecyl)phosphonium cations and bis(trifluoromethylsulfonyl)imide and
tris(pentafluoroethyl)trifluorophosphate anions., establishing the anion and cation effects
on charging and charge transport. Additionally, poly(2-methoxy-5-(2′-ethylhexyloxy)-1,4phenylenevinylene)
and poly(9,9-dioctylfluorene-co-benzothiadiazole) were gated with
EMI FAP further establishing the utility of EMI FAP as a highly stable electrolyte gate,
and the generality of charge transport behavior in highly oxidized semiconducting
polymers.
COIL-4:303
Electrochemical Performance of Mno2 Electrodes in Neutral Aqueous Electrolytes
and in Protic Ionic Liquids (PIL)
Carlos Alberto Castro Ruiz (1) , carlos.alberto.castro.ruiz@umontreal.ca, C.P. 6128,
Succ. Centre-Ville, Montréal Québec H3C 3J7, Canada ; Dominic Rochefort (1) ; Daniel
Bélanger (2) . (1) Département de Chimie, Université de Montréal, Montréal Québec H3C
3J7, Canada (2) Département de Chimie, Université du Québec à Montréal, Montréal
Québec H3C 3P8, Canada
In recent years, electrochemical capacitors or supercapacitors (SCs) have attracted
much attention for their power enhancement compared to batteries and fuel cells, and
higher energy densities than common capacitors. Several transition metal oxides
(RuO2, IrO2, NiO, CoOx, SnO2 and MnO2) were tested as electrode materials for
pseudocapacitors. Among these oxides, MnO2 due to its low cost, satisfactory
electrochemical performance and natural abundance is considered as one of the most
promising materials for SCs in many technological applications ranging from mobile
devices to electric vehicles. In this contribution, we will report on the electrochemical
behaviour of MnO2 in protic ionic liquid electrolytes. Thus, the MnO2 films
electrochemically deposited on Ti and ITO substrates were compared and
characterized. Further information about synthesis, characterization by SEM, XRD, CV,
Raman and UV-vis spectroscopy and stability performance will be reported.
Spectroelectrochemical experiments have been carried out to study the changes in the
optical properties of the MnO2 films (on ITO) which are linked to the oxidation state of
the material. Further developments on task-specific ionic liquids for electrolytes in
metal-oxide based SCs are expected to increase their charge storage properties.
COIL-4:304
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Formation of Solvated Electrons in TMPA[Tf2N] Observed with Femtosecond
Time-Resolved Near-Infrared Spectroscopy
Koichi Iwata (1) , koichi.iwata@gakushuin.ac.jp, 1-5-1 Mejiro, Toshima-ku Tokyo 171-
8588, Japan ; Manping Ye (1) . (1) Department of Chemistry, Gakushuin University,
Toshima-ku Tokyo 171-8588, Japan
When an electron is suddenly created in a solvent, it is rapidly solvated. The structure
and its fluctuation of the solvent can be examined if the solvation process of the electron
is recorded. The solvated electron is a major research interest for radiation chemistry.
We observe the initial solvation process of electrons generated in
trimethylpropylammonium-bis (trifluoromethylsulfonyl)imide (TMPA[Tf2N]) with
femtosecond time-resolved near-infrared spectroscopy. Electrons are generated in the
ionic liquid by photoirradiation with a 240 nm light pulse. Absorption spectra of the
generated electrons are observed with a probe pulse of white light continuum. Both of
the 240 nm pump pulse and the white light are generated from the amplified Ti:sapphire
laser output with the width of 35 fs. Time-resolved spectra are recorded for the
wavelength range between 900 and 1500 nm with InGaAs diode arrays. An absorption
band of the solvated electron is observed in the near-infrared region. The absorption
maximum is located at around 1050 nm, which is in agreement with the result of
nanosecond time-resolved absorption spectroscopy already reported. The absorption
band of the electron shows a wavenumber shift of 740 cm -1 as the time delay changes
from 0 fs to 1.1 ns. In water, however, the absorption band changes the position by
more than 5000 cm -1 in 2 ps. The electron solvation process in the ionic liquid is
markedly different from the electron solvation in ordinary polar solvents. Kinetics of the
spectral peak shift observed in the ionic liquid is represented by a double exponential
decay function. It suggests the presence of two or more distinctively different solvation
environments for electrons in TMPA[Tf2N].
COIL-4:305
Aggregation in Ionic Liquids Modulated by Hydration and Ionic Medium
Louis A Madsen (1) , lmadsen@vt.edu, Mail code 0212, Blacksburg VA 24061, United
States ; Jianbo Hou (1) ; Zhiyang Zhang (1) . (1) Department of Chemistry, Virginia Tech,
Blacksburg VA 24061, United States
Understanding the subtle associations between ions in ILs presents an enduring
challenge. While several groups have made significant advances, basic questions
remain. We have investigated transport in four ILs using multinuclear NMR, separately
quantifying diffusion coefficients of water, cations, and anions. We have probed ILs over
a wide range of concentrations in water solution, and have also studied ILs absorbed
into ionic polymer membranes, systematically varying both hydration level and IL uptake
level. ILs in ionic polymer membranes provide promising candidates for “artificial
muscle” mechanical actuators that possess large strains per unit voltage. In highly
hydrated IL solutions, cation/anion diffusion ratios agree (via Stokes-Einstein) with the

esults of density-based ion radius calculations, e.g., rcation/ranion = 1.4 for [C2mim][BF4].
The anomalous cation/anion diffusion ratios observed so far for pure ILs undoubtedly
arise from selective ion aggregation effects. When ILs diffuse inside an ionic polymer,
ion associations are modulated by interactions between mobile cations and anions, and
drag from fixed -SO3 - lining the polymer's hydrophilic channels. Surprisingly, cations
diffuse substantially faster (≤ 3X) at low hydration, revealing the prevalence of anionic
aggregates. At high hydration, isolated anions diffuse faster (≤ 4X) than cations, which
experience more drag from the polymer-fixed sulfonates. We will discuss aggregation
models (see figure), our progress toward quantifying aggregate populations, and
correlations with macroscopic actuator bending behaviors.
COIL-4:306
Charge Transport in Ionic Liquids, Molten Salts and Electrolyte Solutions
Hemant K Kashyap (1) , kashyaphemant@gmail.com, E309 Chemistry Building, Iowa
City Iowa 52242, United States ; Claudio J Margulis (1) . (1) Chemistry, University of Iowa,
Iowa City Iowa 52242, United States
It is well established that for room-temperature ionic liquids (RTILs), molten salts and
electrolyte solutions the ratio of impedance vs. NMR derived conductivities is Λimp/ΛNMR
∼ 0.9-0.5. 1-2 The deviation from NMR results described by the parameter ∆, which is
defined as ∆=1 - Λimp/ΛNMR (see Figure 1), has often been used to describe the degree
of so-called ion pairing. 1 The concept of ion pairing is easily understood in the case of
electrolyte solutions, but is less clear in a liquid solely composed of ions. While a
number of measurements and computer simulations have agreed on these findings, we
are still missing a clear physical understanding of charge transport in ionic liquids. This
is important if we want to improve our ability to use these materials in energy
applications. In this meeting we present computational results that in comparison with
experiments attempt to address the physical origin of the observed values of ∆. We
focus in particular on the origin and possible mechanism of ion transport. Our
preliminary results indicate that the origin of the above deviation is different for RTILs
and electrolyte solution. Figure 1: Comparison of molar ionic conductivities
obtained from NMR or Nernst-Einstein (NE) and current auto-correlation function
(CACF) in the case an ionic liquid, a molten salt and an electrolyte solution. 1. (a)
Tokuda et. al. J Phys Chem B 2005 109 (13), 6103-6110. (b) Tokuda et al. J Phys
Chem B 2006, 110 (6), 2833-2839. 2 Kanakubo et al. J Phys Chem B 2007, 111 (8),
2062-2069.
COIL-4:307
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Radiation Chemistry of Ionic Liquids for Energy Applications

James F. Wishart (1) , wishart@bnl.gov, Bldg. 555, Upton NY 11973, United States ; R.
Dale Rimmer (1) ; Jasmine L. Hatcher (1) ; Masao Gohdo (1) . (1) Chemistry Department,
Brookhaven National Laboratory, Upton NY 11973, United States
Ionic liquids (ILs) can make major contributions to the establishment of a sustainable
energy economy through their use in sophisticated technologies for the production,
storage and efficient consumption of energy. Some of the most intriguing applications
involve the exposure of ILs to extreme conditions of reactivity such as very high or low
electrochemical potentials, plasma discharges, photolysis or ionizing radiation. As an
example, ILs may be used in new schemes for the recycling of spent nuclear fuel that
would close the loop on the nuclear fuel cycle, resulting in much more efficient use of
natural resources and dramatic reductions in the volume and longevity of radioactive
waste. They will also be exposed to radiation during the extraction of precious rare earth
elements from naturally occurring deposits. We use radiation chemical and
photochemical methods to study reactivity that is relevant to these important
technologies. Since ILs used for nuclear separations and mineral extraction systems will
be subjected to ionizing radiation that will degrade their performance over time, we use
pulse radiolysis and other techniques to elucidate radiation-induced reaction pathways
as a function of ionic liquid composition in order to minimize the effects of degradation
on the proposed extraction systems. We also use pulse radiolysis and time-resolved
laser techniques to examine how ILs affect electron transfer reactions and the
dynamical response of ILs to charge migration. This information will be useful in the
design of optimal IL-based systems for advanced devices such as supercapacitors,
electrochromic displays and windows, photoelectrochemical solar cells, and batteries.
We will present our recent results on reactivity in ionic liquids and discuss the
implications for their use in sophisticated technologies. This work was supported by the
U. S. Department of Energy Office of Basic Energy Sciences under contract #DE-AC02-
98CH10886.
COIL-4:308
Prediction of Enzymatic Conversion in Ionic Liquid Using Molecular Dynamics
Simulations
Yoon-Mo Koo (1) , ymkoo@inha.ac.kr, 253 Yonghyun-dong, Nam-gu, Incheon, Republic
of Korea ; Sung Ho Ha (2) . (1) Department of Biological Engineering, Inha University,
Incheon 402-751, Republic of Korea (2) Department of Chemical Engineering and
Nano-Bio Technology, Hannam University, Daejeon 305-811, Republic of Korea
Room temperature ionic liquids (ILs) have recently been very popular as green solvents
due to their unique physicochemical properties of negligible vapor pressure, nonflammability,
excellent thermal stability and a strong ability to dissolve a wide range of
organic and inorganic compounds. They also have great potential as reaction media or
co-solvent for enzymatic reaction. Their use can improve activity, selectivity, and
stability of enzyme. In this presentation, the application of ILs in biocatalysis will be
mainly addressed. For Lipase-catalyzed direct esterification of glucose in pure ILs, we

have developed a new procedure referred to as 'water-mediated supersaturation' to
prepare a high concentration of sugars in ILs. The glucose concentrations in the
supersaturated [Emim][TfO] and [Bmim][TfO] were 19 and 10 times higher, respectively,
than the solubility of glucose in the ILs at 25°C. Higher dissolved concentration of
glucose in the supersaturated solution led to an increase in the reaction rate and
conversion. To understand this phenomena, the change in molecular interactions in
water-mediated [Emim][TfO] system and pure [Emim][TfO] system was explored using
all-atoms molecular dynamics simulations. We found that diffusivity of all components in
the system ([Emim] + , [TfO] - , and glucose) in water-mediated [Emim][TfO] tends to be
higher than that in [Emim][TfO]. Through the hydrogen bonding occupancy statistics and
radial distribution function analysis, glucose molecules are found to interact more with
water and anion, but less with other glucose molecules in water-mediated [Emim][TfO]
as compared to those in [Emim][TfO]. Our simulation study shows that water acts as a
co-solvent that disrupts glucose-anion and glucose-glucose interactions which
consequently increases glucose solubility.
COIL-4:309
Understanding Solutions of Salts in Ionic Liquids
Tom Welton (1) , t.welton@imperial.ac.uk, Exhibition Road, London . SW7 2AZ, United
Kingdom ; Matthew Y Lui (1) ; Lorna Crowhurst (1) ; Jason P Hallett (1) ; Patricia A Hunt (1) ;
Heiko Niedermeyer (1) . (1) Department of Chemistry, Imperial College, London SW7
2AZ, United Kingdom
In spite of the huge amount of interest that ionic liquids have generated, understandings
of how they solvate solute materials are very poor and results regarding the crucial
solvent property of polarity of ionic liquids are directly contradictory. Sometimes ionic
liquids are reported to be polar and at others they are said to be non-polar. We report
here results that resolve these contradictions and reveal a completely new solvation
paradigm for solutions of salts in ionic liquids. In all molecular solvents, including
water, salts dissolve to give a variety of solute species, such as contact ion pairs,
solvent separated ion pairs or free solvated ions, but in all cases the solute cation and
anion require each other's proximity in order to preserve charge neutrality. We
demonstrate that ionic liquids, conversely, solvate individual solute ions completely as
the ionic liquid itself is capable of preserving charge neutrality. This has far-reaching
consequences, in areas as diverse as synthesis and electrochemical device
applications. Our studies of the charge-transfer salt 1-ethyl-4-
(methoxycarbonyl)pyridinium iodide, Kosower's salt, which was initiated to investigate
the ion-paring behaviour above also showed remarkable results regarding the polarity of
ionic liquids. In a single set of measurements it was shown that the ionic liquids were
both non-polar (position of absorption band) and highly polar (intensity of absorption
band). This apparent contradiction has been resolved using the concept of timescales,
so resolving an active debate in the literature.
COIL-4:310

New Ionic Liquid Catalyst Systems for Valorization of Biomass Resources
Anders Riisager (1) , ar@kemi.dtu.dk, Technical University of Denmark, Lyngby 2800,
Denmark ; Tim Ståhlberg (1) ; Shunmugavel Saravanamurugan (1) ; Olivier Nguyen Van
Buu (1) ; Andreas J. Kunov-Kruse (1) ; Peter Fristrup (1) . (1) Centre for Catalysis and
Sustainable Chemistry, Department of Chemistry, Technical University of Denmark,
Lyngby, Denmark
The impending exhaustion of fossil resources and climate change has prompted an
intensified research for establishing new and better pathways for obtaining
carbonaceous chemicals and fuels from renewable sources. Carbohydrates constitute
in this context an essential source representing 75% of the worlds renewable biomass
with cellulose (a glucose polymer) being the most abundant. In a future carbohydratebased
chemical industry furanic compounds like 5-(hydroxymethyl)furfural (HMF),
formed by the triple dehydration of hexoses (i.e. glucose and fructose), is expected to
play a key role. HMF is primarily considered to be a starting material for its diacid
counterpart 2,5-furandicarboxylic acid (FDA), which is a very attractive monomer
replacement of terephthalic acid in polyesters and plastics. Secondarily, reduction of the
furan ring yields compounds suitable as solvents or fuels. Furthermore, rehydration of
HMF led to formation of levulinic acid which is yet another important renewable platform
chemical that can serve as a valuable source to produce, e.g. food flavoring agents,
plasticizers and succinic acid and derivatives. Despite the obvious potential of HMF as
key intermediate chemical, efficient and industrial suitable synthetic routes to HMF are
still not accomplished nor are upgrading technology for processing HMF into other
industrially useful chemicals. The current presentation will address the unique potential
offered by applying ionic liquid systems in valorization of biomass resources, and
highlight new catalytic systems relying on ionic liquids which are viable for converting
hexose carbohydrates into HMF and important derivatives hereof, including FDA and
alkyl levulinates.
COIL-4:311
Multiple Structural and Dynamical Behaviour of Ionic Liquids: A Microscopic View
Barbara Kirchner, University of Leipzig, Email: bkirchner@uni-leipzig.de
Barbara Kirchner (1) , bkirchner@uni-leipzig.de, Linnestr. 2, Leipzig Saxonia 04103,
Germany . (1) Department of Physical and Theoretical Chemistry, University of Leipzig,
Leipzig Saxonia 04103, Germany
Describing the liquid as well as the gas phase of complicated liquids such as ionic
liquids (ILs) will continue to be a nontrivial task. [1] This is due to the fact that ionic
liquids contain multiple aspects of structural and dynamical behaviour. The complete
picture of ionic liquids forms by considering the sum of these aspects. In this
presentation we will show the decomposition into different intermolecular forces in ionic
liquids and the consequences of their unequal weights. [2-5] We will also present the ab

initio molecular dynamics simulations of one [Emim][EtSO4] ion pair at different
temperatures and with different functional groups in order to explore the gas phase. The
structural properties as well as the conformational dynamics resembles to the
experimentally observed fact that [Emim][EtSO4] distills at higher temperatures than
other ILs. Next, the classical simulations of [Bmim] revealing the dynamical
heterogeneity is discussed. [6] Finally, some ab initio simulations results of an IL
mixture will be given. Literature: [1] Topics in Current Chemistry, 290, 213, (2010) [2]
Angew. Chem. Int. Ed., 41, 3639, (2008), [3] J. Phys. Chem. A, 112 , 8430, (2008),
[4] Phys. Chem. Chem. Phys.,12 (27) 7473, (2010) [5] J. Mol. Struct., 972 , 22, (2010)
[6] J. Phys. Chem. B, 115 (4) 693, (2011)
COIL-4:312
Do We Already Know Everything?
Luís Paulo N. Rebelo (1) , luis.rebelo@itqb.unl.pt, Av. da República, Oeiras Oeiras 2780-
901, Portugal ; José N. Canongia Lopes (1) ; Cristina S. Pereira (1) ; José M. S. S.
Esperança (1) ; Isabel M. Marrucho (1) ; Ana B. Pereiro (1) ; Magdalena Kowacs (1) ;
Mohammad Tariq (1) ; Mara G. Freire (1) ; Helena I. M. Veiga (1) ; João M. M. Araújo (1) . (1)
Instituto de Tecnologia Química e Biológica (ITQB), Oeiras 2780-901, Portugal
In spite of the tremendous increase in the last decade in our understanding of the
structure, type and strength of interactions, and dissolution quality of many classes of
ionic liquids - as well as their impact on living organisms, and the environment in
general - many important details remain to be uncovered. Most of the remaining
challenges are due both to the overwhelming number of liquid salts comprising this
group of chemical compounds and their inherent chemical diversity. As a consequence,
many “neat” ionic liquids can be found at the boundary with mixtures (e.g., protic ionic
liquids), while others are more closely related either to the group of traditional molten
salts or to that of traditional surfactants, with a lack of clear distinctions along the
continuum. Therefore, the characteristics transform more or less smoothly as one scans
across the range of classifications, focusing first one group, then the next. We will
address some of the aforementioned topics by illustrating part of our work at ITQB,
which involves studies of: (i) chain and morphology effects, (ii) absolute negative
pressure regimes, (iii) ion-pairs versus clusters in the gas phase, (iv) salting-in/out
effects, (v) combined alkane-perfluoralkane-polar outcomes, (vi) protein stability and
activity, (vii) dissolution of bio-molecules and macromolecules, (viii) crystallization
phenomena, and (ix) biocompatibility and the activity of microorgasnisms.
COIL-4:313
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Combination of Ammonia and/or Oxygen with an Ionic Liquid for the
Delignification of Miscanthus

Héctor Rodríguez (1)(2) , hector.rodriguez@usc.es, Rúa Lope Gómez de Marzoa, s/n,
Santiago de Compostela A Coruña 15782, Spain ; Sasisanker Padmanabhan (1) ;
Geoffrey Poon (1) ; John M Prausnitz (1) . (1) Department of Chemical and Biomolecular
Engineering, University of California, Berkeley, Berkeley CA 94720, United States (2)
Department of Chemical Engineering, University of Santiago de Compostela, Berkeley
CA 94720, United States
Miscanthus, a wild grass, is a suitable source for production of bioethanol. A possible
option in the pretreatment of miscanthus, to make its cellulose and hemicellulose more
easily hydrolyzable, is its dissolution in an ionic liquid. It is desirable to reduce the lignin
content in the pretreated material, to improve the performance of the subsequent
hydrolysis step. In this work, gaseous ammonia and/or oxygen were used to enhance
the delignification of miscanthus dissolved in 1-ethyl-3-methylimidazolium acetate at
140 °C. After dissolution at a pressure of 9 bar, water was added as antisolvent to
regenerate the dissolved biomass. In a next step, an acetone/water mixture was used to
remove carbohydrate-free lignin from the regenerated biomass. The lignin content in the
final product was around 10 %, much lower than the ca. 23 % lignin content of the raw
dry miscanthus. This lignin reduction was achieved without diminution of cellulose or of
total carbohydrates recovered, relative to the recovery achieved with the ionic liquid
pretreatment in contact with air or nitrogen at the same pressure (9 bar).
COIL-4:314
Degradation of Poly(Ethylene Terephthalate) Wastes Using Ionic Liquids
Suojiang Zhang (1) , sjzhang@home.ipe.ac.cn, P.O. Box 353, #1 Beiertiao,
Zhongguancun, Haidian District, Beijing, China., Beijing Beijing 100190, China ; Qian
Wang (1) ; Xingmei Lu (1) ; Zengxi Li (1)(2) ; Xiangping Zhang (1) ; Chunshan Li (1) . (1) Institute of
Process Engineering, Chinese Academy of Sciences, China (2) Graduate University of
Chinese Academy of Sciences, China
The amount of Polyethylene terephthalate (PET) wastes has been increasing
significantly year by year and PET wastes do not decompose readily in nature,
therefore, the effective recycling of PET wastes has received wide attention for the
preservation of resources and protection of environment. Although several methods
have been proposed for recycling PET wastes, it suggested that the most attractive
method is chemical glycolysis into the corresponding monomers or raw chemicals. It
has been reported that ionic liquids could used in the degradation of PET into the
monomers bis(2-hydroxyethyl terephthalate)(BHET). Hui Wang etc [1] found that 1-butyl-
3-methylimidazolium tetrachloroferrate ([bmim]FeCl4) can be used to catalyze the
depolymerization of PET. But the conversion of PET and the selectivity of BHET are
lower. Therefore, the further study of ionic liquids that can degrade PET effectively is
critical. In this study, kinds of Fe-containing ionic liquids [Cnmim][FeCl4] (n = 2, 4, 6, 8)
have been synthesized according to synthesis mothods of the other metal-containing
ionic liquids, characterized for Electrospray Ionization-Mass Spectrum and Raman
spectroscopy, and the degradation of PET wastes in these ionic liquids has been

measured. It is found that the conversion of PET wastes increase when the length of
cations' alkyl increases but selectivity of BHET has little change. When the length of
cations' alkyl increased from 2 to 8, the conversion of PET wastes increased from
86.1% to 94.7% under the same conditions. [1] Hui Wang, Ruiyi Yan, Zengxi Li, et al.
Catal. Commun., 2010, 11(8): 763-767.
COIL-4:315
Evaluation of the Performance of Tricationic Ionic Liquids for Different Separation
Problems
Fabrice MUTELET (1) , fabrice.mutelet@ensic.inpl-nancy.fr, 1 rue Grandville, NANCY
54001, France ; Jean-Charles MOISE (1) ; Jean-Noël JAUBERT (1) . (1) Laboratoire
Réactions et Génie des Procédés (CNRS UPR 3349) - Ecole Nationale Supérieure des
Industries Chimiques, NANCY 54001, France
Much of the interest in ionic liquids is based on their promise as green substitutes for
traditional industrial solvents such as volatile organic compounds. Development of safer
and environmentally friendly processes and products is needed to achieve sustainable
production and consumption patterns. New chemical products, such as ionic liquids,
which are of great interest to the chemical and related industries because of their
attractive properties as solvents, should be considered. Ionic liquids are comprised of
an asymmetric, bulky organic cation and a weakly coordinating organic or inorganic
anion. A large number of possible combinations allows for the ability to 'fine tune' the
solvent properties for a specific purpose. Physical and chemical properties of ILs are not
only influenced by the nature of the cation and the nature of cation substituents but also
by the polarity and the size of the anion. These features infer to ILs numerous
applications, in organic synthesis, separation processes and electrochemistry. This
study presents thermodynamic properties of six trigeminal tricationic ionic liquids with
polar chain grafted on cation. Information on interactions of this class of ionic liquids
with solutes containing polar functional groups can be obtained with infinite dilution
activity coefficients. In the present work we report infinite dilution activity coefficients
data obtained with several families of ionic liquids. Then, we discuss interactions
between ionic liquids and organic molecules in terms of thermodynamic solvation
theories. Then, the performance of this class of ionic liquids for different separation
problems is evaluated.
COIL-4:316
Modeling the Solubility of Carbon Dioxide in Ionic Liquids with the PC-SAFT
Equation of State
Fabrice MUTELET (1) , fabrice.mutelet@ensic.inpl-nancy.fr, 1 rue Grandville, NANCY
54001, France ; Yushu CHEN (1) ; Jean-Noël JAUBERT (1) . (1) Laboratoire Réactions et
Génie des Procédés (CNRS UPR 3349) - Ecole Nationale Supérieure des Industries
Chimiques, NANCY 54001, France

Ionic liquids (ILs) are currently receiving much attention due to their interesting physicochemical
properties: negligible vapor pressure, high thermal stability, liquid in a large
range of temperature, etc. For these reasons, ILs are being postulated as promising
alternative solvents for a number of technological applications in the context of green
processes. The structural effect on physico-chemical properties should be intensively
studied in terms of the identity of the cation and anion, variation of the side chain in the
cation. Such comprehensive studies enhance the knowledge necessary to design and
optimize ionic liquids for many applications. This knowledge can be obtained by
experimental techniques and/or simulations. A main advantage of the use of equation of
state versus the other techniques is the speed in which these calculations are
performed. A theory like PC-SAFT that is based in statistical mechanics offers several
advantages. The first advantage is that each of the approximations made in the
development of SAFT such as the chain and association terms has been verified
against molecular simulation results. In this way, the range of applicability and the
shortcomings of each term in the equation of state have been assessed. A second
advantage is that the SAFT parameters have physical meaning. The PC-SAFT is a
useful tool in which the effects of molecular structure on the thermodynamic properties
can be separated and quantified. For example, non-ideal contributions such as chain
length and/or molecular shape, molecular association and polar interactions can be
introduced in the development of the equation. In this work, we present the application
of the PC-SAFT equation of state to predict the solubility of gases in ionic liquids. The
equation has been first applied to the pure Ils in order to determine the pure molecular
parameters. The solubility of CO2 in the ionic liquids is predicted with good accuracy
using this equation of state.
COIL-4:317
Role of Ionic Liquids in the Future of the Thorium Based Nuclear Fuel Cycle
Erica L Stoner (1) , elstoner@crimson.ua.edu, Box 870336, Tuscaloosa AL 35487,
United States ; Steven P Kelley (1) ; Robin D Rogers (1) . (1) Department of Chemistry and
Center for Green Manufacturing, The University of Alabama, Tuscaloosa AL, United
States
Ionic liquids (ILs) have shown promise in the area of separations and are currently
being explored as a means of nuclear waste processing, where they may have promise
in replacing organic solvents and providing new avenues for liquid-liquid extraction.
While most IL research in this particular arena has focused on possible uses with spent
nuclear reactor fuel from the uranium cycle currently employed in the U.S., little
attention has been paid to using ILs to help overcome similar separations challenges
faced by using a thorium based fuel cycle. The U.S. currently uses the once through
uranium cycle, but the limited supply of uranium ore and the possibility that the U.S. will
have to rely on imported fuel offers additional challenges to the widespread
implementation of this type of nuclear fuel cycle. While the use of thorium as nuclear
fuel does not overcome all challenges associated with nuclear energy, it is does offer
certain benefits over using uranium including a) lower operating costs due to higher

abundance and a lower need for importation, and b) a reduced production of weapons
grade isotopes during the fuel cycle which reduces proliferation concerns. Considering
the task of developing a nuclear reactor system from beginning to end there is a unique
research opportunity to integrate the use ILs throughout the reactor cycle. Continued
study of thorium in ILs will also help further the understanding of fundamental thorium
chemistry. This presentation will provide an overview of our motivation for this research,
our current results, and our future challenges.
COIL-4:318
Design of Organic-Inorganic Hybrid Type Ion-Gels by In-Situ Polymerization
Method
Kousuke Yoshida (1) , matsumi@jaist.ac.jp, Furo-cho, Chikusa-ku, Nagoya 464-8601,
Japan, Nagoya Aichi 464-8601, Japan ; Sonu R Shankar (2) ; Noriyoshi Matsumi (2) . (1)
Graduate School of Bioagricultural Sciences, Nagoya University, Nagoya Aichi 464-
8601, Japan (2) School of Materials Science, Japan Advanced Institute of Science and
Technology, Nomi Ishikawa 923-1292, Japan
Design of highly conductive and thermally stable electrolyte is a matter of universal
concern for a variety of ionics devices. In the present study, we undertook the design of
organic-inorganic hybrid type ion-gels by in-situ polymerization method. 1) A radical
polymerization of ionic liquid monomer with acrylate group and 2) Sol-gel condensation
of alkoxysilane/alkoxyborane were carried out simultaneously to give highly transparent
and homogeneous hybrid materials in good efficiency. First, hybrid materials
composed of silicate glass and comb like polymerized IL were prepared. The hybrid
materials obtained showed maximum ionic conductivity of 3.0 x 10 -4 Scm -1 at 51 o C. An
incorporation of boron atom as borosilicate glass was found to be quite effective to
enhance ionic conduction (2.6 x 10 -3 Scm -1 at 51 o C). This is because of promotion of
salt dissociation in the presence of such Lewis acidic structure, and also of softness of
the resulting matrix. From the thermogravimetric analysis (TGA), all the materials
obtained here were stable up to 400oC

Cellulose based organoboron ion-gels were synthesized via condensation of cellulose
with BH3 or mesitylborane in 1-butyl-3-methylimidazolium chloride ([BMIm][Cl]). Ionic
conductivity of ion-gels was evaluated by ac-impedance method. The obtained ion-gels
showed ionic conductivity of 3.4×10 -3 ~4.1×10 -4 Scm -1 at 51 o C. When mesitylborane
was employed instead of BH3, resulting ion-gels exhibited higher ionic conductivity. High
boron content resulted in increased dissociation of LiCl as observed from VTF
parameter corresponding to carrier ion number. Condensation between 6-Otritylamylose
and mesitylborane was carried out to prepare borylated amylose. Ion-gel
matrices was prepared by mixing LiTFSI and 1-ethyl-3-methylimidazolium TFSI
([EMIm][Tf2N]) with the borylated amylose. Ionic conductivity of this material was
1.1×10 -4 Scm -1 at 51 o C. This matrix showed high decomposition temperature (50%
loss) of higher than 430 o C. Acknowledgement We are grateful to financial support
for the present study by New Energy and Industrial Technology Development
Organization (NEDO) of Japan.
COIL-4:320
Transition Metals and Alloys Electrodeposition from Choline Chloride Based Ionic
Liquids
Laura Sanchez (1) , laura.sanchez@tecnalia.com, Paseo Mikeletegi 2, Parque
Tecnológico Miramón, San Sebastián Guipúzcoa 20009, Spain ; Uxoa Izagirre (1) . (1)
Materials for Energy Group, Tecnalia Research and Innovation, San Sebastian
Guipuzcoa 20009, Spain
Elecrolitic deposition of different transition metals and alloys from choline chloride: urea
(1:2) and/or choline chloride: etilen glicol (1:2) based ionic liquids mixed with metallic
salts have been studied. The results have shown that homogeneous coatings of Zn,
nanostructured Cu and different types of Cr (nano chrome, black chrome and hard
chrome) can be successfully achieved by adjusting process parameters such as current
density, temperature or metallic salt concentration amongst others. Apart from pure
metals, the electroplating of alloys such as Zn/Sn alloys has been also studied from
choline chloride: urea (1:2) ionic liquids. The results revealed that Zn/Sn alloys with
significantly richer composition in Zn (70% w/w) than those obtained in aqueous
electrolytes (30 % w/w Zn max.) can be achieved using this type of ionic liquids. The
obtained coatings have been structurally characterized by means of SEM/EDS
microcopy, optical microscopy and/or AFM microscopy and functionally characterized
by means of adhesion tests or salt spray fog corrosion tests amongst others. The
electrodeposition experiments have been completed performing a bath life study of the
nanochrome electroplating bath, obtaining that coatings with satisfactory aspect can be
obtained until 150 A/hl have been passed through the bath. Finally, toxicological tests
have been carried out to the ionic liquid bath used for the hard chrome plating in order
to asses its environmental risks. The results of such tests have revealed that this ionic
liquid is not really degradable, is harmful to aquatic organisms and that, therefore, it
might cause long term adverse effects in the aquatic environment.

COIL-4:321
1-Alkyl-3-Methlyimidazolium Chloride Ionic Liquids on Gold Surfaces:
Adsorption, Friction and Morphology
Jose Nuno Canongia Lopes (1)(2) , jnlopes@ist.utl.pt, Av Rovisco Pais, Lisboa Portugal,
Portugal ; Mohammad Tariq (1)(2) ; Ana Paula Serro (2) ; Rogerio Colaço (2) ; Benilde
Saramago (2) ; Luis Paulo N. Rebelo (1) . (1) Instituto de Tecnologia Quimica e Biológica /
UNL, Oeiras 2780 157, Portugal (2) Centro de Quimica Estrutural, Instituto Superior
Tecnico / UTL, Oeiras 2780 157, Portugal
The adsorption of surfactants on solid surfaces has been the subject of numerous
studies because of the widespread technological application of this phenomenon in
wetting, adhesion, nano-fabrication, cleaning and degreasing of metal surfaces. Ionic
liquid surfactants are a new class of surfactants exhibiting many promising features
compare to their conventional counterparts' viz., they can retain the micellar structures
up to relatively high temperatures (200 o C), the versatile nature of their homologous
series allows to design novel biodegradable, non-toxic compounds with different head
groups and specific features. It would be interesting to exploit their unique properties in
various surface science applications. This fact motivates us to study the adsorption,
frictional and morphological behaviour of a commonly studied series of 1-alkyl-3methylimidazolium
chloride ionic liquid surfactants at solid surface namely gold. The
Quartz Crystal Microbalance studies revealed that ILs readily adsorbed at gold
surfaces, the friction coefficient increases as the alkyl side chain grow longer and all ILs
show distinct morphology after adsorption at gold surfaces as observed using Atomic
Force Microscopy. Moreover, some interesting effects of concentration and surface
treatment on the adsorption phenomena and different surfaces (e.g., silicon) on
morphologies have also been observed. [1] M. Tariq et al., Colloid Surf. A (2011) 377,
361
COIL-4:322
Efficient Biodegradation of Common Ionic Liquids by Sphingomonas
Paucimobilis
Jose Palomar (1) , pepe.palomar@uam.es, Cantoblanco Universidad, Madrid Madrid
28049, Spain ; Concepcion Abrusci (2) ; Francisco Rodriguez (3) ; Fernando Catalina (4) . (1)
Chemical Engineering, Universidad Autonoma de Madrid, Madrid Madrid 28045, Spain
(2) Molecular Biology, Universidad Autonoma de Madrid, Madrid 28049, Spain (3)
Chemical Engineering, Universidad Complutense de Madrid, Madrid 28040, Spain (4)
Instituto de Ciencia y Tecnologia de Polimeros, Consejo Superior de Investigaciones
Cientificas, Madrid 28010, Spain
The biodegradation of ionic liquids (ILs) was evaluated by an indirect impedance
technique, through which carbon dioxide production was measured during bioassay
time. The biodegradation study was focused to find a microorganism able to efficiently

degrade common IL compounds. For the fist time, a bacteria strain of Sphingomonas
paucimobilis was employed in biodegradability tests of ILs, carried out for 37
commercial imidazolium-, pyridinium-, pyrrolidinium-, ammonium- and phosphoniumbased
ILs, including the sample 12 different anions and 14 different cations. Our results
show that many common ILs, even those previously noted as no biodegradable, can be
successfully biodegraded by S. paucimobilis bacterium at 45 ºC. We found that 20 ILs
among 37 compounds studied can be considered “easily biodegradable” (60 %
biodegradability in 28-day period). The selection of anion can drastically increase the
rate of biodegradation of these solvents. The different alkyl chain and head group of
cation has also shown influence on IL biodegradability, but in a lower extent. The genus
of S. paucimobilis bacteria seems capable of adapting to high concentrations of ILs.
Petri dish tests showed, after incubation for 24 hours at 45ºC, an active growth of S.
paucimobilis in media containing extremely high IL concentrations (0.5 g/L). In sum,
current results suggested the possibility of biotreatment for the rapid and ultimate
mineralisation of widely used ILs, which were noted as recalcitrant to biodegradation in
previous standard tests with other microorganisms.
COIL-4:323
Synthesis of Ionic Liquids with Low Halide Content Having Sulfonate and
Carboxylic Acid Derivatives by Using Micro-Reactor.
jung bok ryu (1) , rjb4575@c-tri.co.kr, 778-1, Ilpaedong Namyangju/kyunggido, Republic
of Korea . (1) Ionic liquid synthesis, C-TRI, kyunggido namyangju/ilpaedong 778-1,
Republic of Korea
Ionic liquids have so many adventages of thermal stability, non-flammability, high ionic
conductivity, non-volatility. But, the residual halide and other impurities have large effect
on physical properties. The problem here is that it's difficult to remove such unwanted
contents in connection with separation and purification. To solve this problem and
improve the durability properties, new type synthesis method of the micro-reactor,
through which imidazolium, pyridinium, pyrrolidinium, ammonium derivatives ionic
liquids with low halide content synthesized with methylsulfate,
trifluoromethanesulfonate, acetate and thiocyanate reagents as intermediate compound
is introduced. In addition, the synthesis conditions of the micro-reactor and the yield
efficiency, halide content and the properties such as conductivity and decomposition
temperature of ionic liquids are depicted.
COIL-4:324
Interfacial Mass Transfer Rates for Liquid-Liquid Systems with Ionic Liquids
Aaron M. Scurto (1) , ascurto@ku.edu, 1530 W. 15th St., 4132 Learned Hall, Lawrence
KS 66045, United States ; Azita Ahosseini (1) ; Jerzy Petera (2) ; Laurence R. Weatherley (1) .
(1) Department of Chemical and Petroleum Engineering, University of Kansas,

Lawrence KS 66045, United States (2) Process and Environmental Engineering,
Technical University of Łódź, Łódź, Poland
Biphasic systems with ionic liquids and various solvents are used as an efficient
platform for reactions and extractions. However, little mass transfer data exists in the
literature for any system involving ionic liquids, which impedes development and scaleup.
This presentation will illustrate the interfacial mass transfer in a model biphasic
system with 1-hexyl-3-methyl-imidazolium bis[trifluoromethylsulfonyl)amide
([HMIm][Tf2N]) and 1-octene. The physical, thermodynamic, and mass transport
properties are highly concentration dependent and have been measured. From phase
equilibrium studies, the IL has very little solubility in the 1-octene phase, but 1-octene
has moderate solubility in the IL phase. This simplifies the analysis as mass transfer
occurs in only 1 direction. Interfacial mass transfer studies have been conducted for
falling droplets of ionic liquid in a continuum of 1-octene in 1 and 2 meter columns. In
addition, detailed studies using a high-speed camera have been used to investigate the
droplet geometry and flight times. The robust mass transfer model of Weatherley and
Petera has been utilized to correlate and predict the mass transfer rates for any
geometry and any hydrodynamic regime based upon limited physical property and
thermodynamic data.
COIL-4:325
Rotational Motion of Probe Molecules in 1-Butyl-3-Methylimidazolium
Hexafluorophosphate Near the Glass Transition
Edward L Quitevis (1) , edward.quitevis@ttu.edu, Box 41061, Lubbock TX 79409, United
States ; Fehmi Bardak (1) ; Justin R. Rajian (1) ; Larry G. Hines Jr. (1) ; Richard A. Bartsch (1) .
(1) Department of Chemistry & Biochemistry, Texas Tech University, Lubbock TX
79409, United States
The rotational motion of rubrene and tetracene in 1-butyl-3-methylimidazolium
hexafluorophosphate ([bmim][PF6]) near the glass transition (Tg = 196 K) was measured
using a photobleaching technique. In the temperature range 190 to 200 K (Tg – 6 K to Tg
+ 4 K), the rotational anisotropy is well fit by a Kohlrausch-Williams-Watts (KWW)
function, Φ(t) = exp[-(t/τ0) β ]. In the case of rubrene, β is constant and equal to 0.96 ±
0.03, whereas in the case of tetracene, β decreases as the temperature is lowered
toward Tg, with β = 1.00 ± 0.03 at T =198 K and β = 0.69 ± 0.08 at T = 191 K. At Tg, the
rotational correlation time is 135 ± 6 s for rubrene and 18 ± 2 s for tetracene, which is
consistent with rubrene being larger in size than tetracene. The values of β for these
probes indicate that rotation is less dispersive for rubrene than for tetracene. Given that
rubrene is larger in size than tetracene, this difference in the behavior of these probes is
consistent with the dynamics in [bmim][PF6] being spatially heterogeneous.
Interestingly, the rotational correlation time follows a fractional Debye-Stokes-Einstein
(DSE) relation,τc ∼ η α /T, with α = 0.65 ± 0.04 for both probe molecules. This suggests
that near Tg, the rotational diffusion of these probe molecules is decoupled from
structural relaxation in the ionic liquid.

COIL-4:326
Self-Assembly of Cationic Surfactants in a Protic Ionic Liquid
Carlos R Lopez-Barron (1) , lopez@udel.edu, 150 Academy St, Newark DE 19716;
Norman J Wagner (1) . (1) Chemical Engineering, University of Delaware, Newark DE
19716, United States
Ionic liquids (IL) represent is a very attractive class of solvents due to their appealing
physicochemical properties. These include thermal and chemical stability, negligible
vapor pressure, high ionic conductivity and wide electrochemical window. In this work
we study surfactant self-assembly in IL and the structure-property relationships for the
shear rheology. Using a combination of experimental methods including rheology,
cross-polarized light microscopy, and small angle neutron scattering, we characterized
the phase diagram of the surfactant/IL model system: Cetyl trimethylammonium
bromide (CTAB)/ethylammonium nitrate (EAN). The isotropic to hexagonal I-H transition
occurred at remarkable high CTAB concentrations (~50 wt %). This transition is marked
by an increase of up to three orders of magnitude in the elastic modulus; which results
in a self-sustaining gel with a yield stress. The onset of the yield stress was temperature
dependent and the I-H transition is perfectly reversible. These characteristics make this
system very promising for applications where a combination of processability and
stillness is crucial.
COIL-4:327
Absorption of CO2 by Acetate Ionic Liquids
Margarida F Costa Gomes (1) , margarida.c.gomes@univ-bpclermont.fr, BP 80026,
Aubière, France ; Ajda Podgorsek (1) ; Stéphane Stevanovic (1) ; Agilio A.H. Padua (1) . (1)
Université Blaise Pascal Clermont-Ferrand & CNRS, Laboratoire Thermodynamique et
Interactions Moléculaires (UMR 6272), Aubière 63171, France
The absorption of carbon dioxide by three ionic liquids with the acetate anion, 1-ethyl-3methylimidazolium
acetate ([C1C2Im][OAc]), 1-butyl-3-methylimidazolium acetate
([C1C4Im][OAc]) and 1-butyl-1-methylpyrrolidinium acetate ([C1C4Pyrro][OAc]), was
studied experimentally at low pressures and as a function of temperature. It was
observed that the imidazolium ionic liquids chemically absorb the carbon dioxide leading
to mole fraction concentrations of CO2 up to 0.2, when in equilibrium with the gas at 0.1
bar. The effect of the addition of water on the absorption of carbon dioxide by the
acetate ionic liquids was studied experimentally at pressures close to atmospheric and
as a function of temperature between 303 and 343 K. It was observed that the
absorption of carbon dioxide decreases with increasing amount of water. The presence
of 0.6 mole fraction of water (around 14% w/w) results in a reduction of carbon dioxide
solubility of 40% and 60%, for [C1C2Im][OAc] and [C1C4Im][OAc], respectively.
Molecular dynamics simulation was used for assessing the molecular mechanisms of
solvation of CO2 in [C1C4Im][OAc] and [C1C4Pyrro][OAc]. Results show that carbon

dioxide is solvated preferentially in the non-polar domain of the solvent, and that the
CO2−anion interactions dominate over the CO2−cation interactions. Molecular
simulations reproduce the experimental solubility of CO2 in the ionic liquid 1-butyl-3methyl
trifluoroacetate, [C1C4Im][TFA], proving that there is no chemical absorption. The
absorption of carbon dioxide by [C1C4Im][OAc] or by [C1C4Pyrro][OAc] is largely underpredicted
by molecular simulation, the higher absorption of CO2 by the acetate ionic
liquids being ascribed to a chemical reaction.
COIL-4:328
Detailed Identification of Radiolysis Products in Imidazolium Bistriflylimide Ionic
Liquids
R Dale Rimmer (1) , Rrimmer@bnl.gov, Bldg 555, Upton NY 11973, United States ;
Jasmine Hatcher (1) ; Bruce D Brownawell (2) ; Shawn Fischer (2) ; James F. Wishart (1) . (1)
Chemistry, Brookhaven National Laboratory, Upotn NY 11973, United States (2)
Environmental Science, Stony Brook University, Stony Brook Ny 11794, United States
Ionic liquids have the potential to play an important role as alternative media for
separations processes in the fuel cycles of advanced nuclear energy systems to help
meet the world's energy needs. In such applications, ILs will be exposed to ionizing
radiation. It is important to understand the factors that control their radiation stability and
whether the chemical changes induced by irradiation of ionic liquids affect their
performance in extraction systems. In this study, the consequences of ionization
radiation exposure to various ionic liquids have been explored. Selected
dialkylimidazolium bistriflylimide salts were exposed to doses of Co-60 gamma radiation
up to 2 MGy, and the radiolysis products were identified using liquid chromatography
and mass spectrometry. The specific damage locations on the dialkyimidazolium
cations were probed and quantified using site-specific deuteration. Sites that were more
susceptible to damage were identified; ionic liquids with modifications to these sites
were also studied in an attempt to enhance the radiation stability. This work was
supported by the U. S. Department of Energy, Office of Basic Energy Sciences, Division
of Chemical Sciences, Geosciences, and Biosciences under contract # DE-AC02-
98CH10886.
COIL-4:329
Solute Diffusion in Ionic Liquids: Solute Size Effects
Anne Kaintz (1) , aek201@psu.edu, 105 Chemistry Building, University Park
Pennsylvania, United States ; Gary Baker (2) ; Alan Benesi (1) ; Mark Maroncelli (1) . (1)
Pennsylvania State University, United States (2) University of Missouri, United States
Reactant diffusion often determines the rates of bimolecular reactions such as, for
example, electron transfer. Recent measurements of diffusion-limited electron transfer
rates have suggested anomalously rapid diffusion in ionic liquids (ILs). These

observations, and the possibility of obtaining information about the effects of reported
nanoscopic domain structure in ionic liquids, motivate our direct measurement of solute
diffusion rates. We have measured diffusion rates of aromatic solutes at infinite dilution
in a series of ionic liquids [Fig. 1]. Measurements were made on a DRX-400 Bruker
NMR with a 5 mm inverse broadband probe with triple axis gradients, running the
longitudinal-eddy-current delay stimulated echo pulse sequence with bipolar gradient
pulse pairs. As found in past studies, diffusion coefficients of the ions comprising these
IL solvents are close to the predictions of the Stokes-Einstein equation with slip
boundary conditions. In contrast, the Stokes-Einstein equation under-predicts the
diffusion coefficients of aromatic solutes by as much as a factor of eight. Similar to what
is found in conventional solvents, departures from Stokes-Einstein predictions are
correlated to the ratio of solute to solvent size, with the largest errors being for the
smallest solute/solvent size ratios. Deviations are much larger in IL solvents than in
conventional non-polar solvents, but are similar to the deviations found for nonpolar
solutes in alcohols. This similarity hints at possible parallels between the heterogeneous
structure of ionic liquids and normal alcohol solvents.
COIL-4:330
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Evaluation of the Formation and Extraction Capability of Cholinium-Based
Aqueous Biphasic Systems: Influence of Different Linear Alkanoate Anions
João M. M. Araújo (1) , jmmda@itqb.unl.pt, Av. da República, Oeiras Oeiras 2780-157,
Portugal ; Filipa Alves (1) ; Luís P.N. Rebelo (1) ; Isabel M. Marrucho (1) . (1) Instituto de
Tecnologia Química e Biológica, www.itqb.unl.pt, Universidade Nova de Lisboa, Oeiras
2781-901, Portugal
Presently, ionic liquids (ILs) are gaining technological and industrial relevance in many
disciplines, allowing therefore their implementation to the design of novel and
sustainable solutions to old problems. Solvent extraction, due to its effectiveness and
economic nature, is by far the most widely used separation technique for antibiotics and
biomolecules. Despite economical advantages of extraction using volatile organic
solvents, recent stringent environmental and safety regulations have made their
applications limited. The development of cost-effective separation techniques based on
liquid-liquid extraction with ILs-based aqueous biphasic systems (ABS), offers clear
advantages over traditional liquid–liquid extractions, in which the use of toxic organic
solvents is unavoidable. The evaluation of the influence of different linear alkanoate
anions on promoting cholinium-based ABS, maintaining the same inorganic salt, is
evaluated in this work. Furthermore, the capacity of the cholinium- based ABS as
extraction media for the partitioning of tetracycline, a broad-spectrum polyketide
antibiotic produced by the Streptomyces genus of Actinobacteria, and the partitioning of
synthetic antibiotics belonging to the class of fluoroquinolones, which have a very broad
spectrum of antibacterial activity will be evaluated. The main driving-force of this work
is the application of such cholinium-based aqueous biphasic systems to the extraction
of APIs (active pharmaceutical ingredients). Choline (a vital amine) generally refers to

various quaternary ammonium salts containing the N,N,N-trimethylethanolammonium
cation and was classified as an essential nutrient for humans by the Food and Nutrition
Board of the Institute of Medicine of the National Academy of Sciences. Therefore, a
new purification approach is proposed: a single concentration step with no further
purification. The obtained API-ILs (new biological active ionic liquids) contains the
original API in the bulk of the benign ionic liquid. The proposed methodology
undoubtedly promises high value for future pharmaceutical/biotechnological
applications.
COIL-4:331
Liquid-Liquid Equilibria of Cholinium-Derived Bistriflamide Ionic Liquids with
Alcohols and Water
José M. S. S. Esperança (1) , jmesp@itqb.unl.pt, Av. da República, Oeiras Oeiras 2780-
157, Portugal ; Anabela J. L. Costa (1) ; Mário R. C. Soromenho (1) ; Ana B. Pereiro (1) ; José
N. C. Lopes (1)(2) ; Isabel M. Marrucho (1) ; Luís P. N. Rebelo (1) . (1) Instituto de Tecnologia
Química e Biológica/Universidade Nova de Lisboa, Oeiras 2780-157, Portugal (2)
Centro de Química Estrutural, Complexo Interdisciplinar, Instituto Superior
Técnico/Universidade Técnica de Lisboa, Oeiras 2780-157, Portugal
Choline is an essential micronutrient, usually grouped as a B-complex vitamin, which is
important in several body functions. Ionic liquids based on the cholinium cation
(trimethyl-hydroxyethylammonium) have been investigated as possible environmentally
friendly alternatives[1] to conventional ionic liquids in distinct research fields.
Nevertheless, most of the ionic liquids based on cholinium cation show higher melting
points than those of common alkyl-imidazolium based ionic liquids, including those with
the bistriflamide (bis(trifluoromethanesulfonyl)imide) anion. To overcome this problem, a
new family of ionic liquids inspired on the cholinium cation, alkyl-dimethylhydroxyethylammonium,
with the alkyl chain ranging from C2 to C5, combined with the
bistrisflamide anion was synthesized. Nockemann et. al. [2] reported that cholinium
bistriflamide shows an UCST-type phase diagram with water with a critical temperature
of about 70ºC. To the best of our knowledge, this is the first example of a totally miscible
bistriflamide based ionic liquid at temperatures not much above room temperature. In
this work, we have measured the temperature-composition phase diagrams of alkyldimethyl-hydroxyethylammonium
bistriflamide ionic liquids (1n

COIL-4:332
Green Synthesis of Tio2 Nanoparticles by Ionic Liquid-Assisted Routes
María Francisco (1) , maria.francisco@usc.es, School of Engineering, Rúa Lope Gómez
de Marzoa, s/n, Santiago de Compostela A Coruña E-15782, Spain ; Borja Rodríguez-
Cabo (1) ; Iago Rodríguez-Palmeiro (1) ; Eva Rodil (1) ; Ana Soto (1) ; Alberto Arce (1) . (1)
Department of Chemical Engineering, University of Santiago de Compostela, Santiago
de Compostela E-15782, Spain
Ionic liquids are generally non-flammable and thermally stable. Moreover they are nonvolatile,
which confers them a great potential as a “green” recyclable alternative to the
traditional organic solvents. Many combinations of cations and anions exist, giving rise
to a wide range of ionic liquids with adjustable solvent properties. Among other
applications, ionic liquids meet the characteristic to be attractive solvent media for
synthesis and separation processes [1]. Recently, a great variety of approaches have
been developed for the synthesis of nanoparticles, which have enhanced the
applicability of many materials. It has been shown that physicochemical properties of
nanomaterials directly depend on the size of their nanoparticles [2], being different from
those of bulk materials. Semiconductor nanoparticles are widely used for biological
labeling and diagnostics, light-emitting diodes, electroluminescent devices, photovoltaic
devices, lasers and single-electron transistors [3,4]. The preparation of anatase
titanium dioxide (TiO2) by two “environmentally friendly” methods is studied in this work.
For that purpose, the ionic liquid trihexyl(tetradecyl)phosphonium chloride, [P6,6,6,14]Cl,
was used alone as liquid medium. Formation of the nanoparticles was carried out by a
fragmentation/dispersion method and by an ultrasonic irradiation method. The asobtained
nanoparticles were characterized by means of ultraviolet-visible absorption
spectroscopy (UV-vis), dynamic light scattering (DLS), X-ray powder diffraction (XRPD)
and transmission electron microscopy (TEM). A comparison between both methods has
been established. [1] K. R. Seddon, J. Chem. Tech. Biotechnol. 68 (1997) 351. [2] A.
P. Alivisatos, J. Phys. Chem. 100 (1996) 13226. [3] J. Hu, L. S. Li, W. Yang, L. Manna,
L. W. Wang, A. P. Alivisatos, Science 292 (2001) 2060. [4] J. Joo, H. Bin Na, T. Yu, J.
Ho Yu, Y. Woon Kim, F. Wu, J. Z. Zhang, T. Hyeon, J. Am. Chem. Soc. 125 (2003)
11100.
COIL-4:333
Distillable Acid-Base Conjugate Ionic Liquids for Cellulose Dissolution and
Processing
Alistair W. T. King (1) , alistair.king@helsinki.fi, Faculty of Science, P.O. Box 55 (A.I.
Virtasen Aukio 1), HELSINKI FIN-00014 University of Helsinki, Finland ; Janne
Asikkala (1) ; Ilpo Mutikainen (1) ; Paula Järvi (1) ; Ilkka Kilpeläinen (1) . (1) Department of
Chemistry, University of Helsinki, HELSINKI 00700, Finland

A necessity for future generations of ionic liquids, destined for wood-based
bioprocessing platforms is a drastically improved recyclability over the initial structures.
As such, we have developed 'distillable' molten acid-base conjugates that efficiently
dissolve cellulose < 100 o C. A temperature dependent shifting of the acid-base
equilibrium toward the unconjugated neutral species, as you increase temperature,
affords a vapor pressure allowing for distillation of the mixture with > 99 % recovery and
purity (Figure 1). As such, we have found that we can dissolve cellulose at the
low temperature range (80-110 o C) with a modest decrease in molecular weight. At the
higher temperature range (> 120 o C) we have been able to effect depolymerization of
the dissolved pulp. Thus we are able to tune the 'dissolution' conditions from dissolution
towards saccharification.
COIL-4:334
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Extraction of High Value Products from Biomass Using Ionic Liquids
Margaret M Nimoh (1) , mnimoh01@qub.ac.uk, David Keir Building, Stranmillis Road,
Belfast Northern Ireland BT9 5AG, United Kingdom ; David W Rooney (1) . (1) School of
Chemistry and Chemical Engineering, Queen[apos]s University of Belfast, Belfast BT9
5AG, United Kingdom
The search for bioactive compounds from natural sources has been going on for
centuries and it is still in progress. The synthesis and isolation of these valuable
compounds make them reasonably expensive; in addition some of the synthesis of
these natural compounds involves huge amounts of volatile organic compounds
(VOCs). In recent years research in ionic liquids (ILs) and biomass dissolution has been
on the increase due to the 'beauty' of this relatively novel solvent to effectively break
down the hard matrix of difficult biopolymers. This is a very big step in the future of
biomass dissolution using ILs, which enables the possibility of completely separating
lignocellulosic biomass into its major polymeric components: cellulose, lignin and
hemicelluloses. We can therefore apply this knowledge in the extraction of bioactive
compounds from other types of biomass. Two types of biomass are considered here;
land biomass (cinnamon bark) and aquatic biomass (macroalgae). The combination of
ILs and supercritical fluids has also been investigated because of the 'greenness' of the
two solvents since carbon dioxide is inexpensive, non-flammable, nontoxic and
environmentally benign. Even though supercritical fluid extractions have been
performed on different types of biomass, the combination with ILs has not been
investigated yet. Our overall aim is to combine the ionic liquids and supercritical carbon
dioxide for the extraction of biologically active ingredients from macroalgae. The effect
of IL pre-treatment of these types of biomass is compared against conventional
methods like Soxhlet extraction, direct maceration, steam distillation and supercritical
carbon dioxide extraction in terms of the percentage yields of the extract recovered and
also their bioactivity. It has been shown that the extracts recovered from the IL
dissolution were higher than that from the conventional methods used.

COIL-4:335
New Cholinium-Derived Bistriflamide Ionic Liquids Family
José M. S. S. Esperança (1) , jmesp@itqb.unl.pt, Av. da República, Oeiras Oeiras 2780-
157, Portugal ; Anabela J. L. Costa (1) ; Isabel M. Marrucho (1) ; Luís P. N. Rebelo (1) ; Mário
R. C. Soromenho (1) . (1) Instituto de Tecnologia Química e Biológica/Universidade Nova
de Lisboa, Oeiras 2780-157, Portugal
Ionic liquids based on the cholinium cation (trimethyl-hydroxyethylammonium) have
been investigated as possible environmentally friendly alternatives to conventional ionic
liquids in distinct research fields. Nevertheless, most of the ionic liquids based on the
cholinium cation show higher melting points than those of common alkyl-imidazolium
based ionic liquids. To overcome this problem, although scarifying on the toxicity, a new
family of ionic liquids inspired on alkyl-dimethyl-hydroxyethylammonium, with the alkyl
chain length ranging from C2 to C5, combined with the bistrisflamide anion was
synthesized. Density and viscosity data for alkyl-dimethyl-hydroxyethylammoniumbased
ionic liquids (n=1,2,3,4,5) combined with the bis(trifluoromethanesulfonyl)imide
anion were measured at atmospheric pressure in the temperature range 283(melting
point, if higher)

on the physical and chemical properties. The uptake behavior and interactions between
RTILs and water adsorbed from the vapor phase was studied by attenuated total
reflectance (ATR) and transmission infrared spectroscopy. The infrared spectra show
the influence of water on the mode and intensity of hydrogen bonding interactions
between water molecules and the cation/anion of the RTIL. The spectral evolution in the
OH stretching region reveals, for example, that changing the anion from BF4 - to Cl -
modifies the water distribution. It is has been suggested that water at the solid/water
interface is “structured” and may have properties different from that of bulk water; the
structured orientation of surface water may extend anywhere from three monolayers to
many molecular diameters. Implications that our experimental results have regarding
the nature of the surface water and its behavior with ILs are discussed.
COIL-4:337
Phosphonium-Based Ionic Liquids as Extractants for Biorefinery Platform
Materials: L-Lactic Acid, L-Malic Acid and Succinic Acid
Isabel M. Marrucho (1) , imarrucho@itqb.unl.pt, Av. República, Apartado 127 2780-901
Oeiras, Portugal ; Filipe S. Oliveira (1) ; João M. M. Araújo (1) ; Rui Ferreira (1) ; Luís P. N.
Rebelo (1) . (1) Instituto de Tecnologia Química e Biológica, ITQB2, Universidade Nova
de Lisboa 2780-901 Oeiras, Portugal
Sustainable economical growth requires safe resources of raw materials for the
industrial production. Today's most frequently used industrial raw material, petroleum, is
neither sustainable, nor environmentally friendly. Biomass presents the potential to
meet the challenges of sustainable and green energy systems, and the development of
biorefineries represents the key for the access to an integrated production of food, feed,
chemicals, materials, goods and fuels of the future [1]. Organic acids are considered to
be platform materials for the chemical industry and constitute a key group among the
building-block chemicals that can be derived from biomass [2]. However, the extraction
processes of these acids from dilute waste water and fermentation broths normally use
organic solvents which imply additional environmental hazards. Ionic liquids play a
central role in the development of new “greener” sustainable technologies, as potential
substitutes of volatile organic compounds [3]. Therefore, the main objective of this work
is to test the efficiency of ionic liquids to extract three short chain organic acids (L-lactic,
L-malic and succinic) from dilute aqueous solutions, as a raw model for the use of ionic
liquids to extract bioproducts from fermentation broths. The effect of the anion's nature
and the concentration of the acid in the aqueous solution on the partition coefficients
was evaluated. Two different approaches to recover the organic acid from the ionic
liquid - distillation at reduced pressure and pH variation - have been tested. [1] B.
Kamm, M. Kamm, Biorefinery - Systems, Chemical and Biochemical Engineering
Quarterly, 18 (2004) 1-6. [2] M. Sauer, D. Porro, D. Mattanovich, P. Branduardi,
Microbial production of organic acids: expanding the markets, Trends in Biotechnology,
26 (2008) 100-108. [3] L.D. Simoni, A. Chapeaux, J.F. Brennecke, M.A. Stadtherr,
Extraction of biofuels and biofeedstocks from aqueous solutions using ionic liquids,
Computers & Chemical Engineering, 34 (2010) 1406-1412.

COIL-4:338
Pyrrolidinium-Based Polymeric Ionic Liquids for Gas Separation Membranes
Liliana C. Tomé (1) , liliana.tome@itqb.unl.pt, Av. República, Apartado 127 2780-157
Oeiras, Portugal ; Luís Paulo N. Rebelo (1) ; Isabel M. Marrucho (1) . (1) Universidade Nova
de Lisboa, Instituto de Tecnologia Química e Biológica, ITQB2 2780-157 Oeiras,
Portugal
The field of ionic liquids (ILs) has bloomed at the interface of many disciplines. The topic
is producing an outstanding variety of products like solvents for chemical and
biochemical reactions, advanced electrolytes or additives in the plastic industry. The
tunability of the chemical composition of ILs, achieved by pairing various organic cations
with numerous anions, allows the fine control of their physicochemical properties and it
has been widely used for the adjustment of the IL characteristics. Exploitation of this
structural modularity coupled with chemical modification of the cation or anion to
incorporate polymerizable groups resulting in the development of polymeric ionic liquids
as a new class of functional polymers. Polymeric ionic liquids present some of the
unique properties of ILs and are finding a wide range of application in polymer chemistry
such as electroactive polymers, porous polymers, nanocomposite materials, among
others. However, polymeric ionic liquids are also very promising materials as gas
separation membranes. In this study, we synthesized polymeric ionic liquids based on
the pyrrolidinium cation combined with different anions such as sulfonates, Ntf2, PF6 and
BF4 by a simple approach that consists in an anion exchange reaction in water soluble
polycations containing halide anions. Polymeric ionic liquids composite membranes with
different percentages of “free” IL were prepared by the casting method. In order to
evaluate the performance of the prepared polymeric ionic liquids composites for use as
gas separation membranes, permeabilities, solubilities and diffusivities of different
gases were determined by time-lag method. The present communication will provide
results for a systematic understanding of the factors that influence gas permeability and
separation selectivity in pyrrolidinium-based polymeric ionic liquid membranes, such as
the variation of chemical nature of the anion, the effect of “free” IL and their
concentration, as well as the structure of the cation.
COIL-4:339
Liquid or Solid-like Behavior of [omim][BF4] at a Solid Interface?
Jose Nuno Canongia Lopes (1) , jnlopes@ist.utl.pt, Av Rovisco Pais, Lisboa Portugal
1049 001, Portugal ; Ralf Kohler (2)(3)(4) ; Jose Restolho (1) ; Rumen Krastev (5)(3) ; Karina
Shimizu (1) ; Benilde Saramago (1) . (1) Centro de Quimica Estrutural, Instituto Superior
Tecnico, Lisboa 1049 001, Portugal (2) Institute of Soft Matter and Functional Materials,
Helmholtz Center Berlin, Berlin 14109, Germany (3) Department of Interfaces, Max-
Planck-Institute of Colloids and Interfaces, Berlin 14109, Germany (4) Department of
Chemistry, Technical University Berlin, Berlin 14109, Germany (5) NMI Natural and
Medical Sciences Institute, University of Tuebingen, Reutlingen 72770, Germany

The objective of this work is to clarify the nature of the lamellar structure reported by
several authors for ionic liquids at solid interfaces. The ionic liquid 1-methyl-3octylimidazolium
tetrafluoroborate,[omim][BF4], has been deposited on a solid aluminum
substrate from ethanol solutions and the resulting interfacial structure was investigated
using atomic force microscopy imaging. The results have been analyzed using
supplementary structural data obtained by molecular dynamics simulations. The main
conclusion is that the behavior of the IL films is strongly dependent on time and
concentration of the IL in solution. After ca 100 hours of equilibration, the structure of
the film has changed -depending on the (initial) concentration of the film-forming
solution- reaching a sponge-like structure if an IL concentration exceeds a threshold
value of ca 0.5 mg/mL.
COIL-4:340
Salting-In/Salting-Out Phenomena in Ionic Liquids: Molecular Dynamics Studies
Jose Nuno Canongia Lopes (1)(2) , jnlopes@ist.utl.pt, Av Rovisco Pais, Lisboa Portugal,
Portugal ; Karina Shimizu (1) ; Carlos Bernardes (1) ; Mara G. Freire (2) ; Isabel M.
Marrucho (2) ; Joao A. P. Coutinho (3) ; Luis Paulo N. Rebelo (2) . (1) Centro de Quimica
Estrutural, Instituto Superior Tecnico, Lisboa 1049 001, Portugal (2) Instituto de
Tecnologia Quimica e Biologica / UNL, Lisboa 1049 001, Portugal (3) Departamento de
Quimica, CICECO, Universidade de Aveiro, Aveiro 3810 193, Portugal
The solubility of ionic liquids in water can exhibit salting-out or salting-in effects upon
addition of distinct inorganic salts or even other ionic liquids. In a recent study, the
existence of preferential specific interactions between the low electrical charge density
(“apolar moiety”) parts of ionic liquid cations and selected inorganic salts has been
studied.[1] These interactions become increasingly favorable as one moves from
salting-out to salting-in regimes and this finding has been corroborated by 1 H-NMR
results and molecular dynamics simulations. The ionic liquid used in that study was 1butyl-3-methylimidazolium
bis(trifluoromethylsulfonyl)imide, [C4C1im][NTf2] and the work
focused on the effect of the nature and concentration of the inorganic salt. In the
present work the scope of that study is expanded to encompass the effects of the size
of the alkyl side chain —by studying ionic liquids based on [C2C1im] + , [C4C1im] + and
[C6C1im] + cations and also [C2SO4] – , [C4SO4] – and [C6SO4] – anions— and the nature of
the salting-out agent —by replacing the usually used inorganic salts by a hydrophilic
ionic liquid. [1] Freire, M. G.; Neves, C. M. S. S.; Silva, A. M. S.; Santos, L. M. N. B.
F.; Marrucho, I. M.; Rebelo, L. P. N.; Shah, J. K.; Maginn, E. J.; Coutinho, J. A. P. J.
Phys. Chem. B 2010, 114, 2004–2014.
COIL-4:341
Synthesis of Cobalt Ferrite Magnetic Nanoparticles in Ionic Liquids
Juliette Sirieix Plenet (1) , juliette.sirieix_plenet@upmc.fr, Laboratory PECSA, case 51, 4
place jussieu, Paris Paris 75252 cedex 05, France ; Laurent Gaillon (1) ; Sophie Neveu (1) ;

Cecile Rizzi (1) . (1) Departement of chemistry, Laboratoire de Physicochimie des
Electrolytes, Colloïdes et Sciences Analytiques, Université Pierre et Marie Curie – Paris
6, UMR7195 CNRS-ESPCI-UPMC, Paris 75252 Paris cedex 05, France
There is continuing interest in magnetic nanoparticles, especially because of their
applications in the fields of imaging and therapy. Among these applications, the
treatment of tumors by hyperthermia has been recognized as very promising, and the
efficiency of cobalt ferrite, CoFe2O4, nanoparticles has been established. For such an
application, control of the particle size and shape is very important. Ionic liquids (IL)
were investigated for the synthesis of nanoparticles because they have particular
properties as non-flammability, non-volatility and, solvation interactions with polar and
nonpolar compounds. Moreover these properties can be modified if the combination
cation-anion changed, what offers an additional benefit to their use. In this work, we
synthesized cobalt ferrite nanoparticles in IL/water mixtures solutions. The imidazolium
IL used were 1-butyl-3-methylimidazolium tetrafluoroborate (BMImBF4), 1-butyl-2,3dimethylimidazolium
tetrafluoroborate (BDMImBF4), 1-methyl-3-octylimidazolium
tetrafluoroborate (OMImBF4) and bromide (OMImBr), in order to study the influence of
the alkyl chain length, of the substitution on the imidazolium ring and of the counter ions
on the size, morphology and stability of the cobalt ferrite nanoparticles. The synthesized
nanoparticles were then characterized with different techniques. The different
experiments showed that ionic liquids decrease the size of the particles compared to the
classical synthesis in aqueous media. Figure 1: Particles synthesized in a)
water, b) BMImBF4/water mixture
COIL-4:342
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Asymmetrical Ether-Functionalized Dicationic Ammonium–Based Room
Temperature Ionic Liquids
Manu Kristian Lahtinen (1) , manu.k.lahtinen@jyu.fi, P.O.Box 35, Jyväskylä - FI-40014,
Finland ; Minna Kärnä (1) ; Jussi Valkonen (1) . (1) Department of Chemistry, University of
Jyväskylä, Jyväskylä P.O.BOx 35 FI-40014, Finland
A new class of ionic liquids, dicationic ILs, has emerged during the last few years. We
have synthesized 20 new asymmetrical dicationic ammonium based compounds and
characterized them by using 1 H and 13 C NMR techniques, mass spectroscopy and
elemental analysis. The synthesis is straightforward: first, a diamine is treated with an
alkyl bromide. After a selective quaternization a monocationic ammonium bromide is
achieved which is then treated with another alkyl bromide to yield an asymmetrical
dicationic ammonium bromide. The ether group can be located on the alkyl groups
and/or in the spacer between the two ammonium groups. A metathesis reaction is used
to achieve an ionic liquid with the desired anion such as TFSI. All the designed TFSI
salts proved to be room-temperature ionic liquids (RTILS) exhibiting broad liquid ranges
(-60 and 300 °C) and high thermal stability. Thermal properties of the these salts were
studied by using TG/DTA and DSC methods. The structural properties of the precursor

omides as well as RTILs (at low-temperatures) were examined by X-ray powder
diffraction. The viscosity properties of the fluid salts were measured as a function of the
temperature and Karl Fischer titration was used to determine their residual water
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content. R1 includes ether group and differs from R2; R2 is typically aliphatic or
aromatic group
COIL-4:343
Influence of Gas Solubility on Supported Ionic Liquid Phase (SILP) Catalyst
Activity in Continuous Gas-Phase Reactions
Andreas Schoenweiz (1) , andreas.schoenweiz@crt.cbi.uni-erlangen.de, Egerlandstr. 3,
Erlangen Bavaria, Germany ; Alexander Buchele (1) ; Wolfgang Arlt (1) ; Marco Haumann (1) ;
Peter Wasserscheid (1) . (1) Department of Chemical and Bioengineering, Friedrich-
Alexander-University Erlangen-Nuremberg, Erlangen Bavaria 91058, Germany
In catalytic SILP materials a porous solid support with large surface area is impregnated
with a thin film of ionic liquid containing a well-defined organometallic catalyst complex.
Even though these catalysts have proved their homogeneous nature in catalysis, they
are macroscopically heterogeneous and can readily be used as fixed beds for
continuous gas-phase operations. Successful application of the SILP concept has been
demonstrated for various chemical reactions including hydroformylation, water-gas shift,
metathesis and methoxycarbonylation reactions. In this contribution the SILP catalyst
concept was applied for continuous gas-phase hydroformylation and hydrogenation
reactions. Our experiments reveal that gas solubility of both substrate and
product in the ionic liquid film can be a crucial parameter for the achievable SILP
catalyst performance. In order to avoid time-consuming experimental screening for
finding an appropriate ionic liquid, prediction programs such as COSMO-RS might be
very helpful for a priori estimation of gas solubilities in different ionic liquids. Recent
results show very good agreement between the calculated solubilities of selected
hydrocarbons in a set of common ionic liquids and the observed SILP catalyst activities
in corresponding hydroformylation and hydrogenation experiments. This correlation
might qualify COSMO-RS as powerful tool for SILP catalyst optimization. For
verification of the COSMO-RS prediction reliability, the calculated solubilities were
compared to experimental data determined from magnetic suspension balance
measurements.
COIL-4:344
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Simple Preparation of Various Types of Magnetic Ionic Liquids
Yumiko Takagi (1) , ytakagi@ed.kagawa-u.ac.jp, 1-1 Saiwai-cho, Takamatsu-City
Kagawa 760-8522, Japan . (1) Department of Chemistry, Kagawa University, Faculty of
Education, Takamatsu-City Kagawa 760-8522, Japan

An ionic liquid is a salt which results in these solvents being liquid below 100 Celsius
degree, or even at room temperature. The methylimidazolium and pyridinium ions have
proven to be good starting points for the development of ionic liquids. The absence of
volatility is one of the most important benefits of ionic liquids, offering a much lower
toxicity as compared to low-boiling-point solvents. Ionic liquids can also make for safer
microwaves methods, because sudden pressure surges are not possible. We tried to
prepare the magnetic Ionic liquids several types of the Ionic Liquid. The role and
nature of cation-anion interactions in ambient-temperature ionic liquids are the subjects
of much current interest. We wish to report here that magnetic ionic liquids have been
prepared via very simple means starting from 1-ethyl-3-methylimidazolium ethyl sulfate
([emim][EtSO4]). During the study to prepare novel magnetic ionic liquids, we found
that an interesting imidazolium salt was formed when [emim][EtSO4] was mixed with an
equimolar amount of cobalt chloride (II) or its hydrate at room temperature. After being
stirred for 30 min. at RT, a dark blue liquid was produced from the mixture. To our
delight, a precipitate was formed from the liquid after standing several days under
argon atmospheric conditions at RT, and it was successful to determine the stricture of
the precipitate by X-ray crystallographic analysis after recrystallization from ethyl
acetate: the compound was identified as bis(1-ethyl-3-methylimidazolium) cobalt
chloride(II)( [emin]2[CoIICl4] )1a. Although we have soon recognized that
[emin]2[CoIICl4] has already been reported by Hitchcock and Yoshida,1 the present
method is much more simple compare to the reported ones. We are expecting that our
protocol may make it possible to prepare various types of magnetic imidazolium salts
very easily.
COIL-4:345
Enantioselective Catalysis in the Presence of Chiral Ionic Liquids
Rafael Krause (1) , krause@itmc.rwth-aachen.de, Worringerweg 1, Aachen 52074,
Germany ; Philipp Oczipka (1) ; Giancarlo Franciò (1) ; Jürgen Klankermayer (1) ; Walter
Leitner (1) . (1) Department of Technical and Macromolecular Chemistry, RWTH Aachen,
Aachen 52074, Germany
Asymmetric transformations can be accomplished using chiral substrates, chiral
catalysts and, in principle, chiral solvents. The first two strategies have been extensively
studied and developed to useful and widely applicable synthetic tools. The application of
chiral solvents as the only source of chiral information in asymmetric catalysis was only
demonstrated in very rare cases. However, in the last few years, the synthesis and the
application of chiral ionic liquids created renewed interest in this field and first studies on
their use as chiral reaction media appeared. [1],[2] Recently, we reported the use of a
chiral ionic liquid (cIL) in combination with tropoisomeric biphenylphosphine ligands in
the rhodium-catalysed hydrogenation. In the chiral reaction medium good
enantioselectivities were obtained in combination with a sulfonated phosphine ligand.
Subsequently, an extension of this approach to novel ionic liquid structures and racemic
atropoisomeric diphenylphosphine ligands like rac-BINAP was established. [3],[4],[5] Herein
we report on the evaluation of the transfer of chiral information in the presence of chiral

ionic liquids on the basis of NMR-investigations and the application of catalytic
hydrogenation reactions as chemical probe. In this respect, interaction of the chiral
counterion with a racemic BINAP-Rh-complex was investigated in the asymmetric
hydrogenation of functionalised olefins. [1] G.Vo-Thanh, B.Péjot, D.Gori, A.Loupy,
Tetrahedron Lett. 2004, 45, 6425. [2] P.S.Schulz, N.Müller, A.Bösmann,
P.Wasserscheid, Angew. Chem. Int. Ed. 2007, 46, 1293. [3] D.Chen, B.Sundararaju,
R.Krause, J.Klankermayer, P.H.Dixneuf, W.Leitner, ChemCatChem 2010, 2, 55. [4]
M.Schmitkamp, D.Chen, W.Leitner, J.Klankermayer, G.Franciò, Chem. Commun. 2007,
39, 4012. [5] D.Chen, M.Schmitkamp, G.Franciò, J.Klankermayer, W.Leitner, Angew.
Chem. 2008, 120, 7449.
COIL-4:346
Nanocomposite I3 - /I - Electrolytes Based on Sol-Gel Polymerisable Ionic Liquids
Marija Čolović (1) , marija.colovic2@ki.si, Hajdrihova 19, Ljubljana Slovenia SI-1000,
Slovenia ; Metka Hajzeri (1) ; Angela Šurca Vuk (1) ; Ivan Jerman (1) ; Adolf Jesih (2) ; Boris
Orel (1) . (1) Department for The Spectroscopy of Materials, National Institute of
Chemistry, Ljubljana Slovenia SI-1000, Slovenia (2) Jožef Štefan Institute, Ljubljana
Slovenia SI-1000, Slovenia
In the field of electrochemical applications most of the interest in ionic liquids 1 is
centered in the design of new electrolytes, but the skepticism regarding the leakage
from the electrochemical systems remains. Replacing of the liquid electrolyte with a
solid or quasi-solid one is expected to solve these problems. Therefore, the ionic liquids
with polymerizable groups are becoming increasingly important, and investigations of
dependence of their conductivity on structural build-up are of great interest. In our
laboratory we introduced alkoxysilane-functionalised bis end-capped imidazolium based
iodide ionic liquids 2 . By sol-gel reactions of hydrolysis and condensation in-situ
formation of tridimensional gel network, which is capable to incorporate sol-gel nonreactive
ionic liquids, is enabled. Appropriate combination of bis end-capped and nonreactive
ionic liquids, after addition of iodine that leads to formation of I3 - /I - redox pair,
reached conductivities up to 10 -3 S/cm. These electrolytes were tested in hybrid
electrochromic devices WO3/electrolyte/Pt up to 15.000 colouring/bleaching cycles.
Light-to-electricity conversion efficiencies in dye-sensitized photoelectrochemical cells
TiO2/electrolyte/Pt strictly depend upon the degree of condensation. [1] H. Ohno, M.
Yoshizawa, Ion Conductive Polymers. In: H. Ohno, Electrochemical aspects of ionic
liquids, Wiley-Interscience, New Jersey, 2005, Ch. 29, p. 347. [2] V. Jovanovski, B.
Orel, R. Ješe, A. Šurca Vuk, G. Mali, S. B. Hočevar, J. Grdadolnik, E. Stathatos, P.
Lianos, J. Phys. Chem. B 109 (2005) 14387. The research has received founding
from the European Community's Seventh Framework Programme INNOSHADE (Grant
Agreement n o 200431) and Centre of Excellence Low-Carbon Technologies (contract n o
MVZT 3211-09-000641).
Coil-4:347

Enthalpies of Formation of 1-Alkyl-3-Methylimidazolium Halides
Yauheni U. Paulechka (1) , paulechka@bsu.by, Leningradskaya 14, Minsk - 220030,
Belarus ; Andrey G. Kabo (1) ; Andrey V. Blokhin (1) ; Marina P. Shevelyova (1) ; Gennady J.
Kabo (1) . (1) Chemistry Faculty and Research Institute for Physical Chemical Problems,
Belarusian State University, Minsk, Belarus
1-Alkyl-3-methylimidazolium compounds are among the most studied room-temperature
ionic liquids (ILs). Their enthalpies of formation can be experimentally determined either
by combustion calorimetry or by reaction calorimetry. The latter method has some
advantages compared to combustion calorimetry such as not so strict requirements to
purity of the studied samples and possibility to make measurements for the compounds
which cannot be burned quantitatively. In this work we determined the enthalpies of the
reactions between 1-methylimidazole and 1-haloalkanes resulting in formation of 1alkyl-3-methylimidazolium
halides ([Cnmim]Hal) in a home-made isoperibol calorimeter.
From the obtained experimental data, the enthalpies of formation for [Cnmim]Hal and
other individual ILs in the liquid and crystalline states were derived. The ideal-gas
enthalpies of formation for the halides were calculated using the methods of quantum
chemistry and statistical thermodynamics. The vaporization enthalpies and the lattice
energies of [Cnmim]Hal were estimated from the experimental and calculated enthalpies
of formation. With the use of the literature data and the results obtained in this work, a
simple correlation for calculation of ∆fH for 1-alkyl-3-methylimidazolium compounds in
the crystalline and liquid states was proposed. The possibilities of the existing
procedures for prediction of the enthalpies of formation were discussed. This work was
supported by Belarusian Republican Foundation for Fundamental Research (grant
Kh10M-082).
COIL-4:348
Partition Coefficients of Alkaloids Through Water and Hydrophobic Ionic Liquids
Two-Phase Systems: Hofmeister Series
Mara G. Freire (1) , maragfreire@ua.pt, Av. República, Ap. 127, Oeiras n.a. 2780-901,
Portugal ; Ana Rita R. Teles (2) ; João A. P. Coutinho (2) ; José N. Canongia Lopes (3) ;
Isabel M. Marrucho (1) ; Luís Paulo N. Rebelo (1) . (1) ITQB2, New University of Lisbon,
Oerias 2780-901, Portugal (2) Chemistry Department, CICECO, University of Aveiro,
Aveiro 3810-193, Portugal (3) Centro de Química Estrutural, Instituto Superior Técnico,
Lisboa 1049-001, Portugal
In the past few years, ionic liquids have received considerable attention due to their
unique properties, and powerful solvation capability for a broad array of materials. Ionicliquid-water
systems proved to be a suitable extractive media for alkaloids, namely
caffeine and nicotine. 1 After a careful tailoring of the ionic liquid nature, a complete
extraction of the alkaloids for the ionic liquid-rich phase was identified. 1 Although the
tailoring of the ionic liquid nature was previously demonstrated 1 , there is a fundamental
lack of information on the influence of diverse inorganic salts on the alkaloids

partitioning. The aim of this work is to obtain a deeper knowledge on the impact of
inorganic salts on the extraction of caffeine and nicotine from aqueous solutions using
phosphonium-based ionic liquids. The selected ionic liquids comprise the
trihexyltetradecylphosphonium-based cation combined with the following anions:
bromide, chloride, bis(trifluoromethylsulfonyl)imide, methanesulfonate, dicyanamide and
bis(2,4,4-trimethylpentyl)phosphinate. It was found that the solutes partitioning increase
with the ionic liquid hydrophilic character. Moreover, both the influence of the aqueous
solution ionic strength (ranging from 0.0 mol·kg -1 to 3.0 mol·kg -1 ) and the salt nature
(with potassium- and sodium-based salts) in the partitioning of caffeine and nicotine
were further investigated. The salts influence towards the course of the solutes partition
coefficients closely follows the Hofmeister series. References [1] Freire, M. G.;
Neves, C. M. S. S.; Marrucho, I. M.; Canongia Lopes, J. N.; Rebelo, L. P. N.; Coutinho,
J. A. P. Green Chem. 12 (2010) 1715-1718.
COIL-4:349
Relative and Inherant Nucleophilicity of [Emim]-Based Ionic Liquids from TGA
and Proton Affinity Calculations
Alistair W. T. King (1) , alistair.king@helsinki.fi, Faculty of Science, P.O. Box 55 (A.I.
Virtasen Aukio 1), HELSINKI FIN-00014 University of Helsinki, Finland ; Arno
Parviainen (1) ; Ilkka Kilpeläinen (1) . (1) University of Helsinki, Department of Chemistry,
HELSINKI 00700, Finland
In relation to our own research area of lignocellulosic biomass processing, three recent
important publications describe the selective reactions of lignocellulosics with neat
imidazolium-based ionic liquids. 1,2 The mechanisms of this reactivity are thought to
occur due to the basicity/nucleophilicity of the anion of the ionic liquid. Several
publications already exist describing the relative nucleophilicity of anions in a short
series of similar ionic liquids through kinetic studies. One notable example even
describes an 'ionic effect', in comparison to molecular solvents. 3 However, no studies
are yet available describing the nucleophilicity of anions from completely different ionic
liquids. Consequently, we have suggested a relative scale of inherant nucleophilicity for
[emim]-based ionic liquids, based upon comparison of TGA decomposition
temperatures, for ionic liquids decomposing via a reverse Menschutkin mechanism.
Comparison of these values with ab initio gas-phase proton affinities (MP2/6-
311+G(d,p)//MP2/6-311+G(d,p)) for the anions of those ionic liquids allows for an initial
approximate correlation with the TGA data and extension of this relative scale. With
further refinement of the data, this may allow for better understanding and perhaps
prediction of phenomena and effects, such as an ability to dissolve cellulose, reactivity
with electrophilic functionalities and predicted thermal stability for both synthesised and
predicted structures. References: 1 T. Liebert, T. Heinze, BioResources, 2008, 3, 576;
G. Ebner, S. SchiehserA. Potthast, T. Rosenau, Tetrahedron Lett., 2008, 49, 7322. 2
Ö. P. Çetinkol, D. C. Dibble, G. Cheng, M. S. Kent, B. Knierim, M. Auer, D. E. Wemmer,
J. G. Pelton, Y. B. Melnichenko, J. Ralph, B. A. Simmons, B. M. Holmes, Biofuels, 2010,
1, 33. 3 J. P. Hallett, C. L. Liotta, G. Ranieri, T. Welton, J. Org. Chem., 2009, 74, 3523.

COIL-4:350
Structural Studies on the Basic Ionic Liquid 1-Ethyl-1,4-
Diazabicyclo[2.2.2]Octanium Bis(Trifluoromethylsulfonyl)Imide and The
Analogous Bromide Salt
Theo Rodopoulos (1)(2) , Theo.Rodopoulos@csiro.au, Box 312, Clayton South Vic 3169,
Australia ; Yansen Lauw (1)(3) ; Thomas Rüther (4)(2) ; Michael D Horne (1)(2) ; Kia S
Wallwork (5) ; Brian W Skelton (6) ; Ian C Madsen (1) . (1) Process Science and Engineering,
CSIRO, Clayton South Vic 3169, Australia (2) Light Metals Flagship, Clayton South Vic
3169, Australia (3) Bragg Institute, ANSTO, Clayton South Vic 3169, Australia (4)
Energy Technology, CSIRO, Clayton South Vic 3169, Australia (5) Australian
Synchrotron, Clayton Vic 3169, Australia (6) School of Biomedical, Biomolecular and
Chemical Sciences, University of Western Australia, Crawley WA 6009, Australia
Ionic liquids have gained enormous interest in the research community due to their
unique properties which makes them appealing to a wide range of applications including
metal electrodeposition. Their physicochemical properties can be tuned through the
selection or modification of the constituent ions. Understanding of the structure-property
relationship in ionic liquids can be improved by knowledge of the solid state structure.
This information in turn can assist the design of new ionic liquids. Recently, the
synthesis of ionic liquids based on 1-alkyl-1,4-diazabicyclo[2.2.2]octanium cations
([CnDABCO] + ) has been reported. 1-3 The [CnDABCO] + cations contain a tertiary nitrogen
atom with a lone pair of electrons in addition to a quaternary nitrogen atom making them
Lewis basic and nucleophilic. Accordingly the [CnDABCO] + cations are able to
coordinate to metal ions. Ionic liquids with significantly enhanced solvating abilities (eg.
for added metal salts) can be formed by combining [CnDABCO] + cations with anions
which also have metal ion coordinating abilities. The 1-ethyl-1,4diazabicyclo[2.2.2]octanium
bis(trifluoromethylsulfonyl)imide ([C2DABCO][NTf2]) ionic
liquid is one example of this. Structural information on [C2DABCO][NTf2] was sought
due to the potentially important coordinating properties of this material. The structure
and phases of [C2DABCO][NTf2] were examined by a range of techniques (DSC,
Raman, single crystal XRD) and synchrotron powder diffraction was used to study its
crystallinity and phases as a function of temperature. A comparison of the ionic liquid
with its analogous bromide precursor provides insights on the relative electrostatic
attraction between the ions and the relative packing density and efficiency in the crystal
lattices and improves our understanding of the structure-property relationship in
[CnDABCO]-based salts. References: 1. Yoshizawa-Fujita, M.; MacFarlane, D. R.;
Howlett, P. C.; Forsyth, M. Electrochem. Commun. 2006, 8, 445. 2. Wykes, A.;
MacNeil, S. L. Synlett. 2007, 1, 107. 3. Chiappe, C.; Melai, B.; Sanzone, A.; Valentini,
G. Pure Appl. Chem. 2009, 81, 2035.
COIL-4:351
Preparation of Thermo-Reversible Ion-Gel Based on a Hierarchical Self-Assembly
of Doubly Thermo-Sensitive ABC-Triblock Copolymer in an Ionic Liquid

Yuzo Kitazawa (1) , d10ga508@ynu.ac.jp, 79-5 Tokiwadai, Hodogaya-ku, Yokohama
Kanagawa 240-8501, Japan ; Takeshi Ueki (1) ; Lucas McIntosh (2)(3) ; Timothy P
Lodge (2)(3) ; Masayoshi Watanabe (1) . (1) Department of Chemistry and Biotechnology,
Yokohama National University, Yokohama Kanagawa 240-8501, Japan (2) Department
of Chemistry, Department of ChemistryUniversity of Minnesota, Minneapolis Minnesota
55455, United States (3) Department of Chemical Engineering & Materials Science,
University of Minnesota, Minneapolis Minnesota 55455, United States
Ionic liquids (ILs) have attracted considerable attention because of their unique
properties, such as negligible volatility, thermal stability, non-flammability, and so on.
Previously, we have reported that poly(benzyl methacrylate) (PBnMA) shows lower
critical solution temperature (LCST) phase behavior in a typical hydrophobic IL, 1-ethyl-
3-methylimidazolium bis(trifluoromethane sulfone)amide ([C2mim][NTf2]).[1] We also
found that diblock copolymer which consists of PBnMA and poly(methyl methacrylate)
(PMMA) block exhibits LCST phase behavior in ILs.[2] In this study, we describe a novel
thermo-reversible ion-gel triggered by the LCST-induced doubly thermo-sensitive selfassembly
of an ABC-triblock copolymer in [C2mim][NTf2]. Each segment of the triblock
copolymer consists of poly(phenylethyl methacrylate) (PPhEtMA), PMMA and PBnMA,
respectively. The PMMA middle block is completely compatible with the IL, irrespective
of temperature and concentration. We have already reported PPhEtMA also shows
LCST phase separation in certain ILs but the phase separation temperature (Tc) is
found to be lower than Tc of PBnMA.[3] Therefore, PPhEtMA and PBnMA (A and C)
blocks are expected to aggregate at different LCSTs in the IL. The phase behavior of
the triblock copolymers was investigated by means of dynamic light scattering (DLS),
dynamic viscoelastic measurements and small angle X-ray scattering. [1] T. Ueki, M.
Watanabe, Macromolecules 2008, 41, 3739. [2] S. Tamura, T. Ueki, K. Ueno, K.
Kodama, M. Watanabe, Macromolecules 2009,42, 6239. [3] K. Kodama, H.
Nanashima, T. Ueki, H. Kokubo, M. Watanabe, Langmuir 2009, 25, 3820.
COIL-4:352
Microwave-Assisted Dissolution and Delignification of Wood Using 1-Ethyl-3-
Methylimidazolium Acetate ([Emim]Oac)
Hui Wang (1) , hwang27@as.ua.edu, Room 228, AIME Building, 720 2nd Street,
Tuscaloosa Alabama 35487, United States ; Gabriela Gurau (1) ; Mirela L. Maxim (1) ;
Robin D. Rogers (1) . (1) Center for Green Manufacturing and Department of Chemistry,
The University of Alabama, Tuscaloosa Alabama 35487, United States
The growing worldwide energy demand has prompted the development of efficient
technologies for converting biomass to biofuels and valuable chemicals. 1 Wood, one of
the most common forms of biomass, is the primary source of cellulose for use in the
paper, fiber, membrane industries. 2 Recently, it was reported that ionic liquids (ILs)
could be used to dissolve wood with recovery of lignin and a cellulose-rich material
(CRM). 2,3 While the original reports for dissolution of pure cellulose indicated that the
use of microwave irradiation facilitated dissolution, the exploration of this technique for

the direct dissolution of wood has been lagging. Here we present our study using
microwave irradiation to directly dissolve wood with the IL, [emim]OAc. We found that at
a loading of 0.5 g wood to 10.0 g IL, modest irradiation (3 s pulses at full power for 2-5
min in a domestic microwave oven with vigorous stirring between pulses) resulted in
dissolution of 95.7% of the added wood in as little as 5 min. The lignin content in the
CRM regenerated from the resulting solution was ca. 10%, much lower than that of the
CRM obtained from dissolution by heating at 110 o C for 16 h (23.5%) 3 or 175 o C for 0.5
h (16.1%). 4 However, an overall lower CRM yield was obtained which may indicate
more wood degradation. This presentation will compare and contrast the several
different dissolution methods we have used for woody biomass. (Acknowledgement:
This research was financially supported by DOE Grant DE-SC0004198 via a
subcontract from 525 Solutions.) REFERENCES (1) Kamm, B. Angew. Chem. Int. Ed.
2007, 46, 5056-5058. (2) Fort D.A.; et al. Green Chem. 2007, 9, 63-69. (3) Sun N.; et al.
Green Chem. 2009, 11, 646-655. (4) Li W.Y.; et al. unpublished results.
COIL-4:353
Electron-Transfer Reaction of Azurin Adsorbed on a Self-Assembled Monolayer–
Gold Nanoparticle Electrode in a Hydrated Ionic Liquid
Nobuhumi Nakamura (1) , nobu1@cc.tuat.ac.jp, 2-24-16 Nakacho, Koganei Tokyo 184-
8588, Japan ; Jun Kuwahara (1) ; Kyoko Fujita (1) ; Keiko Yokoyama (2) ; John H Richards (2) ;
Harry B Gray (2) ; Hiroyuki Ohno (1) . (1) Department of Biotechnology and Life Science,
Tokyo University of Agriculture and Technology, Koganei Tokyo 184-8588, Japan (2)
Beckman Institute, California Institute of Technology, Pasadena CA 91125, United
States
There is a consensus that ionic liquids (ILs) have numerous superior qualities as
solvents. The application of ILs as reaction media for biomolecules has also been
explored. To date, we have studied hydrated ILs as novel solvents for proteins.
Hydrated ILs maintain the basic properties of pure ILs, but a small amount of water
considerably improve protein solubility. Here, we report the effects of hydrated ILs on
the electron-transfer (ET) kinetics of Pseudomonas aeruginosa azurin (Az) on a 1:1
mixed self-assembled monolayer (SAM)–gold nanoparticle (AuNP) electrode. We
fabricated the AuNP electrode, and then a mixed SAM electrode was prepared by
immersing the AuNP electrode into 200 μM mixed ethanol solutions of 1-nonanethiol
and 8-hydroxy-1-octanethiol. Az was immobilized by soaking the SAM-AuNP electrode
in a 100 μM Az solution. Hydrated choline dihydrogen phosphate ([ch][dhp]) containing
35 wt% water was used as an electrolyte. Az dissolved in hydrated [ch][dhp] without any
pretreatment. The Raman bands of Az in hydrated [ch][dhp] were very similar to those
in buffer solution. Cyclic voltammograms of Az immobilized on the SAM-AuNP electrode
The image cannot be displayed. Your computer may not have enough memory
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are shown in Figure 1A. A clear redox couple was observed at 0.105 V vs.
Ag/AgCl in hydrated [ch][dhp]. The peak-to-peak separation was only 46 mV, even at a
scan rate of 5 V s -1 . The estimated rate constant for electron tunneling through the
mixed SAM was 200 s -1 , which was higher than that in water.

COIL-4:354
Carbon Dioxide Absorption by Aprotic Heterocyclic Amine Functionalized Ionic
Liquids
Samuel Seo (1) , sseo3@nd.edu, 311 Stinson-Remick Hall, Notre Dame IN 46556,
United States ; Joan F Brennecke (1) ; Bhabani S Mallik (1) ; Elaine M Mindrup (1) ; William F
Schneider (1) . (1) Department of Chemical and Biomolecular Engineering, University of
Notre Dame, Notre Dame IN 46556, United States
Non-volatility, good thermal stability and high CO2 solubility make Ionic Liquids (ILs) a
promising replacement for current volatile solvents used in a wide variety of
applications, including CO2 capture and co-fluid vapor-compression refrigeration. One of
the most attractive advantages is that the physiochemical properties can be varied by
tuning cation/anion combinations and chemical substituents. The reaction enthalpy of
ILs with CO2 is directly related to the CO2 capacity and regeneration energy, and this
binding energy can also be tuned. Gurkan et al. [1] have shown that tethering amine
functional groups to the anion leads to a reaction stoichiometry of one mole CO2 for
each IL. In a recent paper, aprotic heterocyclic anions, or “AHAs”, have been introduced
to bind CO2 with reaction energies that are suitable for gas separations, without
suffering large viscosity increases [2]. The CO2 absorption isotherms were obtained at
a total of five temperatures (22, 40, 60, 80 and 100°C) for
trihexyltetradecylphosphonium pyrrolide ([P66614][2-CNpyr]). The enthalpy and entropy
calculated from the experimental data agrees well with the computational values from
molecular electronic structure calculations at G3 level. Since a wide range of tunability
of the reaction enthalpy is possible for these AHAs, we have synthesized and
characterized a series of ILs with different heterocyclic anions and the same
phosphonium cation that span a wide range of predicted reaction enthalpies. The
capacity of CO2 in each AHA-based IL was experimentally measured and absorption
isotherms were obtained at pressures between 0 and 1 bar at 22°C. The experimental
results are in remarkably good agreement with computed enthalpies of IL-CO2 reaction
products from computational simulation.
COIL-4:355
Synthesis and Characterization of Lithium Ion Conductors Based on Ionic Plastic
Crystals
Yusuke Muramatsu (1) , yu-muramatsu@sophia.ac.jp, 7-1 Kioi-cho, Chiyoda-ku Tokyo
102-8554, Japan ; Masahiro Yoshizawa-Fujita (1) ; Yuko Takeoka (1) ; Masahiro
Rikukawa (1) . (1) Department of Materials & Life Sciences, Sophia University, Chiyoda-ku
Tokyo 102-8554, Japan
In this study, 1-methyl-2,3,4,6,7,8-hexahydropyrrolo[1,2-a]pyrimidin-1-ium
bis(trifluoromethylsulfonyl)amide ([C1DBN][N(Tf)2]) was synthesized as a new class of
lithium ion conductors (Fig.1). [C1DBN][N(Tf)2] showed the solid-solid phase transitions

at -55.4 ºC and -4.4 ºC and the melting point at 93.4 ºC. The highest temperature solid
phase was denoted as phase I, and the subsequent lower temperature solid phases
were denoted as phases II and III. The final entropy of fusion (∆Sf) was 38.6 J mol -1 K -1 ,
which was close to the Timmermans criterion value (∆Sf < 20 J mol -1 K -1 ) for molecular
plastic crystals. In general, the ∆Sf of ionic materials with the N(Tf)2 anion is higher than
the criterion due to the residual entropy of melting for the N(Tf)2 anion. [C1DBN][N(Tf)2]
was mixed with given amounts of LiN(Tf)2. When LiN(Tf)2 of over 3 mol% was added to
the matrix, a new endothermic peak was observed at -80.0 ºC. The ionic conductivity of
[C1DBN][N(Tf)2] in solid phases was in the range of 10 -9 - 10 -7 S cm -1 . When LiN(Tf)2 of
1 mol% was added to the matrix, the ionic conductivity of the composite in solid phases
increased up to 10 -4 S cm -1 . The ionic conductivity of the composite with 10 mol%
LiN(Tf)2 in phase I was over 10 -3 S cm -1 , which was 4 orders higher than that of
[C1DBN][N(Tf)2].
COIL-4:356
SRN1 Reaction of Aliphatic Nitro Compounds in Ionic Liquids
Akio Kamimura (1) , ak10@yamaguchi-u.ac.jp, 2-16-1, Tokiwadai, Ube Yamaguchi 755-
8611, Japan ; Seiichi Toyoshima (1) . (1) Department of Applied Molecular Bioscience,
Yamaguchi University, Ube Yamaguchi 755-8611, Japan
SRN1 reaction is a unique reaction that proceeds via a single electron transfer process.
The reaction is usually performed in either liquid ammonia or dipolar aprotic solvent
such as DMSO and HMPA. We thought that ionic liquids would be a new reaction
solvent for the SRN1 reaction because it promotes the electron transfer process. In this
paper we present the first use of ionic liquids in the SRN1 reaction of aliphatic nitro
compounds. Treatment of gem-dinitro compounds and potassium salt of αsulfonylester
in ionic liquids resulted in smooth progress of SRN1 reaction to give
corresponding coupling product in good yield. Many types of ionic liquids were useful.
For example, ionic liquids that have an imidazolium or ammonium unit worked well for
the reaction. Anionic part such as [TFSA] or [PF6] gave good results. Kinetic analysis
showed that the SRN1 reaction in ionic liquids took slightly longer hours than the
conventional SRN1 reaction in DMSO. The ionic liquids were recyclable and effectively
progressed the reaction in iteration use if ionic liquids were washed with water after the
reaction to remove nitrite salts. Thus, we have successfully demonstrated that ionic
liquids will be a new reaction solvent for SRN1 reaction.
COIL-4:357
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Hydrophobic Zwitterion/Acid Composites as Anhydrous Proton Conductors for
Fuel Cell Electrolytes
Kensuke Shimada (1) , kensuk-s@sophia.ac.jp, 7-1 Kioi-cho, Chiyoda-ku Tokyo 102-
8554, Japan ; Masahiro Yoshizawa-Fujita (1) ; Yuko Takeoka (1) ; Masahiro Rikukawa (1) . (1)

Department of Materials & Life Sciences, Sophia University, Chiyoda-ku Tokyo 102-
8554, Japan
In this study, the composites of a hydrophobic zwitterion, 3-(trioctylammonio)propane-1sulfonate
(TOAPS), and H3PO4 were prepared, and their thermal and electrolyte
properties were investigated. The concentration of H3PO4 in the composites was in the
range of 40 - 90 mol%. Although TOAPS was a white solid showing the melting point at
190 o C, the composites were quite viscous liquids at room temperature except for 80
mol%. The onset thermal decomposition temperatures (Td) of TOAPS and H3PO4 were
219 o C and 150 o C, respectively. The Td of the composites was about 300 ºC when the
H3PO4 concentration was below 70 mol %. The Td value was about 150 ºC higher than
that of H3PO4. The thermal stability of H3PO4 was improved by adding the hydrophobic
zwitterion. H3PO4 showed the ionic conductivity of over 10 -1 S cm -1 at 120 o C. The ionic
conductivity of the composites decreased with increasing the concentration of TOAPS
due to the decrease in the number of carrier ions. The composite with 90 mol% H3PO4
showed the highest conductivity among the composites of 2 x 10 -2 S cm -1 at 120 o C.
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COIL-4:358
Systematic Study of Dispersion Interactions in Ion Clusters of Typical Ionic
Liquids
Jason D Rigby (1) , jason.rigby@monash.edu, Wellington Road, Clayton Victoria 3800,
Australia ; Ekaterina I Izgorodina (1) ; Douglas R MacFarlane (1) . (1) School of Chemistry,
Monash University, Clayton Victoria 3800, Australia
There are many more possible ILs than could ever reasonably be synthesized and
characterized in any foreseeable timeframe. It is therefore of particular interest to
harness modern computational techniques from first principles to predict the
thermodynamic and transport properties of ILs, with the view of identifying useful
anion/cation combinations, thus eliminating timely and wasteful synthesis. While longranged
Coulombic (electrostatic) interactions can generally be accounted for quite
easily, it has been shown that in order to accurately model ILs, it is imperative that
correlated levels of theory be used, with dispersion interactions being an integral part of
describing the physical nature of ILs 1,2 . In order to better understand the importance of
dispersion in systems comprising of multiple ion pairs, we present a fully ab initio study
employing a second-order perturbation theory method, MP2, on four typical ILs, namely
[NMe4]BF4, [c1mim]BF4, [c3mim]BF4 and [c4mim]BF4. Each IL was modeled
systematically by constructing ion clusters of n ion-pairs with n = 1, 2, 4, 6 and 8. A
thorough analysis of the interaction energy components such as dispersion, exchange,
charge transfer, and induction was performed using the Effective Fragment Potential
method. 3 From this work we show how these components of the interaction energy
change with increasing size of the ion clusters, highlighting the growing contribution of
dispersion interactions per ion pair. Additionally, the effect of increasing alkyl chain
length in the imidazolium-based cation on inter-ionic interactions was also considered.

(1) Izgorodina, E. I.; Bernard, U. L.; MacFarlane, D. R. The Journal of Physical
Chemistry A 2009, 113, 7064. (2) Izgorodina, E. I. Physical Chemistry Chemical
Physics 2011, 13, 4189. (3) Gordon, M. S.; Freitag, M. A.; Bandyopadhyay, P.; Jensen,
J. H.; Kairys, V.; Stevens, W. J. The Journal of Physical Chemistry A 2000, 105, 293.
COIL-4:359
Insights into Lithium Coordination in Ionic Liquid Electrolytes for Lithium
Batteries
Paul M Bayley (1) , pmbayley@gmail.com, Burwood Hwy, Burwood Victoria 3125,
Australia ; Adam S Best (2) ; Leslie J Lyons (3) ; Douglas R MacFarlane (4) ; Maria Forsyth (1) .
(1) ITRI, Deakin University, Burwood Victoria 3125, Australia (2) Division of Energy
Technology, CSIRO, Clayton Victoria 3168, Australia (3) Department of Chemistry,
Grinnell College, Grinnell IA, United States (4) School of Chemistry, Monash University,
Clayton Victoria 3800, Australia
A small group of Ionic Liquids (ILs) have been shown to be compatible with lithium
electrochemistry. Their low volatility make ILs ideal for lithium batteries, particularly for
large-scale application, such as electric vehicles, where safety is of paramount concern.
The principle drawback of these materials is the low diffusivity of the ions relative to
conventional organic electrolytes as well as the discrepancy between the diffusivity of
the two cations (IL cation > Li + ). In this work a range of molecular additives (Toluene,
THF, 1NM3, TG) are added to an IL electrolyte and studied by multinuclear NMR to
elucidate their affect on the coordination and transport properties of the system. 1,2
Importantly, for every system, the lithium ions were the most affected by the presence of
the additive, particularly at lower temperatures. 7 Li spin-lattice (T1) measurements
clearly show the trend of how much the additive is influencing the lithium ion
environment, ranging from no influence (Toluene) to a progressively greater change
(TG > 1NM3 > THF), molecular additives are an important tool to create the optimal
safe electrolyte for lithium batteries. (1) Bayley, P. M.; Lane, G. H.; Lyons, L. J.;
MacFarlane, D. R.; Forsyth, M. The Journal of Physical Chemistry C 2010, 114, 20569.
(2) Bayley, P. M.; Best, A. S.; MacFarlane, D. R.; Forsyth, M. Physical Chemistry
Chemical Physics 2011, 13, 4632.
COIL-4:360
Understanding Dynamic Heterogeneity in Ionic Liquids Using the Ultrafast
Excited-State Isomerization of a Stilbene-Like Fluorescence Probe
Minako Kondo (1) , muk31@pau.edu, 104 Chemistry Building, University Park PA 16802,
United States ; Xiang Li (1) ; Mark Maroncelli (1) . (1) Department of Chemistry, Penn State
University, Univeristy Park PA 16802, United States
Solvation, rotational and reactive dynamics of several probes has been studied in wide
varieties of room temperature Ionic Liquids (ILs). Experimental and computational

studies show that dynamics occurring on the picosecond time scale are often nonexponential.
In a few cases this non-exponential kinetics has been shown to indicate the
presence of dynamic heterogeneity of the sort well-known in glass-forming liquids. In
the present study, the ultrafast excited-state reaction of the stilbene-like molecule, 2-[4-
(dimethylamino)styryl]benzothiazole (DMASBT, Fig.1) was used to further investigate
dynamic heterogeneity in ionic liquids. Steady state electronic spectroscopy and timecorrelated
single photon counting measurements with 25 ps time resolution were used
to measure the rate of the DMASBT reaction in conventional solvents and ILs. Results
in conventional solvents indicate that isomerization about the double bond is the
dominant non-radiative decay process. The reaction rate depends strongly on both
solvent viscosity and polarity. In most conventional solvents exponential kinetics are
observed, with time constants ranging between 20-100 ps. In contrast, the reaction is
considerably slower and non-exponential in the ionic liquids examined to date.
Measurements of the excitation wavelength dependence of the kinetics show that this
non-exponentiality is the result of dynamic heterogeneity. We are currently attempting to
model these excitation-dependent measurements using the measured solvation
response of the ionic liquids studied and simple models of the dependence of the
reaction rate on solvation energy. Figure 1. DMASBT
COIL-4:361
Thiol-Ene Coupling Reactions of an Oleyl-Based Precursor: Synthesis of Novel
Lipid-Inspired Ionic Liquids.
Arsalan Mirjafari (1) , mirjafari@usouthal.edu, 307 N University Blvd., Mobile Alabama
36688, United States ; Richard A O[apos]Brien (1) ; Kevin N West (2) ; James H Davis,
Jr. (1)(2) . (1) Department of Chemistry, University of South Alabama, Mobile Alabama
36688, United States (2) Department of Chemical and Biomolecular Engineering,
University of South Alabama, Mobile Alabama 36688, United States
It is challenge to design imidazolium-based ILs (the most common IL class) that
incorporate progressively more lipophilic structural elements while maintaining melting
points below room temperature. The Tm values of these ILs increase significantly once
an appended N-alkyl group exceeds seven carbons in length. Herein, we report that by
using the thiol-ene reaction, a series of lipid-inspired ILs with very low Tm values can be
synthesized. Each of the ILs has a long chain alkyl appendage related to those of
natural fatty acids. The synthesis process has three steps starting from 1methylimidazole
and high-purity fatty alcohols and leads to the imidazolium-based ILs
with long saturated alkyl chains containing sulfur moieties. This discovery may have
dramatic impacts for IL use in heat-transfer fluids, lubricants and gas storage
applications.
COIL-4:362
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The Binary Ph2PCl/GaCl3 System: A Room-Temperature Molten Medium for P-P
Bond Formation
Jan J. Weigand (1) , jweigand@uni-muenster.de, Corrensstr. 30, Münster NRW 48149,
Germany ; Michael H. Holthausen (1) ; Neil Burford (2) . (1) Institut für Anorganische und
Analytische Chemie, Westfälische Wilhelms-Universität Münster, Münster NRW 48149,
Germany (2) Department of Chemistry, Dalhousie University, Halifax Nova Scotia B3H
4J3, Canada
An equimolar reaction mixture of Ph2PCl and GaCl3 at room temperature results in the
formation of a melt consisting of the donor–acceptor complex Ph2PCl-->GaCl3, the
chloro(diphenylphosphanyl)diphenylphosphonium cation [Ph2(Cl)PPPh2] + , and the
counteranions [GanCl3n+1] – (n = 1, 2, 3). The melt has been characterized by Raman and
NMR spectroscopy and is compared with the reaction mixture of Ph2PCl and GaCl3
observed in solution (CH2Cl2). The melt provides a facile and reactive source of the
diphenylphosphenium cation [Ph2P] + , as demonstrated with use for P–P bond insertion
into (PhP)5, to give the 2,3,4,5-tetraphosphanyl-1,4-diphosphonium dication, and
reductive coupling with gallium metal to give the diadduct Cl3GaPPh2PPh2GaCl3. [1] We
were able to extend this chemistry by intercepting the diorganophosphenium cation
[Ph2P] + with P4 to consecutively insert into the P–P bonds. This approach resulted in the
formation of the cationic cages [Ph2P5] + , [Ph4P6] 2+ , and [Ph6P7] 3+ .
[2] References: 1. J. J.
Weigand, N. Burford, A. Decken, Eur. J. Inorg. Chem. 2008, 4343. 2. J. J. Weigand, M. H. Holthausen, R.
Fröhlich, Angew. Chem. Int. Ed.. 2009, 48, 295.
COIL-4:363
Functionalized Ionic Liquids with Highly Polar Polyhydroxylated Appendages and
their Rapid Synthesis Via Thiol-Ene Click Chemistry
Arsalan Mirjafari (1) , mirjafari@usouthal.edu, 307 N University Blvd., Mobile Alabama
36688, United States ; Richard A O[apos]Brien (1) ; Kevin N West (2) ; James H Davis,
Jr. (1)(2) . (1) Department of Chemistry, University of South Alabama, Mobile Alabama
36688, United States (2) Department of Chemical and Biomolecular Engineering,
University of South Alabama, Mobile Alabama 36688, United States
Over the past decade, functionalized or “task-specific” ionic liquids (TSILs) have found
utility in a wide array of applications, ranging from catalysis to separations. Typically,
functional groups in TSILs have been heteroatom-based, and their synthesis
complicated by unwanted byproducts. Impressed by the power of the click paradigm, we
investigated the thiol-ene reaction with different ene-functionalized ionic liquids (ILs) by
reacting them photochemically with 1-thioglycerol, yielding polyhydroxylated ILs in a
single step. Four different ILs were selected as ene substrates for the study.
Imidazolium and quaternary ammonium-based cations with either N-vinyl or N-allyl
appendages were chosen to assess the effect, if any, of having the alkene moiety
connected directly to the center of the cationic charge versus being separated from it by
one carbon unit. In addition, two different anions were employed to discern any control

over the course of the thiol-ene reaction. We chose 1-thioglycerol for our initial study in
order to demonstrate the incorporation of a desirable functional group (-OH) into an IL
by way of the orthogonal reaction of ene-bearing IL ions.
COIL-4:364
Solubility of Mixed Gases Containing Carbon Dioxide in Imidazolium Based Ionic
Liquids
chaojun shi (1) , cshi@nd.edu, 182 Fitzpatrick Hall, notre dame IN 46556, United States ;
Joan Brennecke (1) . (1) department of chemical and biomolecular engineering, University
of Notre Dame, notre dame IN 46556, United States
Ionic liquids (ILs) can be used for a wide range of gas separations because there are
significant differences in the solubility of various gases in ILs. Also, of primary
importance in evaluating CO2/ILs systems for chemical reactions involving permanent
gases is the solubility of those gases in ILs in the presence of CO2. Recently several
groups have reported that the presence of CO2 increases the solubility of other gases
that are poorly soluble in the ionic liquid phase. However, some other groups
demonstrated that there is no significant improvement of the gas solubilities in the CO2/
ILs biphasic systems compared to pure gas solubilities. Therefore, it is important to
further investigate the phase behavior of these ionic liquid / CO2 systems. Here, we
investigate the solubility of pure N2, and gas mixtures with different compositions (90/10
and 75/25 N2 to CO2 mole ratios) in imidazolium based ionic liquids and compare these
results to pure gas solubilities and previous reports. A series of experiments were
performed at preset temperatures and liquid compositions by means of a very precise
fixed volume view-cell coupled with an online gas chromatography. A temperature
range from (296 to 333) K was investigated with pressures up to about 1000 psi. The
enhancement of the solubility of N2 by CO2 is relatively modest under the conditions
investigated. We have also investigated the solubility of multicomponent gas mixtures
(argon, nitrogen and oxygen) in the ionic liquids in the presence of CO2.
COIL-4:365
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Synthesis of Lipid-Like Ionic Liquids with Diverse Alkyl Appendages via Thiol-
Ene Reaction
Kaila M Mattson (1) , kmm708@jaguar1.usouthal.edu, 307 N University Blvd., Mobile
Alabama 36688, United States ; Richard A O[apos]Brien (1) ; Arsalan Mirjafari (1) ; Kevin N
West (2) ; James H Davis, Jr. (1)(2) ; Samuel M Murray (2) . (1) Department of Chemistry,
University of South Alabama, Mobile Alabama 36688, United States (2) Department of
Chemical and Biomolecular Engineering, University of South Alabama, Mobile Alabama
36688, United States

Recently our group explored the impact of side-chain unsaturation in ionic liquids (ILs)
with relation to the fluid-mosaic model and its dramatic effect on melting points.
Influenced by the synthetic power of click chemistry, we investigated the thiol-ene
reaction with different ene-functionalized ILs by reacting them photochemically with
alkylthiols, yielding lipid-like ILs in a single step. In addition, we employed differential
scanning calorimetry to study the effects of both long and branched appendages upon
IL melting points. Several different ILs were selected as ene substrates for the study.
Imidazolium-based cations with either N-allyl, N-decenyl or N-undecenyl chains were
chosen to assess the effect, if any, of having the sulfur moiety at various chain lengths
from the center of the cationic charge. In addition, two different anions were employed
to discern any control over the course of the thiol-ene reaction. Several straight chain
and branched thiols were studied, which incorporated a series of alkyl, including stearylbased,
and branched thioether-based appendages into the IL framework. The synthetic
methodology as well as the impact of these structural modifications upon IL melting
points will be discussed.
COIL-4:366
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Charge Type Effects on Bimolecular Electron Transfer Reactions in C4mpyrr NTf2
Masao Gohdo (1) , mgohdo@bnl.gov, Bldg.555, Upton NY 11973, United States ; James
F. Wishart (1) . (1) Department of Chemistry, Brookhaven National Laboratory, Upton NY
11973, United States
Electron transfer reactions underlie many of the important applications of ionic liquids
(ILs), including solar cells, fuel cells and batteries. The unusual dynamical properties of
ILs, and the fact that they are composed solely of ions, have important mechanistic
consequences for reactions involving charge redistribution. Interactions between solutes
and IL cations and anions can be affected by changing the charge of the solute.
Depending on the reactant charges, preferred solvation environments may change
during the course of charge transfer. Furthermore, electrochemical experiments have
shown that the diffusion constants of redox-active species may depend on charge type
much more strongly in ILs than in conventional solvents. To explore these effects, we
are studying intermolecular redox reaction mechanisms in ionic liquids to quantify their
dependence on reactant charge types and the physical properties of the ILs. For our
preliminary studies we are measuring a series of electron transfer reactions between
quasi-isostructural biaryl electron donors (biphenyl anion, phenylpyridinyl radical, methyl
viologen monocation, etc.) and substituted p-benzoquinones in C4mpyrr NTf2. We use
pulse radiolysis to generate solvated electrons in the IL, which react with the biaryl
scavengers to produce radical redox intermediates of different charge types that react
with the benzoquinones. Compared to electrochemical methods, pulse radiolysis has
certain merits: the reduced species are generated homogeneously in solution instead of
near a polarized electrode surface; the redox kinetics can be directly observed down to
the nanosecond time scale, and it is usually possible to spectroscopically observe both
the reductant and oxidant. The effects of different charge types on the diffusion

coefficients of the reactants and their electron transfer rates will be discussed, also
taking the thermodynamics into account. This work was supported by the U. S.
Department of Energy Office of Basic Energy Sciences under contract #DE-AC02-
98CH10886.
COIL-4:367
Pressure-Equilibrium Curves of Typical Natural Gas Components in a Blend of
Imidazolium Based Ionic Liquid for Selective Absorption
Peter Janiczek (1) , peter.janiczek@proionic.com; Roland St. Kalb (1) ; Gerhard
Thonhauser (2) ; Thomas Gamse (3) ; Leopold Braeuer (4) . (1) Research and Development,
proionic GmbH, Grambach 8074, Austria (2) Chair of Drilling Engineering, Mining
University Leoben, Leoben 8700, Austria (3) Institute of Chemical Engineering and
Environmental Technology, Graz University of Technology, Graz 8010, Austria (4)
Technology Development and Application, OMV Exploration & Production, Vienna
1020, Austria
Obtaining sales-specifications for natural gas is essential all over the world. Among
others, carbon dioxide (CO2) and hydrogen sulphide (H2S) are two impurities, which are
present almost in every natural gas reservoir. Chemisorption with aqueous amine
solutions is a common technique for cleaning the gas, but possesses some
disadvantages, which could be avoided by using Ionic Liquids (ILs) as washing media.
Applying the method of the isochoric equilibrium cell a blend of two imidazolium based
ILs was tested for the absorption of CO2, H2S and methane (CH4). Using a 50wt% Nmethyldiethanole-amine
solution and CO2, the apparatus was checked with literature
data for its reproducibility and accuracy. Here, equilibrium data for the mentioned gases
in the IL-Blend are presented at 273.15 K, 313.15 K and 353.15 K and pressures
ranging from 10 kPa to 9 MPa depending on the type of gas as a part of a successful
feasibility study.
COIL-4:368
Mechanism of CO2 Capture by Amino Acid Ionic Liquids Appears to be
Dramatically Altered by the Presence of Water
Jonathan L McDonald (1) , jlm312@jaguar1.usouthal.edu, 307 N University Blvd., Mobile
Alabama 36688, United States ; Paul Hixon (1) ; Richard E Sykora (1) ; James H Davis,
Jr. (1)(2) . (1) Department of Chemistry, University of South Alabama, Mobile Alabama
36688, United States (2) Department of Chemical and Biomolecular Engineering,
University of South Alabama, Mobile Alabama 36688, United States
Proteinogenic amino acids have attracted considerable attention as candidates for use
in task specific ionic liquids (TSIL) for reversible CO2 capture. Several groups have
reported efficient and reversible capture by such ILs under rigorously dry conditions.
However, we observed that capturing CO2 using amino acid ILs (AAILs) is hugely

impacted by the presence of water, and that the amino acid anions appear to play only
a transitory role. As additional CO2 and water contact these ILs, acid-base chemistry
appears, effectively, to force protonation of the amino acid anions by water, resulting in
crystallization of neutral amino acids from the IL milieu. In such instances, the net CO2
capture process over time appears to be one of [cation] + OH - => [cation] + [carbonate] -
and/or 2[cation] + [bicarbonate] 2- . Significantly, these complications do not appear to
arise in the capture of CO2 in wet gas streams by ILs based upon amino acids of the
type RNH-(CH2)x-SO3 - . The apparent difference in the behavior of the latter appears to
be driven by the very large pKb difference between R-CO2 - and R-SO3 - species.
Supporting our assertion that water complicates CO2 capture by amino acid anions, a
crystalline CO2 complex of the glycine anion was serendipitously isolated, the salt
2[N1111] + ·[glycine carbamate] 2- being characterized by X-ray diffraction. Formation of this
salt appears to be at odds with computational predictions that amino anions in AAILs
preferentially sequester CO2 as carbamic acid. Significantly, when re-dissolved in water
and exposed to additional CO2 the former salt precipitates pure glycine in quantitative
amounts. Although our survey of other amino acid anions remains incomplete, the
phenomenon of CO2-driven precipitation of parent amino acids appears to be general.
At a minimum, these results suggest that under common flue gas conditions, the role of
the amino acid anion in CO2 capture is open to question.
COIL-4:369
Behavior of Ionic Liquids in Bulk and at Interfaces from MD Simulations
Oleg Borodin (1) , oleg.borodin@us.army.mil, 2800 Powder Mill Rd, Adelphi MD, United
States ; Dmitry Bedrov (2) ; Justin Hooper (2) . (1) Army Research Laboratory, Adelphi MD,
United States (2) Wasatch Molecular Inc, Salt Lake City, United States
Utilizing the transferable, quantum chemistry-based, polarizable APPLE&P force field,
we have studied ionic liquids and crystals with potential applications from lithium
batteries to supercapacitors to hypergolic fuels. We systematically investigated the
influence of polarization effects on the accuracy of properties predicted from molecular
dynamics simulations of various room temperature ionic liquids (ILs). Simulations using
polarizable APPLE&P force field were compared with corresponding simulations using
two types of non-polarizable force fields: 1) in which the atom based polarizability was
set to zero for all atoms (non-polarizable APPLE&P potential) and 2) a force field
obtained using the Force Matching approach that reproduces as accurately as possible
intermolecular forces predicted by the polarizable model. For all ILs we found that
turning off polarization interactions results in significant slowing down (factor of 2-7) of
ion dynamics and related transport properties. Ion-ion structural correlations are
noticeably effected if polarization interactions are not taking into account. While in many
ILs these effect is modest, in some ILs such as e.g. those containing cyano-based
anions (N(CN)2, C(CN)3, B(CN)4) turning off polarization leads to qualitatively different
ion-ion structural correlations compared to those obtained from simulations using
polarizable force field. We also investigated influence of polarization on interfacial
properties of ILs such as surface tension at the IL-vacuum interface. This work was

supported by the Air Force Office of Scientific Research, STTR Phase-II contract
#FA9550-09-C-0110 to Wasatch Molecular Inc. and University of Utah.
COIL-4:370
Synthesis of Nanoparticles Using Ionic Liquids as Capping Ligands by
Solvothermal Method
Eun H. Cha (1) , chaeunhee@korea.ac.kr, baebangmyn sechulri 165, Asan choongnam
336-795, Republic of Korea . (1) Graduate school of green energy engineerinf, Hoseo
university, Asan choongnam 336-795, Republic of Korea
The effects of ionic liquids as capping ligand and also solvent on the morphology and
phase of the CdSe/ZnS nanoparticles were studies. Colloidal CdSe/ZnS nanoparticles
were synthesized using various ionic liquids, that is 1-methyl-3-methyl -imidazolium
bis(trifluoromethylsulfonyl)imide (EMIMTFSI), 1-buthyl-3-ethylimidazolium
bis(trifluoromethylsulfonyl)imide(BMIMTFSI), 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide
(HMIMTFSI),1-Octyl-3-methylimidazolium (trifluoromethylsulfonyl)
imide (OMIMTFSI) and trihexyltetradecylphosphonium bis(trifluoromethyl sulfonyl) imide
(P6,6,6,14TFSI), In particular, the morphology evolves from dots to rods upon the longer
alkyl chains of imidazolium cation. The CdSe/ZnS nanoparticles which were
synthesized using P6,6,6,14TFSI with octadecen(ODE) exhibited the smaller size than that
synthesized using imidazolium and controlled phase from zinc-blende to wurtzite by
increasing the volume ratio of P 6,6,6,14TFSI.
COIL-4:371
Ionic Liquids which try to be Like Hydrazine
Stefan Schneider (1) , stefan.schneider@edwards.af.mil, 10 East Saturn Blvd, Bldg
8451, Edwards AFB CA 93524, United States ; Yonis Ahmed (1) ; Michael Rosander (1) ;
Tommy Hawkins (1) . (1) Air Force Research Laboratory, Edwards AFB CA 93524, United
States
Ionic liquids (ILs) are getting more and more attention because of many remarkable
properties such as low volatility, low flammability, high ion mobility, and excellent
chemical and thermal stabilities. Due to these properties, ILs are being increasingly
investigated for all kinds of liquid applications, including the niche area of energetic
materials. Currently, hydrazine and its derivatives are state-of-the-art rocket fuels.
Ongoing investigation on energetic ILs in our laboratory led to the first discovery of ILs
as hypergolic fuels, and from an environmental perspective, these ILs could provide an
alternative to the highly toxic hydrazine fuels used today. Prospective design strategies
for ILs which would emulate properties that make hydrazine such a useful propellant
fuel are discussed.
COIL-4:372

A New Approch to Strong Ionicity Ionic Liquids (Siils)
Ana B. Pereiro (1) , anab@itqb.unl.pt, Av. da República, EAN, Oeiras Oeiras, Portugal ;
Joao M. M. Araújo (1) ; Jose M. S. S. Esperança (1) ; Isabel M. Marrucho (1) ; Luis P. N.
Rebelo (1) . (1) Instituto de Tecnologia Química e Biológica, UNL,, Oeiras 2780-157,
Portugal
Nowadays, the investigation of ionic liquids (ILs) is on the leading edge of the most
promising science and technology, and ILs are, therefore, gaining wide technological
and industrial relevance in many disciplines, allowing for the design of novel and
sustainable solutions to old problems. This work exploits a new scientific branch of the
ILs field, one that is almost unexplored. It lays on the significant increase of the
Coulombic character of these compounds through the solubilisation of simple inorganic
salts (ISs) in their milieu. Therefore, at very low cost, ionicity is increased while the
liquid state status is still preserved. A new class of ILs, the Strong Ionicity Ionic Liquids
(SIILs) will emerge. A systematic understanding of the complex chemistry behind the
SIILs has been achieved by monitoring several thermodynamic and transport
properties. The determination of different properties of these mixtures, namely, their
ionic conductivity, density, viscosity, refractive index, and thermal stability, have been
carried out as a function of the IS content. Walden plots have been used to clarify the
role of the inorganic salts in SIILS. These data are paramount for the development of
thermodynamic models. Molecular level insights on the interionic interactions and the
liquid structure have been provided by NMR studies. Also, this technique has been used
to understand the underlying mechanism of solubilisation. The establishment of
preferential interactions simultaneously with functional groups of both the cations and
the anions is the cause of this enhancement of the conductivity of these mixtures.
COIL-4:373
Ionic Liquids for Enzymatic Sensing
Kevin J Fraser (1) , kevin.fraser@dcu.ie, National Centre for Sensor Research,
Glasnevin Dublin Dublin 9, Ireland ; Caroline Barry (1) ; Robert Byrne (1) ; Fernando Benito-
Lopez (1) ; Susan Warren (2) ; Eithne Dempsey (2) ; Dermot Diamond (1) . (1) National Centre
for Sensor Research, Dublin City University, Dublin Dublin 9, Ireland (2) Department of
Science, Institute of Technology Tallaght (ITT Dublin), Dublin Dublin 24, Ireland
Point-of-care (POC) glucose biosensors play an important role in the management of
blood sugar levels in patients with diabetes. One of the most commonly used enzymes
in glucose biosensors is Glucose Oxidase (GOx). It is a biorecognition enzyme, which
recognises the glucose molecule and acts as a catalyst to produce gluconic acid and
hydrogen peroxide in the presence of glucose and oxygen. [1] Ionic liquids (ILs) have
evolved as a new type of solvent for biocatalysis, mainly due to their unique and tunable
physical properties. [2] Amperometric biosensors employing ILs have been reported
previously, for example, ([BMIM][BF4]) has been used as a mediator in a
electrochemical H2O2 biosensor [3] . This interest is driven by the need to find molecular

environments in which enzymes are highly stabilized while retaining redox activity; and
in which substrate transport to, and product transport from, the enzyme is not inhibited
In this paper, we report the response characteristics of various enzymatic sensors
(optical and electrochemical [4] ) that incorporate RTIL's as an integral part of their
structure. Our results suggest that these sensing platforms can be incorporated into
flexible materials such as carbon cloth and incorporated into wearable sensor platforms
for monitoring important parameters related to athlete performance, and health. [1] J.
Newman, P. Turner, “Home glucose biosensors: a commercial perspective”. Biosensors
and Bioelectronics, vol.20, pp. 2435-2453. [2] Zhao, H. (2010), Methods for stabilizing
and activating enzymes in ionic liquids—a review. Journal of Chemical Technology &
Biotechnology, 85: 891–907. doi: 10.1002/jctb.2375 [3] Liu.Y, Shi.L, Wang. M, Li.Z, Liu.
H and Li. J, Green Chem 7:655 – 658 (2005). [4] S. Y. Yang, F. Cicoira, R. Byrne, F.
Benito-Lopez, D. Diamond, R. A. i. n. M. Owens and G. G. Malliaras, Chem.Commun.,
2010, 46, 7972-7974.
COIL-4:374
Natural Fiber Welding – Visualizations of Polymer Reorganization
Luke M. Haverhals (1) , haverhal@usna.edu, 572M Holloway Rd MS-9B, Annapolis, MD
MD 21402, United States ; Matthew P. Foley (1) ; Robert W. Burdon (1) ; Hugh C. De
Long (2) ; Paul C. Trulove (1) ; Jeff W. Gilman (3) ; Mauro Zammarano (3) ; Doug M. Fox (4) . (1)
Department of Chemistry, United States Naval Academy, Annapolis MD 21402, United
States (2) Directorate of Mathematics, Information and Life Sciences, Air Force Office of
Scientific Research, Arlington VA 22203, United States (3) Polymer Division, National
Institute of Standards and Technology, Gaithersburg MD 20899, United States (4)
Department of Chemistry, American University, Washington DC 20016, United States
Data are presented that demonstrate a biopolymer processing methodology we call
“natural fiber welding”. During fiber welding, precise amounts of a suitable ionic liquid
solvent are applied to selected areas (volumes) of a biopolymer material. Solvents swell
and mobilize biopolymers as they penetrate the natural fibrous materials. The process
opens selected portions of natural fibers and renders them accessible to modification
and follow on chemistry. Biopolymers congeal and form complex biopolymer
composites upon removal of the ionic liquid. In addition to the amount, type, and purity
of solvents utilized, other factors such as time, temperature, and pressure control the
amount of biopolymer reorganization observed and the extent to which native
biopolymer structure is disrupted. Data are presented that characterize selected
examples of fiber welded materials. In particular, fluorescently labeled biopolymers
(fluorescent microscopy) aid in the visualization of polymer movement as a function of
process variables. Fluorescence microscopy data are complimented with an assortment
of other bulk and surface specific characterization techniques such as mechanical
testing, powder x-ray diffraction, scanning electron microscopy, and attenuated total
reflectance infrared spectroscopy.
COIL-4:375

Activiy Coefficients at Infinite Dilution In [Epy][ESO4]
Emilio J. González (1) , emiliojgg@fe.up.pt, Faculty of Engineering-Rua Dr. Roberto
Frias s/n, Porto 4200-465, Portugal ; Begoña González (2) ; Beatriz Orge (2) ; Eugenia A.
Macedo (1) . (1) LSRE Laboratory of Separation and Reaction Engineering, Associate
Laboratory LSRE/LCM, Department of Chemical Engineering, University of Porto, Porto
4200-465, Portugal (2) Advanced Separation Processes Group, Department of
Chemical Engineerinng, University of Vigo, Vigo Pontevedra 36310, Spain
From the industrial point of view, the selection of suitable solvents for liquid-liquid
extraction or azeotropic and extractive distillations can be carried out knowing the
activity coefficients at infinite dilution of the key components in the solvent. The classical
way to measure the phase equilibrium has been through the use of ebullometry or static
differential techniques, which are not appropriate in the diluted region, as the values
given are not very accurate. This diluted region is of great importance when trying to
obtain a high purity product. In order to obtain precise data on the behaviour in this
region it is necessary to use specific techniques such as gas-liquid chromatography, the
dilutor technique, etc. Furthermore, the use of activity coefficients at infinite dilution,
simultaneously with equilibrium data and excess enthalpies allows for group interaction
parameters and g E models more reliable. In this work the gas-liquid chromatography is
used to determine the activity coefficients at infinite dilution of several polar solutes
(ketones, alcohols, ethers and esters) in the ionic liquid 1-ethylpyridinium ethylsulfate.
Measurements were carried out at four different temperatures between 313.15 K and
373.15 K using the ionic liquid as stationary phase.
COIL-4:376
RAFT Controlled Free Radical Polymerisation in Ionic Liquids: An Indication of
Domain Segregation
Simon Puttick (1) , pcxsp3@nottingham.ac.uk, B3, University Park, Nottingham
Nottinghamshire NG7 2RD, United Kingdom ; Jaouad El Harfi (1)(2) ; Derek J Irvine (1)(2) ;
Kristofer J Thurecht (3) ; Peter Licence (1) . (1) School of Chemistry, University of
Nottingham, Nottingham, United Kingdom (2) Process and Environmental Research
Division, Faculty of Engineering, University of Nottingham, Nottingham, United Kingdom
(3) Australian Institute for Bioengineering and Nanotechnology, University of
Queensland, Brisbane, United Kingdom
The free radical polymerisation of methyl methacrylate (MMA) controlled by reversible
addition fragmentation chain transfer (RAFT) polymerisation in a number of imidazolium
ionic liquids is reported. 1,2 Observations of the affect of the anion and cation of the ionic
liquid on both the rate of conversion of monomer and on the evolution of molecular
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weight throughout the reaction were made. Several RAFT agents were used to
control the reaction and differences in the level of control that the RAFT agent affected
upon the reation were observed. The observed effects of all variables investigated are

linked to two emerging theories; the idea of nanostructural organisation in ionic liquids
and the theory that radical species are protected in an ionic liquid environment. 1. S.
Puttick et al, J Mater Chem, 2009, 19, 2679-2682. 2. S. Puttick et al, in preparation.
www.nottingham.ac.uk/ionicliquids
COIL-4:377
ThermophIL: An Application for Ionic Liquids Property Estimation
Pedro J. Carvalho (1) , quijorge@ua.pt, Campus Universitário de Santiago, Aveiro Aveiro
3810-193, Portugal ; Ramesh L. Gardas (2) ; João A.P. Coutinho (1) . (1) Departamento de
Química, CICECO, Universidade de Aveiro, Aveiro Aveiro 3810-193, Portugal (2)
Department of Chemistry, Indian Institute of Technology Madras, Chennai 600-036,
India
Ionic liquids (ILs) are a class of neoteric solvents composed of large organic cations and
organic or inorganic anions that cannot form an ordered crystal and thus remain liquid at
or near room temperature. The outstanding characteristics of these fluids, and the easy
manipulation of their properties due to the possibility of interchange among thousands
of cations and anions, make of the ILs “designer” solvents with a wide range of
foreseeable applications.Despite the exponential focus on ILs, both by academia and
industry, the availability of thermophysical properties data is still limited and with
questionable quality, making difficult the development of correlations and predictive
models for these properties. It was however possible after a critical analysis of the
available experimental data, complemented with further data measured at our lab to
propose a number of predictive methods for the thermophysical and equilibrium
properties of ionic liquids.Based on the correlations and group contribution methods
developed at our research group a on-line computer application was developed for the
prediction of a number of thermophysical and equilibrium properties such as density,
isobaric expansivity and isothermal compressibility, viscosity, surface tension, speed of
sound, ionic conductivity, heat capacity, water solubility and carbon dioxide solubility in
a wide temperature range.The application developed will be presented and it will be
discussed how it can be used for Computer Aided Molecular Design of Task Specific
Ionic Liquids. Acknowledgments Pedro J. Carvalho acknowledges the financial
support from Fundação para a Ciência e a Tecnologia through his PhD.
(SFRH/BD/41562/2007).
COIL-4:378
Separation of Sour Gases (CO2 and CH4) using Ionic Liquids
Pedro J. Carvalho (1) , quijorge@ua.pt, Campus Universitário de Santiago, Aveiro Aveiro
3810-193, Portugal ; João A.P. Coutinho (1) . (1) Departamento de Química, CICECO,
Universidade de Aveiro, Aveiro Aveiro 3810-193, Portugal

A class of neoteric organic solvents have gained an unprecedented bursting of interest,
both by academia and industrial medium, in recent years. Ionic liquids (ILs) large
organic cations and asymmetrical organic or inorganic anions compel these molecules
to remain liquid at or near room temperature, while presenting, among others
properties, negligible vapor pressures, high thermal stability, large liquidus range,
nonflammability and high solvation capacity. The tunable properties of ILs, through an
endless combination of cations and anions, allow the design of solvents for the
development of more efficient and sustainable processes and products.Nonetheless,
and despite of the promising properties of ILs, further research is still required in order
to make them solvents feasible candidates for real applications. Being a key parameter
in the design of equilibrium stage– and rate–based separations, reliable gas solubility
data is of most interest and a fundamental step towards the development of industrial
applications, either by the data itself or by developing predictive and simulation tools to
aid in the development of such applications.Using a high pressure cell, previously used
for extensive studies of CO2 solubilities, VLE isotherms up to 363 K and pressures up to
100 MPa were measured for mixtures of CO2 or CH4 with several aprotic and protic
ionic liquids. A comparison and evaluation of basic, fluorinated and protic ILs in a wide
range of pressures and temperatures, aiming at a better understanding of the
mechanisms of solvation of CO2 and CH4, was performed. Acknowledgments Pedro
J. Carvalho acknowledges the financial support from Fundação para a Ciência e a
Tecnologia through his PhD. (SFRH/BD/41562/2007).
COIL-4:379
Preparation of Amino Acid Ionic Liquid/Zwitterion Mixture and Analysis of
Aggregation State
Takuro Matsumoto (1) , 50007251067@st.tuat.ac.jp, 2-24-16, Naka-cho, Koganei Tokyo,
Japan ; Satomi Taguchi (1) ; Hiroyuki Ohno (1) . (1) Department of Biotechnology, Tokyo
University of Agriculture and Technology, Koganei Tokyo 184-8588, Japan
Ionic liquids have been studied as self-assembly media. The self-assembled structures
of ions in ionic liquids lead to the development of functional matrix. Since assembly of
ordinary ions was found as crystals, we focused on the zwitterions. Zwitterion, in which
both cation and anion are tethered with covalent bond, could avoid ion exchange
reaction in ionic liquids. In this study, we prepared amino acid ionic liquid (1-ethyl-3methylimidazolium
leucine: [emim][Leu]) and phosphonium type zwitterion (sulfobutyltri-n-octylphosphonium
betaine: ZI) mixtures, and their aggregation state was analyzed.
A mixture of n[emim][Leu] (n=1, 3) and ZI was obtained as a gel. Against these,
5[emim][Leu]/ZI was obtained as liquid. The mixtures obtained as gel were investigated
by polarized optical microscope (POM). There were spherulites having maltese crosses.
For further analysis on the assembled structure of mixtures, X-ray diffraction (XRD) was
performed. Four peaks with d-spacing of 16.7 (5.3°), 8.3 (10.7°), 5.5 (16.2°) and 4.2 Å
(21.3°), in other words, d-spacing ratio of 1:1/2:1/3:1/4 was observed. These peaks
were characteristic for a lamellar structure. Also, [emim][Leu]/ZI mixture showed halo
attributed to amorphous phase. The ionic conductivity of [emim][Leu], [emim][Leu]/ZI,

and [emim][Leu]/ZI/H2O mixtures on heating has been measured using alternating
current impedance method. The ionic conductivity of 5[emim][Leu]/ZI/10H2O (gel) is
higher than that of 5[emim][Leu]/ZI (liquid). The results suggested that aggregated
structure of ZI in ionic liquids contributed to provide higher ionic conductivity.
COIL-4:380
Synthesis of Ionic Liquids to Keep Glucose Oxidase Activity in the Presence of
Small Amount of Water
Kento Nagata (1) , 50007251053@st.tuat.ac.jp, coganeisi nakatyo 2-24-16, tokyo 184-
8588, Japan ; Mitsuru Abe (1) ; Hiroyuki Ohno (1) . (1) Department of Biotechnology, Tokyo
University of Agriculture and Technology, tokyo coganeisi nakatyo 2-24-16 184-8588,
Japan
Polar ionic liquids are only excellent solvents for cellulose under mild condition. We
have been studying the ILs to enable following three processes such as dissolution and
hydrolysis of cellulose, and glucose oxidation. In the present study, we have designed
the anode for glucose oxidation in IL with glucose oxidase (GOD). When the amounts
of added water to the polar ILs increased, the solubility of cellulose considerably
dropped. It is necessary to maintain the GOD activity in ILs containing small amount of
water. However, GOD is easily denatured in ILs containing small amount of water. It,
therefore, is not easy to prepare ILs containing small amount of water in which
cellulose is soluble and GOD retains its activity for glucose oxidation. The smallest
amount of water in the IL, in which GOD retains its activity, was studied for several ILs.
GOD activity was evaluated with cyclic voltammetry (CV) measurement. GOD kept the
activity in [C2(OH)mim][(MeO)(H)PO2] with smaller amount of water than that in
[C2mim][(MeO)(H)PO2]. Hydroxyl group on the cation seems to be effective to lower the
water content keeping GOD activity in the ILs. To confirm the effectiveness of hydroxyl
groups for lowering the water content, we prepared tris(2hydroxyethyl)methylammonium
(THEMA) cation, and was coupled with [(MeO)(H)PO2]
anion. GOD activity was retained in [THEMA][(MeO)(H)PO2] with 18 wt% water, and it
was smaller than that for other [(MeO)(H)PO2] salts examined in this study. Then, we
prepared a few [THEMA] salts and investigated the GOD activity in these ILs with small
amount of water. GOD activity was retained in [THEMA][glycolate] containing only 5
wt% water. This is the first report on the glucose oxidation in ILs with such a small
amount of water.
COIL-4:381
Complete Solvation Response of Coumarin 153 in Ionic Liquids
Mark Maroncelli (1) , maroncelli@psu.edu, 104 Chemistry Building, University Park
Pennsylvania 16802-4615, United States ; Xin-Xing Zhang (2)(3) ; Min Liang (1) ; Nikolaus P
Ernsting (2) . (1) Department of Chemistry, Pennsylvania State University, University Park
Pennsylvania 16802-4615, United States (2) Department of Chemistry, Humboldt

University, Berlin 12489, Germany (3) Department of Physical Science, Nankai
University, Berlin 12489, Germany
Solvation dynamics is the time-dependent response of a solvent to changes in the
charge distribution of a solute. This dynamics constitutes a fundamental property of
polar fluids and is important for determining frictional solvent effects on charge transfer
processes. The solvation response of ionic liquids differs from that in conventional polar
solvents in that it spans a very broad time range. While nearly half of the response
takes place in the first 5 ps, significant relaxation components persist to the nanosecond
time domain. For this reason, complete characterization of the solvation response in
ionic liquids is difficult and few such measurements have been reported to date. We
have used a combination of time-correlated single photon counting and broadband
fluorescence upconversion to fully characterize the solvation dynamics of coumarin 153
in a variety of ionic liquids. The solvents studied include 14 neat ionic liquids and
mixtures of one imidazolium-based IL and acetonitrile. Series of pyrrolidinium ionic
liquids in which the alkyl content of the cation, as well as imidazolium ionic liquids in
which the anion component was systematically varied, were used to help identify the
primary factors determining the observed response. We find that the solvation response
of all of the neat ionic liquids is well described by a substantial sub-picosecond
component followed by a stretched exponential behavior covering the few picosecond to
nanosecond range. The dynamics in the ionic liquid + dipolar solvent mixtures is better
fit using a triple exponential function. Our results indicate that the fast component of
solvation originates from inertial motions, while the slow component, which is correlated
to solvent viscosity, is due to diffusional motions. Solvation response functions predicted
based on dielectric continuum models and recent dielectric relaxation measurements
are similar to but typically faster than the observed response.
COIL-4:382
Hydrogen Bonding and Halogen···Halogen Bonding Patterns
Polina Oliferenko (1) , poliferenko01@qub.ac.uk, David Keir Building, Stranmillis Mews,
Belfast Northern Ireland BT9 5AG, United Kingdom ; Kenneth R. Seddon (1) . (1) QUILL
Centre, The Queen[apos]s University of Belfast, Belfast BT9 5AG, United Kingdom
Hydrogen bonds and their halogen···halogen counterparts are important structure
determinants in crystal structures and ionic liquids. The abundance of crystallographic
information available from the Cambridge Crystallographic Database has been analysed
using novel custom-designed fitting functions based on the orientational distribution
function formalism. Contact distance/angle distribution maps are built for three major
hydrogen bond contacts (O-H···O=C, N-H···O=C, C-H···O=C, with C-H···H-C as a
reference) and three major halogen···halogen bond contacts (Cl···Cl, Br···Br, I···I, with
F···F as a reference). Based on these empirical distributions, a set of analytically
approximated maps was derived and relative contact energies were calculated (Fig. 1).
Such intermolecular contact energies correlate well with quantum chemically calculated
binding energies. The proposed methodology can be used in molecular design of ionic

liquids, crystals, and supramolecular assemblies. Extension to the analysis of
crystallographic information contained in the Protein Data Bank is also possible, which
can find application in bioinformatics and drug design. Fig. 1. Case study of
CH···O=C contact: 1) raw data distribution map, 2) analytically approximated map, 3)
potential energy map, and 4) correlation with quantum chemically calculated energies
COIL-4:383
Thermophysical Properties of the 1-Ethyl-3-Methylimidazolium Alkylsulfate
Family
José M. S. S. Esperança (1) , jmesp@itqb.unl.pt, Av. da República, Oeiras Oeiras,
Portugal ; Anabela J. L. Costa (1) ; Isabel M. Marrucho (1) ; Luís P. N. Rebelo (1) . (1) Instituto
de Tecnologia Química e Biológica/Universidade Nova de Lisboa, Oeiras 2780-157,
Portugal
Density and viscosity data for 1-ethyl-3-methylimidazolium-based ionic liquids combined
with the n-alkyl sulfate anion (n=1,4,6,8) and hydrogen sulfate were measured at
atmospheric pressure in the temperature range 283

Portugal, Porto Porto 4200-465, Portugal ; Irene Domínguez (2) ; Elena Gómez (2) ;
Ángeles Domínguez (2) . (1) Department of Chemical Engineering, University of Porto,
Porto Porto 4200-465, Portugal (2) Department of Chemical Engineering, University of
Vigo, Vigo Pontevedra 36310, Spain
Ionic liquids (ILs) have emerged as a novel alternative to traditional organic solvents
due to their non-volatile nature. For the last years, ionic liquids are being studied as
separation agents for several mixtures containing alkanes and aromatic compounds.
The liquid-liquid equilibrium (LLE) data of the ternary systems heptane (1) + toluene (2)
+ 1-butyl-3-methylimidazolium methylsulfate [BMim][MSO4] (3) or 1-butyl-3methylimidazolium
bistrifluoromethylsulfonylimide [BMim][NTf2] (3) ionic liquids (ILs)
were determined at T = 298.15 K and atmospheric pressure, with the objective of
studying the influence of the anion of the ILs on the separation of aromatic from
alkanes. Solubility curves were obtained by the cloud point method and tie-lines
compositions were determined by density measurements. It is remarkable that the
miscibility region in the system containing [BMim][NTf2] is considerably wider than in the
system containing [BMim][MSO4]. An analysis of the influence of the anion of the
imidazolium-based ionic liquids on the extraction was evaluated in terms of the solute
distribution ratio (β) and selectivity (S). Comparing the behavior of both systems, the S
values are higher for the system containing [BMim][MSO4], and on the other hand, the β
values are higher where [BMim][NTf2] is used as solvent, being higher than the unity at
lower compositions of benzene in the upper phase. The degree of consistency of the
experimental LLE data was ascertained using the Othmer-Tobias and Hand equations.
The experimental data of liquid-liquid equilibria of the ternary systems were satisfactorily
correlated with the Non-Random Two-Liquid (NRTL) and UNIversal QUAsi-Chemical
(UNIQUAC) thermodynamic models.
COIL-4:385
On the Negative Pressure Regime of Ionic liquids
José M. S. S. Esperança (1) , jmesp@itqb.unl.pt, Av. da República, Ap. 127, Oeiras
Oeiras 2780-157, Portugal ; Helena I. M. Veiga (1) ; José N. Canongia Lopes (1)(2) ; Luís P.
N. Rebelo (1) . (1) Instituto de Tecnologia Química e Biológica/Universidade Nova de
Lisboa, Oeiras 2780-157, Portugal (2) Instituto Superior Técnico/Universidade Técnica
de Lisboa, Oeiras 2780-157, Portugal
Absolute negative pressure regimes constitute a specific subclass of superheating [1],
one in which p < 0. Under such condition, the liquid is under tension and is
thermodynamically metastable [2] with respect to the vapour phase – if both
superheating and supercooling are achieved, then, the liquid is under a double
metastable state (in respect to both the solid and the vapor). In order to achieve this, it
is necessary to define the imposed external thermodynamic constraints to the system,
namely, pressure and temperature (p, T) constant or total volume and temperature (V,
T) constant. Negative pressure regimes are not forbidden for systems that cannot
expand infinitely (condensed phases such as liquids and solids). Absolute negative

pressure states can be held for considerable periods of time, in spite of their
metastability, permitting the measurement of physical properties of substances[3] and
their mixtures, as well as, liquid-liquid phase equilibria[4]. In this work, several different
ionic liquids, 1-alkyl-3-methylimidazolium bis(trifluoro methylsulfonyl)imide, 1-alkyl-3methylimidazolium
alkylsulfonates, 1-alkyl-3-methylimidazolium alkylsulfates and
trihexyl(tetradecyl)phosphonium with different anions, were tested at absolute negative
pressures to define their practical limit of metastability. Working temperatures ranged
from -50ºC to 200ºC and it was possible, for the first time, to achieve values greater
than tensions of -600 bar. Distinct partially immiscible binary mixtures (ionic liquid +
conventional solvent) were selected and the liquid-liquid phase diagrams - already
available for normal, positive pressures - were extended by mapping the negative
pressure domain. [1] A. Imre, K. Martinás, L. P. N. Rebelo, J. Non-Equilib. Thermodyn.
23 (1998) 351. [2] P.G. Debenedetti, Metastable Liquids (Princeton Univ. Press,
Princeton, New Jersey, (1996) [3] H.I.M. Veiga, L. P. N. Rebelo, M. Nunes da Ponte, J.
Szydlowski, International Journal of Thermophysics. 22, 4 (2001). [4] Z.P. Visak, L.P.N.
Rebelo and J. Szydlowski, J. Phys. Chem. B, 107 (2003) 9837-9846.
COIL-4:386
Influence of the Cation and Its Alkyl-Side Chain of Pyridinium and Imidazolium-
Based Ionic Liquids on Thermal Properties
Noelia Calvar (1) , noecs@uvigo.es, LSRE-Laboratory of Separation and Reaction
Engineering, Associate Laboratory LSRE/LCM, Department of Chemical Engineering,
Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias s/n, Porto 4200-465,
Portugal, Porto Porto 4200-465, Portugal ; Elena Gómez (2) ; Eugénia A Macedo (1) ;
Ángeles Domínguez (2) . (1) Department of Chemical Engineering, University of Porto,
Porto Porto 4200-465, Portugal (2) Department of Chemical Engineering, University of
Vigo, Vigo Pontevedra 36310, Spain
In recent years, there has been a dramatic increase in research on ionic liquids (ILs) as
potential alternatives to organic solvents in chemical processes. The choice and
evaluation of an IL for a certain application requires knowledge of its thermophysical
properties. In this work, melting (Tm), glass (Tg), cold crystallization (Tcc) and freezing
(Tf) temperatures and heat capacities (Cp) as a function of temperature are presented
for pyridinium-based ILs: 1-ethyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide
(C2MpyNTf2), 1-propyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide (C3MpyNTf2)
and 1-butyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide (C4MpyNTf2). The aim
of this work is to study the influence of the alkyl chain of the cation on the thermal
properties. In addition, the comparison of the results obtained in this work with
previously determined experimental data about ILs containing imidazolium-based ILs
with the same alkyl-side chain and anion (CnMimNTf2 with n = 2,3,4) has allowed us to
analyze the influence of the cation on the thermal analysis. Measurements of phase
transition temperatures were performed using a Mettler-Toledo differential scanning
calorimeter (DSC), model DSC822 e , together with Mettler-Toledo STAR e software
version 9.3. Measurements for thermal analysis were performed by cooling the samples

from 140ºC to -120ºC followed by heating from -120ºC to 140ºC. The rates of cooling
and heating depend on the behavior of the studied IL and the heat capacities of the
compounds were determined using the sapphire method.
COIL-4:387
Influence of Li-Ion Transporting Species on Ionic Conductivity in Litfsi Doped N-
Butyl-N-Methylpyrrolidinium Bis(Trifluoromethanesulfonyl)Imide Ionic Liquid.
Jagath Pitawala (1) , jagath@chalmers.se, Condensed Matter Physics, Gothenburg SE-
41296,, Sweden ; Aleksandar Matic (1) ; Patrik Johansson (1) ; Per Jacobsson (1) . (1)
Department of Applied Physics, Chalmers University of Technology, Gothenburg SE-
41296,, Sweden
We investigate the coordination and the ionic conductivity in LiTFSI doped N-butyl-Nmethylpyrrolidinium
bis(trifluoromethanesulfonyl)imide (PyR14TFSI) ionic liquid (IL) over
a large molar concentration range, 0.005≤x≤0.5, xLiTFSI/(1-x)IL using Raman
spectroscopy and dielectric spectroscopy. We find that the concentration dependence of
the average coordination number (N) can be divided into three regimes. For low
concentrations, x≤0.05, we find a large coordination number, N˜4-6, and a rather weak
interaction between Li-ion and the TFSI anion. At intermediate concentrations, from
0.05 to 0.2, N is around 2 pointing towards Li(TFSI)2 - ionic clusters. At higher
concentrations, x>0.2, N decreases future, indicating the transition to more complex
structures. The change of the coordination number is also reflected in the ionic
conductivity, which shows a crossover in the concentration dependence in the same
concentration range. For low concentrations, the decrease in conductivity is relatively
moderate whereas a more rapid decrease is found for x>0.05. Thus, the stronger
interactions between Li-ion and the TFSI anions decrease the overall mobility of the
ions in the system. Figure 1. Comparison of the coordination number (N) and
the relative change in the room temperature ionic conductivity as a function of LiTFSI
concentration. The dotted lines are only guides to the eye.
COIL-4:388
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Biocidal Activity and Surface Properties of New Quaternary Ammonium Based
Ionic Liquids Against Wood Destroying and Blue Staining Fungi.
Jadwiga Zabielska-Matejuk (1) , J_Matejuk@itd.poznan.pl, ul. Winiarska 1, Poznan
Wielkopolska 60-654, Poland ; Andrzej Skrzypczak (2) ; Anna Stangierska (1) . (1) Wood
Protection Department, Wood Technology Institute, Poznan Wielkopolska 60-654,
Poland (2) Department of Chemical Technology, Poznan University of Technology,
Poznan Wielkopolska 60-965, Poland
In presented paper we examined new class of IL: mono- and bis-quaternary ammonium
based 1-alkylimidazolium and N,N-dimethylalkylammonium derivatives: nitrates,

tetrafluoroborates and with organic anions such as formates, acetates and propionates.
The fungicidal activity of sixteen potential wood preservatives was determined
employing screening agar-plate method, agar-block and soil- block tests. Experiments
were carried out on Scots pine (Pinus sylvestris L.) and on beech (Fagus sylvatica L.)
wood. The the antifungal properties have been correlated with surface activity of tested
IL. The most active compounds against brown and white rot fungi were those with
eight carbon substituents and two quaternary nitrogen atoms. The ED50, ED100 and LD
values for all three fungi were the highest in the case of ionic liquids with the decyl and
dodecyl substituent. The fungicidal value of new bis-quaternary ammonium and
imidazolium nitrates and tetrafluoroborates for Coniophora puteana ranged from 0.7
kg/m 3 to 2.9 kg/m 3 , for Trametes versicolor ranged from 3.9 kg/m 3 to 6.3 kg/m 3 . The
greatest effectiveness of action against soft- rot fungi was demonstrated by monoammonium
tetrafluoroborate and mono-imidazolium nitrate.The toxic values on beech
reached from 9.9 to 11.7 kg/m 3 (1.7 – 1.9 times bigger than of copper-chromium
reference preservative). Toxic value on Scots pine were under 4.0 kg/m 3 . Resistance
of ionic liquids to water leaching is connected with chemical structure and
hydrophobicity. Comparison of ionic liquids adsorption isotherms demonstrated, that the
experimental data on equilibrium sorption on soil better fitted Freundlich adsorption
model than Langmuir adsorption model. Hydrophobic bis-ammonium tetrafluoroborate
was more difficulty sorbed on soil than hydrophilic salts. Acknowledgements This
research project was supported financially by the polish Ministry of Science and Higher
Education Grant No. NN 309 070636
COIL-4:389
Self-Aggregation in Water of Ionic Liquids Containing Short Alkyl Chain
Imidazolium Cation and a Non Steroidal Drug as Anion
Corine Tourne-Peteilh (1) , tourne@enscm.fr, UFR Pharmacie, 15 avenue Charles
Flahault, Montpellier France 34094, France ; Jean-Marie Devoisselle (1) ; Andre Vioux (1) ;
Patrick Judeinstein (2) ; Martin In (3) ; Lydie Viau (1) . (1) Institut Charles Gerhardt Montpellier,
Montpellier 34000, France (2) Departement NMR, Institut de Chimie Moléculaire et des
Matériaux d’Orsay, Orsay 91405, France (3) Laboratoire Charles Coulomb, Montpellier
34095, France
Recently, [CnMIm][Ibuprofenate] ionic liquids (ILs) have been included by sol-gel
processing in mesoporous silica materials called Ionogels and evaluated as drug
delivery system (1). To investigate the key parameters involved in the structure-function
relationship of Ionogels: i.e (i) influence of ILs on material structuration and controlled
release rate, (ii) physico-chemical properties of drug molten salts (focusing on aqueous
solubility), we were interested in the self- aggregation of [CnMIm][Ibuprofenate] series in
aqueous conditions. In this study, we investigated the aggregation in water of
[CnMIm][Ibuprofenate] (n = 4, 6, 8) and compared our results with classical [CnMIm][Cl]
ILs. The CAC was determined by surface tension, conductivity, photon correlation
spectroscopy and by Pulsed Gradient Stimulated Echo (PGSE)-NMR. Main results
indicated that [CnMIm][Ibuprofenate] have significant surface activity and self-

assembled in water. The CACs obtained by different techniques were correlated to the
cation alkyl chain length. Free energies of aggregation, DGm°, decreased significantly
vs. [CnMIm][Cl] due to a cooperative effect inside the aggregates between the opposite
charges and the alkyl chains. Thus, significant CAC decreases were obtained leading to
CAC [C4MIm][Ibuprofenate] = CAC [C10MIm][Cl]. On health care point of view, this could
be a great advantage to use short alkyl chain imidazolium cations (n ≤ 8) that are known
to be less cytotoxic than those of n > 8. Unexpected aggregates morphologies have
been observed depending on the concentration, from micelles to multi-lamellar vesicles
or lamellar phases. (1) L. Viau et al., Chem. Comm., 2010, 46, 28-230.
COIL-4:390
Prediction of Liquid-Liquid Equilibria of (Ionic Liquid + Hydrocarbons) Ternary
Systems by COSMO-RS
Ana R. Ferreira (1) , ana.rute@ua.pt, Campus Universitário de Santiago, Aveiro 3810-
193; Mara G. Freire (1) ; Jorge C. Ribeiro (2) ; Fernando M. Lopes (2) ; João G. Crespo (3) ;
João A. P. Coutinho (1) . (1) Department of Chemistry, University of Aveiro, CICECO,
Aveiro 3810-193, Portugal (2) Refinaria do Porto, Petrogal S.A., Matosinhos 4452-852,
Portugal (3) Department of Chemistry, Universidade Nova de Lisboa, Faculdade de
Ciências, CQFB/REQUIMTE, Caparica 2829-516, Portugal
The extraction of organic compounds and aromatic/alkane separation from hydrocarbon
matrixes plays an important role in refinery processes. Nowadays the separation
processes use conventional organic solvents that are often toxic and harmful to the
environment or present an inadequate performance. The application of ionic liquids
(ILs) with their unique and tunable properties can be an advantageous alternative as
solvents in less complex processes for aromatics and non aromatics extraction from
hydrocarbon streams. Therefore it is essential the understanding of the ternary liquidliquid
equilibrium between ionic liquid and hydrocarbons streams. As the combination
of ionic liquid ions is unlimited, it is important the development of predictive models that
aid the ionic liquid selection with a higher potential to refinery extraction processes.
Aiming this purpose, COSMO-RS capability on describing LLE IL+ hydrocarbons ternary
systems was evaluated. COSMO-RS is a totally predictivemethod based on
unimolecular quantum calculations and it is shown that COSMO-RS provides a
surprisingly good description of the available data. Thus COSMO-RS can be used to aid
the understanding of the influence of the ILs structure on the phase behavior and for ILs
screening for use in extraction processes.
COIL-4:391
Prediction of Liquid-Liquid Equilibria of (Ionic Liquid + Hydrocarbons) Binary
Systems by COSMO-RS
Ana R. Ferreira (1) , ana.rute@ua.pt, Campus Universitário de Santiago, Aveiro 3810-
193, Portugal ; Mara G. Freire (1) ; Jorge C. Ribeiro (2) ; Fernando M. Lopes (2) ; João G.

Crespo (3) ; João A. P. Coutinho (1) . (1) Department of Chemistry, University of Aveiro,
CICECO, Aveiro 3810-193, Portugal (2) Refinaria do Porto, Petrogal S.A., Matosinhos
4452-852, Portugal (3) Department of Chemistry, Universidade Nova de Lisboa,
Faculdade de Ciências, CQFB/REQUIMTE, Caparica 2829-516, Portugal
Ionic liquids are attracting the interest of both academia and refining companies as
potential solvents for the extraction of specific compounds from hydrocarbons' streams.
For such a purpose, the knowledge of the mutual solubilities between ionic liquids and
hydrocarbons is required. Due to the large number of possible combinations of ionic
liquids and hydrocarbons it is necessary the development of predictive models to
forecast a general picture of the liquid-liquid equilibria. The capability of COSMO-RS
(Conductor-like Screening Model for Real Solvents) to predict the LLE of (IL +
hydrocarbon) binary systems is here evaluated. It is shown that COSMO-RS, a
predictive method based on unimolecular quantum calculations, allows a semiquantitative
description of the LLE experimental data for the systems studied. Moreover,
COSMO-RS almost provides a correct qualitative trend of the phase behavior
dependence regarding the ionic liquids and molecular compounds nature.
COIL-4:392
The Study of Independent Solvent Effect for S1

Understanding the Dissolution Mechanism of Nucleobases in 1,3-
Dialkylimidazolium Acetate Ils: In Situ NMR Spectroscopy and Insights from Ab
Initio Calculations
João M. M. Araújo (1) , jmmda@itqb.unl.pt, Av. da República, Oeiras Oeiras 2780-157,
Portugal ; R. Ferreira (1) ; José N. C. Lopes (1) ; Isabel M. Marrucho (1) ; Luís P. N. Rebelo (1) .
(1) Instituto de Tecnologia Química e Biológica, www.itqb.unl.pt, Universidade Nova de
Lisboa, Oeiras 2781-901, Portugal
Neoteric solvents engineering is one of the most promising areas in the evolving field of
“green” sustainable technologies, a category which includes supercritical CO2, aqueous
biphasic systems, and ionic liquids. Room Temperature Ionic Liquids (RTILs) are
revolutionizing the world of solvents due to the unique combination of their many
interesting properties. The tunable nature of the solubility of various compounds -
including molecules of pharmaceutical and biological interest - in RTILs makes
extraction with RTILs attractive for many separation and purification processes.
Exploring new applications requires fundamental understanding of phase behavior. In
the present work, we disclose the solvation mechanism of three selected nucleobases,
namely, uracil, thymine, and adenine, in RTILs of the 1,3-dialkylimidazolium acetate
family. Nucleic acid bases, nitrogenous heterocyclic nucleic acids that form the
structural units of DNA and RNA, are ubiquitous in nature, presenting a paramount
importance as biochemical compounds. Their chemistry influences different synthetic
pathways as well as enzyme systems and dictates the structure and properties of living
cells and organisms. In situ NMR studies of uracil, thymine and adenine dissolved in 1ethyl-3-methyl-imidazolium
acetate ([C2mim][CH3COO]) and 1-butyl-3-methylimidazolium
acetate ([C4mim][CH3COO]) show that hydrogen bonds (HB) command the
dissolution mechanism and that both cation and anion participate in the solvation
process. For that, the 1,3-dialkylimidazolium acetate RTILs were considered to be
bifunctional solvation ionic liquids. The analysis of the solvation sites of the selected
nucleic acid bases in 1,3-dialkylimidazolium acetate RTILs were accomplish by DFT
methods, corroborating the spectroscopic results.
COIL-4:394
Investigating the Effect of Imidazolium Based Ionic Liquids on the Free Radical
Polymerisation of Methyl Methacrylate
Emma K Steeds (1) , pcxes2@nottingham.ac.uk, University Park, Nottingham
Nottinghamshire NG7 2RD, United Kingdom ; Jaouad El Harfi (1)(2) ; Derek J Irvine (1)(2) ;
Peter Licence (1) . (1) School of Chemistry, The University of Nottingham, Nottingham
Nottinghamshire NG7 2RD, United Kingdom (2) Process and Environmental Research
Division, Faculty of Engineering, The University of Nottingham, Nottingham
Nottinghamshire NG7 2RD, United Kingdom
Free radical polymerisation (FRP) in ionic liquids has been shown to increase the rate of
polymerisation and to dramatically increase the molecular weights of the polymers

formed. It has been shown that block co-polymers can be formed in ionic liquids using
FRP, which is not possible in conventional organic solvents without a control agent (e.g.
ATRP or RAFT). To explain these observations a protected radical theory was
proposed. The following work provides further evidence towards the protected radical
theory. The FRP of methyl methacrylate (MMA) in imidazolium based ionic liquid
[C2C1Im][EtOSO3] has been studied. A novel “two step” approach has been developed,
whereby the initiator 2,2'-azobisisobutyronitrile (AIBN) is heated for 24 h at 80 ºC in
[C2C1Im][EtOSO3], prior to MMA addition. Overall increasing the AIBN concentration
decreases the molecular weight of PMMA. The two step method yields higher molecular
weight PMMA, with a general decrease in the polydispersity index (PDi), than in the
general FRP reactions. In conventional organic solvents, e.g. toluene, no radical
species remain and polymerisation is unsuccessful but in this ionic liquid significant
yields of PMMA are obtained, providing strong evidence of radical protection.
http://www.nottingham.ac.uk/ionicliquids/
COIL-4:395
Multidisciplinary Study of Coordination Sphere of Cu(II) in Highly Concentrated
Ionic Liquids Solutions
Cinzia Chiappe (1) , cinziac@farm.unipi.it, Via Risorgimento 35, Pisa Pisa 56126, Italy ;
Ugo Bardi (2) ; Stefano Caporali (2) ; Christian S Pomelli (1) ; Marco Malvaldi (1) . (1) Chimica e
Chimica Industriale, Università di Pisa, Pisa Pisa 56126, Italy (2) Chimica [quot]Ugo
Schiff[quot], Università degli Studi di Firenze, Firenze Firenze 50019, Italy
Given their wide electrochemical windows and good ionic conductivity ILs are a good
electrochemical material. A host of metals and alloys can be deposited in ILs, and their
use offers advantages respect to aqueous baths, such as operating open plating baths
at variable temperature without the release of vapors and a lack of hydrogen
embrittlement processes due to the hydrophobic nature of many of them. The
electrodeposition of metals and alloys from ILs is generally slower than in aqueous
solution since the ionic concentration in these media result lower. Recently has been
demonstrated that ILs solutions with high metals concentration can be achieved by
directly dissolving the salts in ILs which have the same anion. In these highly
concentrated solutions, the interactions between metal and anions can be so strong to
negatively affect the electron transfer, limiting the electroreduction efficiency. Thus
knowing the nature and the size of the metal ions coordination spheres plays a key role
for the application of such systems as real alternative to the traditional plating baths. We
report the results of an in depth investigation on the coordination sphere of Cu(II) ions in
some different ILs by means of angle resolved X-ray photoelectron spectroscopy (AR-
XPS), cyclic voltammetry, ESI-MS and DFT calculations. The ILs considered are
chosen to have anions with different coordinating capacities. Since the XPS surface
sensitivity can be varied by the variation of the detection angle of the photoemitted
electrons, a careful evaluation of the intensity of the electrons emitted by copper
provides an estimation of the radii of its coordination sphere in static conditions for the
different ILs. The same parameters were achieved, in dynamic condition, by means of

cyclic voltammetry. Finally, both the two sets of data were compared and discussed with
the results of DFT calculations.
COIL-4:396
Locality and Fluctuations: Trends in Imidazolium-based Ionic Liquids and Beyond
Katharina Wendler (1) , scholze@mpip-mainz.mpg.de, Ackermannweg 10, Mainz,
Germany ; Stefan Zahn (2) ; Florian Dommert (3) ; Robert Berger (4) ; Christian Holm (3) ;
Barbara Kirchner (2) ; Luigi Delle Site (1) . (1) Max Planck Institute for Polymer Research,
Germany (2) University of Leipzig, Germany (3) University of Stuttgart, Germany (4) TU
Darmstadt, Germany
Accurate prediction of ionic liquids' properties is impeded by the lack of fundamental
insight into the underlying physics. Thus, there is a vivid interest in elucidating the
governing interactions, Coulomb and van der Waals forces as well as hydrogen bonding
and their subtle interplay. The results can be employed in the development of classical
models or in the interpretation of experimental data. In previous work on MMIM Cl, the
electric dipole moment distribution was found to be rather broad, indicating a strong
degree of fluctuation, but the electrostatic properties were rather local. Further studies
confirmed the strong electrostatic screening. It remained an open question whether this
behavior might represent a “true ionic liquid” signature. Three different imidazoliumbased
ionic liquids, 1,3-dimethylimidazolium chloride, 1-ethyl-3-methylimidazolium
thiocyanate, and 1-ethyl-3-methylimidazolium dicyanamide, were investigated by Car-
Parrinello simulations. Indeed, common behavior as a broad electric dipole moment
distribution of the ions and a related very high degree of locality was found to
characterize all these systems. The molecular electric properties seemed to be local on
the scale of the size of an 1-ethyl-3-methylimidazolium cation. Going beyond
imidazolium-based systems, the same features were observed for the protic ionic liquid
monomethyl ammonium nitrate. These results gave strong support to the hypothesis of
rattling ions in long-living ion cages proposed in the last years. Furthermore, the high
locality and strong screening might be the reason of the success of classical force fields
with reduced ion charges.
COIL-4:397
RTIL Based Liquid Membranes for Ion Separations
E. Esipova (1) , noumy1986@rambler.ru, Moscow, Russian Federation ; A. Vendilo (1) ; K.
Popov (2) ; D. Petukhov (3) ; A. Eliseev (3) . (1) Institute of Reagents and High Purity
Substances (IREA), Moscov, Russian Federation (2) Department of Physical and
Colloid Chemistry, Moscow State University of Food Production, Moscow, Russian
Federation (3) Department of Chemistry, M.V.Lomonosov State University, Moscow,
Russian Federation

A Cs + transfer from its nitrate salt aqueous solution placed in anode chamber to a
cathode chamber filled with water under voltage gradient through 1-butyl-3methylimidazolium
bis[trifluoromethyl)sulphonyl]imide ([BMIM][N(Tf)2]) layer with either
18-crown-6 (18C6) or dibenzo-18-crown-6 (DB18C6) is studied. In absence of crown
ether c.a. 50 % of Cs + has been accumulated in a RTIL phase within 4 hours. The
process stops when 50% of a cation still remains in the initial solution. At the same time
no any increase of cesium concentration at anode is observed. This indicates that the
formation of either neutral or anionic species of cesium with RTIL's anions, e.g.
[CsN(Tf)2] o , [Cs{N(Tf)2}2] – . The neutral or negatively charged species do not strip into
the anode compartment and partly stay in the RTIL's phase in equilibrium with anode
compartment when the voltage gradient becomes compensated by the concentration
gradient. When 18C6 is added to the ionic liquid phase, then 90% of cesium placed
initially in the anode chamber, move both to RTIL's phase (44 %) and to cathode
compartment (46 %) within the same period of time. This is also consistent with the
stability constants and NMR based chemical speciation model which assumes the
formation of cationic species in presence of 18C6 excess: [Cs(18C6)2] + . An increase of
the voltage gradient or a change of 18C6 for DB18C6 enhances the transportation
process. A separation of a model equimolar mixture of Cu 2+ and Cs + is also studied. It is
demonstrated that Cs + is selectively transmitted to a cathode compartment and a better
separation is achieved when EDTA is added to the anode chamber. The supported
membranes based on [BMIM][N(Tf)2], crown ether and a porous Al2O3 are also studied.
COIL-4:398
Control of Water Content in Hydrophobic Ionic Liquid by Adding Hydrated
Zwitterions
Yoritsugu Ito (1) , nerazzurri-centrale.4@jcom.home.ne.jp, Naka-cho, Koganei Tokyo,
Japan ; Yuki Kohno (1) ; Hiroyuki Ohno (1) . (1) Department of Biotechnology, Tokyo
University of Agriculture and Technology, Naka-cho, Koganei Tokyo 184-8588, Japan
Ionic liquids (ILs) containing hydrophobic ions show liquid/liquid biphasic separation
after mixing with water. These hydrophobic IL/water biphasic systems have been
exploited as novel systems for extraction, separation, and condensation of target
compounds. The mixtures would provide many interesting applications when the water
content of the IL phase was controlled accurately. We focused on zwitterions (ZIs), in
which both cation and anion were covalently tethered, as an additive to change the
hydration state of the hydrophobic ILs without further phase exchange, since ZIs
maintain their ion pairs. In this study, we investigated the effect of added ZI structure on
the water content of the IL phase. The water content of 1-butyl-3-methylimidazolium
bis(trifluoromethanesulfonyl)imide ([bmim][Tf2N]) phase was analyzed after mixing it
with an equal amount of several ZIs in the presence of excess amount of water. The
water content of the IL phase strongly depended on the ZI structure. When three
different ZIs were added to the IL, the water content of the IL phase increased to 0.9,
1.0, and 1.8 wt%, while that of water-saturated IL phase without ZI was 0.4 wt%. The
partition of the ZIs between aqueous and IL phase was analyzed with 1 H NMR.

Relatively hydrophobic ZI, having long alkyl chain on the imidazolium cation, was found
partially in the IL phase. However, less hydrophobic ZIs were mainly dissolved in the
aqueous phase. On the other hand, when more hydrophobic ZIs were added to the
mixture, the water content of the IL phase increased dramatically. These results clearly
indictated that the increased water content in the IL phase was comprehended to be the
result of the increased partition of ZIs into the IL phase.
COIL-4:399
IV-SFG Studies on Ionic Liquid / Alkane Interfaces
Yasunari Sakai (1) , sakai@mat.chem.nagoya-u.ac.jp, Furo-cho, Chikusa-ku, Nagoya
Aichi 464-8602, Japan ; Takashi Iwahashi (1) ; Yoshimi Ogawa (1) ; Tatsuya Ishiyama (2) ;
Akihiro Morita (2) ; Doseok Kim (3) ; Yukio Ouchi (1) . (1) Department of Chemistry, Nagoya
University, Naogya Aichi-ken 464-8602, Japan (2) Department of Chemistry, Tohoku
University, Sendai Miyagi 980-8578, Japan (3) Department of Physics, Sogang
University, Seoul 121-742, Republic of Korea
The interfacial structures of ionic liquid (IL) / molecular liquid are important for liquidliquid
extraction, two phase reaction and so on. For fundamental understanding of
theses issues, we have investigated local structures of IL / alkane interfaces, using
infrared-visible sum frequency generation spectroscopy (IV-SFG). IV-SFG is a second
order nonlinear spectroscopic technique, and thus provides interface sensitive
vibrational spectra. In our study, two ILs, 1-butyl-3-methylimidazolium
hexafuluorophosphate ([bmim]PF6) or 1-butyl-3-methylimidazolium
bis(trifluoromethylsulfonyl)amide ([bmim][TFSA]), and two alkanes, n-hexane-d14 or noctane-d18,
were used to construct IL / alkane interfaces. Our IV-SFG study revealed
interesting features on the alignment of SO2 group of the [TFSA] anion. The relative
sign of SF signal of the SO2 group at the air / [bmim][TFSA] interface is opposite to that
at the [bmim][TFSA] / alkane interface. This result indicates that the SO2 group points
toward the opposite directions at air / [bmim][TFSA] and [bmim][TFSA] / alkane
interfaces. It is well known that SO2 group points to the [bmim][TFSA] phase at the air /
[bmim][TFSA] interface, indicating that the SO2 group points to the alkane phase at the
alkane/ [bmim][TFSA] interface. The spectra from the butyl chain of [bmim] cation
revealed that the orientation angle of CH3 of butyl chain from the surface normal is
larger at IL / alkane interface than at air / IL surface. The angle at IL / alkane interface
also showed the IL dependence. The CH3 of the butyl chain at [bmim][TFSA] / alkane
interface orients more horizontally than the one at the [bmim]PF6/ alkane interface. We
have found that the structure of IL / alkane interface is much different form that of the air
/ IL surface, which may reflect upon the characteristics of extractions and reactions.
COIL-4:400
Stability Constants of Cs + and Gd 3+ Complexes with Crown Ethers in Rtils

K. Popov (1) , ki-popov@mtu-net.ru, Moscow, Russian Federation ; A. Vendilo (2) ; E.
Esipova (2) ; I. Filimonov (2) ; V. Chistov (2) ; D. Djigailo (3) ; I. Pletnev (3) ; M. Lajunen (4) ; H.
Rönkkömäki (5) . (1) Department of Physical and Colloid Chemistry, Moscow State
University of Food Production, Moscow, Russian Federation (2) Institute of Reagents
and High Purity Substances (IREA), Moscow 107076, Russian Federation (3)
Department of Chemistry, M.V.Lomonosov State University, Moscow, Russian
Federation (4) Department of Chemistry, University of Oulu, Finland (5) Finnish Institute
of Occupational Health, Oulu, Finland
Complexes of Cs + and Gd 3+ with 18-crown-6 (18C6), dibenzo-18-crown-6 (DB18C6),
dibenzo-21-crown-7 (DB21C7) and dibenzo-24-crown-8 (DB24C8) are studied with
133 1 o
Cs and H technique at 25 to 50 C in six hydrophobic RTILs:
trioctylmethylammonium salicylate ([TOMA][Sal]), tetrahexylammonium
dihexylsulfosuccinate ([THA][DHSS]), 1-butyl-3-methylimidazolium hexafluorophosphate
([BMIM][PF6]), 1-butyl-3-methylimidazolium bis[trifluoromethyl)sulphonyl]imide
([BMIM][N(Tf)2]), 1-hexyl-3-methylimidazolium bis[trifluoromethyl)sulphonyl]imide
([HMIM][N(Tf)2]), and 1-(2-ethylhexyl)-3-methylimidazolium
bis[trifluoromethyl)sulphonyl]imide ([EtHMIM][N(Tf)2]), and in three hydrophilic RTILs Nbutyl-4-methyl-pyridinium
tetrafluoroborate ([BMPy][BF4]), 1-butyl-3-methylimidazolium
tetrafluoroborate ([BMIM][BF4]) and 1-butyl-3-methylimidazolium dicyanamide
([BMIM][N(CN)2]). The stability constants (logK) as well as ∆H and ∆S values are
measured. Cesium is found to form complexes CsL and CsL2 with 18C6 and DB18C6
in [BMIM][N(Tf)2], [HMIM][N(Tf)2] and [EtHMIM][N(Tf)2] while in [TOMA][Sal],
[BMIM][PF6], and [THA][DHSS] only CsL species are formed. In [BMIM][N(Tf)2] with
higher denticity crowns DB21C7 and DB24C8 the formation of only CsL complexes was
observed. The stability constants K1 for Cesium complexes in RTILs are generally
much higher then those reported for water. The only one exception registered is a case
of task-specific RTIL [THA][DHSS], in which an anion of ionic liquid competes for Cs +
with 18-crown-6 and therefore diminishes the logK1 of [Cs(18-crown-6] + complex. At the
same time the values for RTILs are much lower then those found for 1,2-dichloroethane.
This conclusion is of importance for extraction of cations from aqueous solutions. It is
noted, that the logK1 values for RTILs fall inside, but not outside the range of those for
molecular solvents, with location between acetonitrile and water. An examination of
logK1 values reveals that the polarity of RTILs fits well into the existing empirical solvent
polarity scale for molecular solvents characterizing them not as “superpolar”, but as
quite normal polar solvents. An increase of temperature decreases the stability
constants of CsL for [HMIM][N(Tf)2], [BMIM][N(Tf)2] and [BMIM][PF6], but increases
them for [TOMA][Sal] and [THA][DHSS]. The trends found for cesium complexes agree
well with the data obtained for [Gd(DB24C8)] 3+ in [BMIM][N(CN)2].
COIL-4:401
New Protic Ionic Liquids of Various Brønsted Acids Based on an Organic Super-
Strong Base and their Physicochemical Properties

Muhammed Shah Miran (1)(2) , d10sa593@ynu.ac.jp, 79-5 Tokiwadai, Hodogaya-ku,
Yokohama Kanagawa 240-8501, Japan ; Hiroshi Kinoshita (1) ; Tomohiro Yasuda (1) ; Md.
Abu Bin Hasan Susan (1)(2) ; Masayoshi Watanabe (1) . (1) Department of Chemistry and
Biotechnology, Yokohama National University, Yokohama Kanagawa 240-8501, Japan
(2) Department of Chemistry, University of Dhaka, Yokohama Kanagawa 240-8501,
Japan
Unique physicochemical properties, such as, high ionic conductivity, low-vapor
pressure, electrochemical stability and non-flammability in combination with proton
conduction under anhydrous conditions have rendered protic ionic liquids (PILs) as one
of the most fascinating electrolytes for electrochemical devices. The burgeoning
demand to have a clear correlation of physicochemical properties with suitable
parameters prompted us to prepare a novel series of PILs and characterize them to
make clear correlations between the properties and the structures. In this study, we
prepared PILs by neutralization of an amidine based super base, 1,8diazabicyclo[5,4,0]undec-7-ene
([DBU]) with different Brønsted acids with wide variation
in the ∆pKa of the constituent amine and the acids. The PILs have been characterized
by measuring melting, crystallization, glass and decomposition temperatures, density,
conductivities, viscosities, vibrational stretching frequency and 1 H-chemical shifts of
N-H bond. The PILs based on DBU have melting temperature less than 100 o C, of
which six were liquid even at ambient temperature. Excellent thermal stability could be
marked for PILs with ∆pKa ≥ 16 which are reminiscent to a prototypal aprotic ionic
liquid (AIL) from thermogravimetric analyses. The analyses of temperature dependence
of NMR chemical shift and FT-IR results reveal the presence of a low-barrier hydrogen
bond (LBHB) between the protonated amine and the anion through N-H bond in varying
extent depending on the ∆pKa in the PILs. The LBHB has been found to play decisive
role in determining the physicochemical properties of the PILs. The ionicity of the PILs
decreases with increasing temperature, with influence being more prominent for low
∆pKa and strong LBHB compared to those with high ∆pKa and weak H-bonds. The
strength of the LBHB may be controlled by varying the structure of the constituent
amine and the acid, in other words the ∆pKa to tune protic ionic liquids for task-specific
applications.
COIL-4:402
Highly Conductive Ionic Liquid Composed of Sulfonium Cations and
Fluorohydrogenate Anions
Ryosuke Taniki (1) , goodryosan@t04bytanuki.mbox.media.kyoto-u.ac.jp; Kazuhiko
Matsumoto (1) ; Rika Hagiwara (1) . (1) Graduate School of Energy Science, Kyoto
university, Sakyo-ku, Kyoto 606-8501, Japan
We report the synthesis and characterization of ionic liquids composed of
fluorohydrogenate anion ((FH)nF - ) and tertiary sulfonium cations: trimethylsulfonium
(S111 + ), dimethyethyllsulfonium (S112 + ), diethylmethylsulfonium (S122 + ) and
triethylsulfonium (S222 + ). Halide salts, S111Br, S112I, S122I and S222I, are purchased or

synthesized by the reactions of dimethylsulfide or diethylsulfide with iodomethane or
iodoethane. Four ionic liquids (S111(FH)1.9F, S112(FH)2.0F, S122(FH)2.0F and S222(FH)2.0F)
are obtained as nonvolatile room temperature ionic liquids by evacuating the products of
the metathesis reaction of S111Br, S112I, S122I or S222I with anhydrous hydrogen fluoride.
Thermogravimetry shows that decomposition temperatures of S111(FH)1.9F, S112(FH)2.0F,
S122(FH)2.0F and S222(FH)2.0F are around 450, 440, 440 and 420 K, respectively. The
molecular weight (MW), melting temperature (Tm), density (r), viscosity (h), ionic
conductivity (s) and electrochemical window (EW) of four ionic liquids are shown in
Table 1. With decrease in the length of side chains, the ionic conductivity is increased
and decomposition temperature is elevated whereas melting temperature and
electrochemical stability are lowered.
MW Tm / K ρ / g cm -3 η / cP σ / mS cm -1 EW / V
S111(FH)1.9F 134 242 1.18 7.8 131 4.1
S112(FH)2.0F 150 227 1.14 8.2 111 4.2
S122(FH)2.0F 164 - 1.11 8.9 91 4.4
S222(FH)2.0F 178 217 1.09 8.3 83 4.9
COIL-4:403
Soft Colloidal Glasses with Structural Color Consisting of Polymer-Grafted Silica
Nanoparticles and Ionic Liquids.
Toshimichi Fukai (1) , b0742105@ynu.ac.jp, 79-5 Tokiwadai, Hodogaya-ku, Yokohama
Kanagawa 240-8501, Japan ; Tomomi Nagatsuka (1) ; Tomohiro Yasuda (1) ; Kazuhide
Ueno (1) ; Masayoshi Watanabe (1) . (1) Department of Chemistry & Biotechnology,
Yokohama National University, Yokohama Kanagawa 240-8501, Japan
Stabilization of colloidal dispersion in aqueous and polar organic media has been
attributed to the electrostatic repulsion between particles that is originated from the
overlap of electric double layer formed on the surface of colloidal particles. In case of
ionic liquids (ILs),however, high ionic strength of ILs makes the electric double layer
thinner and attenuates the electrostatic repulsion between colloidal particles because of
charge screening effect. Thus, bare colloidal particles usually aggregate in ILs. In order
to improve colloidal stability through steric repulsion and excluded volume effect,
compatible polymer chains with ILs are grafted onto the surface of silica particles. In this
study, poly(methyl methacrylate) (PMMA) was grafted on silica nanoparticles by
surface-initiated atom transfer radical polymerization (ATRP). The PMMA-grafted silica
nanoparticles were dispersed in 1-alkyl-3-methylimidazolium ([Cnmim])-based ILs with
different anionic structures. In dilution system, the PMMA-grafted silica nanoparticles
were stably dispersed in [Cnmim][NTf2] and [C4mim]PF6. However, the hydrodynamic
radius in [C4mim]PF6 was smaller than that of in [C4mim][NTf2]. Furthermore, the
PMMA-grafted silica nanoparticles were not stabilized in [C4mim]BF4. The compatibility
between PMMA and ILs varied depending on anionic structures of ILs. When the

particle concentrations were increased in [Cnmim][NTf2], colloidal dispersions changed
from sol to colloidal glass that exhibited homogeneous, non-brilliant, angle-independent
structural color. However in mixtures of [C4mim][NTf2] and [C4mim]PF6, the structural
color disappeared with increasing molar fraction of [C4mim]PF6. It was revealed that the
appearance of structural color requires highly swollen PMMA chain due to high
compatibility between the grafted polymer chains and ILs.
COIL-4:404
Novel Organic Ionic Plastic Crystals with Cyanate Anions
Judith Janikowski (1) , judith.janikowski@monash.edu, Building 19, Melbourne Victoria
3800, Australia ; Douglas MacFarlane (2) ; Jenny Pringle (1)(2) . (1) Department of Materials
Engineering, Monash University, Melbourne Victoria 3800, Australia (2) School of
Chemistry, Monash University, Melbourne Victoria 3800, Australia
In the field of ionic liquids and organic ionic plastic crystals the physical properties are
directly linked to the structural characteristics. This gives the possibility of property
design according to desired application through simple structural change. To further
understand this relationship a novel cyanate anion was combined with established
cations, such as pyrrolidinium and imidazolium derivatives, to give a new family of
organic ionic plastic crystals. Synthesis of the desired products can be achieved through
the use of silver salts, as shown in Scheme 1, as well as via exchange resins.
Scheme 1: Synthesis of an organic ionic plastic crystal via the corresponding silver salt.
Here we report the synthesis and physical properties, including conductivity and thermal
behaviour, of a range of new pyrrolidinium and imidazolium salts utilizing the cyanate
anion.
COIL-4:405
Hydrophobic and Polar Ionic Liquids
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Yukinobu Fukaya (1) , yuki-f@cc.tuat.ac.jp, 2-24-16, Naka-Cho, Koganei Tokyo 184-
8588, Japan ; Hiromitsu Hattori (1) ; Hiroyuki Ohno (1) . (1) Department of Biotechnology,
Tokyo University of Agriculture & Technology, Tokyo 184-8588, Japan
The reason for a great deal interest in ionic liquids should be due to their utilities in a
wide variety of applications and methodologies. Importantly, exploiting the flexibility of
ion designing afford an opportunity to tune various properties including polarity, solvent
miscibility, and so forth. Moreover, dual functional ionic liquids can be obtained by
design of both cation and anion to play specific roles. To date, we have been focusing
on the polarity, especially hydrogen bonding characteristics, of ionic liquids, and
prepared a series of polar ionic liquids with sufficient polarity to dissolve various
materials including scarcely soluble polymers. Ionic liquids with both highly polarity and
lower solubility in water should provide various advantages. Here we describe the first

example of hydrophobic and polar ionic liquids, and discuss about the effect of
component ions on the physico-chemical properties and the solubility to water of the
resulting ionic liquids. Throughout our studies of cationic structure on physcico-chemcial
properties, we found that tetraalkylphosphonium methylphosphonate ([Pn,n,n,m][1]) were
obtained as polar ionic liquids with strong hydrogen bonding characteristics, especially
hydrogen bonding basicity. For example, the Kamlet-Taft b value for these
phosphonium based ionic liquids were over 1.3 which are much higher than
alkylimidazolium salts (β value = ca. 1.0). Then we examined the miscibility of these
phosphonium based ionic liquids with water. Among these ionic liquids, we found that
[Pn,n,n,m][1] with relatively long alkyl chain length showed phase separation after mixing
with water. More interestingly, we found that tri-n-hexyl-n-octylphosphonium
methylphosphonate shows unique lower critical solution temperature behavior after
mixing with water. We estimated the polarity of ionic liquid rich phase, and found that
these ionic liquids shows relatively higher hydrogen bonding basicity than that of
alkylimidazolium chloride based polar ionic liquids after mixing with water.
COIL-4:406
Passivation of Aluminium AA5083 Alloy Using Ionic Liquids
Peipei Huang (1) , phuan@deakin.edu.au, 221, Burwood Highway, Burwood Victoria
3125, Australia ; Patrick Howlett (1) ; Douglas MacFarlane (2) ; Maria Forsyth (1) . (1) Institute
for Technology Research and Innovation (ITRI), Deakin University, Burwood Victoria
3125, Australia (2) School of Chemistry, Monash University, Clayton Victoria 3800,
Australia
Aluminium, as the current collector in lithium batteries, has shown reduced corrosion
susceptibility in room temperature molten salts. Furthermore, ionic liquids have been
previously shown to be effective in corrosion protection of magnesium, by forming a
protective surface film 1 . This research work explores the potential of particular ionic
liquids in corrosion mitigation of aluminium alloys. The interaction between these ionic
liquids and aluminium AA5083 alloy was characterised by the following techniques:
Optical Profilometry, Secondary Electron Microscopy (SEM), Potentiodynamic
Polarisation (PP), Cyclic Voltammetry (CV) and Scanning Electrochemical Microscope
(SECM). The role of acid content and potential bias, both anodic and cathodic, were
also investigated, in order to optimise the film formation conditions thus develop a
robust surface film. 1. Howlett, P.C., Efthimiadis, J., Hale, P., Van Riessen, G.A.,
MacFarlane, D.R., Forsyth, M., Characterization of the magnesium alloy AZ31 surface
in the ionic liquid trihexyl(tetradecyl)phosphonium bis(trifluoromethanesulfonyl)amide,
Journal of the Electrochemical Society 157 (2010) no.11, C392-C398.
COIL-4:407
Low Voltage Anodising of AZ31 Magnesium Alloy Using
Trihexyl(Tetradecyl)Phosponium Bis(2,4,4-Trimethylpentyl)Phosphinate
([P6,6,6,14][( I c8)2PO2]) IL

Julie-Anne Latham (1) , julie-anne.hill@monash.edu, Wellington Road, Clayton Victoria
3800, Australia ; Patrick Howlett (2) ; Maria Forsyth (2) . (1) Materials Engineering, Monash
University, Clayton Victoria 3800, Australia (2) ITRI, Deakin University, Burwood
Victoria 3125, Australia
Ionic liquids (ILs) have recently been investigated as a green alternative to chromate
conversion coatings for the corrosion protection of magnesium (Mg) alloys. Previous
research has found that ILs are capable of forming a corrosion protective film
comparable to the chromate conversion coating on Mg alloy using
trihexyl(tetradecyl)phosphonium bis(trifluoromethanesulfonyl)amide ([P6,6,6,14][NTf2]) IL.
Due to the success of phosphorus based inhibitors on stifling corrosion on Mg alloys,
trihexyl(tetradecyl)phosphonium bis(2,4,4-trimethylpentyl)phosphinate
([P6,6,6,14][( i C8)2PO2]) is being investigated as a good candidate for film formation on
AZ31 Mg alloy. Furthermore, [P6,6,6,14][( i C8)2PO2] appears to be a promising candidate
for low-voltage anodising of AZ31. This study focuses on the effect of different treatment
conditions, including current density, temperature, and final voltage, on the corrosion
properties of the films formed on AZ31.
COIL-4:408
Dependence of the Thermophysical Properties of a CN-Series of Ionic Liquids
Mara G. Freire (1) , maragfreire@ua.pt, Av. República, Ap. 127, Oerias n.a. 2780-901,
Portugal ; Catarina M. S. S. Neves (2) ; Mohammad Tariq (1) ; João A. P. Coutinho (2) ; Isabel
M. Marrucho (1) ; José N. Canongia Lopes (3) ; Luís P. N. Rebelo (1) . (1) ITQB2, New
University of Lisbon, Oeiras 2780-901, Portugal (2) Chemistry Department, CICECO,
University of Aveiro, Aveiro 3810-193, Portugal (3) Centro de Química Estrutural,
Instituto Superior Técnico, Lisboa 1049-001, Portugal
Most ionic liquids present remarkable physicochemical properties, a fact that has led to
a burgeoning area of research concerning their characterization. An important feature of
ionic liquids is based on the possibility of tuning their physical/chemical properties by
varying the nature of the cation and/or the anion, and at least, theoretically, it should
always be possible to tailor a given ionic liquid for a specific application. As a result, an
adequate database regarding their physical properties is still far from being
accomplished. The aim of this work is to explore the dependence of several
thermophysical properties — density, viscosity, and refractive index — of ionic liquids
containing anions substituted with the cyano group (–CN). The selected ionic liquids
include the 1-ethyl-3-methylimidazolium and 1-butyl-3-methylimidazolum cations
combined with the [SCN] - , [N(CN)2] - , [C(CN)3] - and [B(CN)4] - anions. Density, viscosity,
and refractive index measurements have been carried out at atmospheric pressure in a
broad temperature range. Results along the homologous series will be presented taking
into account the effect of the –CN group on the thermophysical properties of ionic
liquids. Several model correlations and predictive methods will be applied to the
description of the experimental data, and the results discussed.

COIL-4:409
Non-Classical Diffusion in Ionic Liquids
Alasdair W. Taylor (1) , Alasdair.Taylor@nottingham.ac.uk, University Park, Nottingham
Nottinghamshire NG7 2RD, United Kingdom ; Peter Licence (1) ; Andrew P. Abbott (2) . (1)
School of Chemistry, University of Nottingham, Nottingham NG7 2RD, United Kingdom
(2) Department of Chemistry, University of Leicester, Leicester LE1 7RH, United
Kingdom
In this study the diffusion coefficient of a cationic ferrocenyl-derivative, 1ferrocenylmethyl-3-methylimidazolium
bis(trifluoromethanesulfonyl)imide,
[FcC1C1Im][Tf2N], has been characterised in a range of 1-alkyl-3-methylimidazolium
ionic liquids of the general form [CnC1Im] + [X] - . The diffusion coefficients for
[FcC1C1Im][Tf2N] in five [CnC1Im][X] ionic liquids were determined as a function of
temperature and the data shown to disobey the Stokes-Einstein equation. This
observation is consistent with the fact that ionic liquids are glass formers, systems in
which non-Stokesian behaviour is well documented. Measured diffusion coefficient data
was used to determine the correlation length, ξ. ξ was found to correlate with the
average size of holes, or voids, rH, within the ionic liquid, see Figure. This interpretation
suggests that a model by which a migrating species can jump between voids or holes
within the liquid is highly appropriate and is consistent with the observed behaviour
measured across a range of temperatures. 1. Taylor et al., PCCP, paper
accepted http://www.nottingham.ac.uk/ionicliquids/
COIL-4:410
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Ligand Effect on Catalytic Activity of Ruthenium Nanoparticles in Imidazolium
Ionic Liquids
Catherine C Santini (1) , santini@cpe.fr, 43 Bd du 11 Novembre 1918, Villeurbanne
France 69616, France ; Gorka Salas (1) ; Paul S Campbell (1) . (1) UMR 5265 C2P2,
CNRS, France
The use of metal nanoparticles (NPs) as catalysts is a topic of growing interest thanks
to its strategic location at the frontier between homogeneous and heterogeneous
catalysis Controlling the size and shape of NPs is of capital importance in order to
control their reactivity. 1-2 An effective way is the synthesis and stabilization of NPs in
organic solvents by reduction of organometallic complexes i.e. (h 4 -1,5cyclooctadiene)(h
6 -1,3,5-cyclooctatriene)ruthenium(0), [Ru(COD)(COT)], under H2 in
the presence of a ligand, in order to avoid agglomeration and metal precipitation. This
method has been extensively used for the synthesis of ruthenium nanoparticles (Ru
NPs) in ionic liquids (ILs) an emerging and environmentally-friendly alternative for NP
synthesis. 2 ILs play a double role, acting as both solvent and stabilizer. 3 In this
communication, we reported that it is possible to combine the properties of ILs to

confine Ru NPs in the nonpolar domains (“nanoreactors”) with the presence of a weak
ligand (L = amine or phosphine) stabilizing particles of a very small size without
impeding their catalytic activity. 4 In each case, Ru@L NPs have been characterized in
situ (TEM, NMR) displaying very small mean diameters (1–2 nm) with narrow size
distribution.Their catalytic activity in the hydrogenation of different unsaturated
compounds (cyclohexadiene, styrene, limonene) has been investigated. Interestingly, it
is found that the addition of such ligands not only enhances RuNP stability, but may
also promote their activity, despite occupying surface sites.[figure 1] 1)
Nanoparticles and Catalysis; Astruc, D., Ed.; Wiley-VCH, Weinheim, 2008 2) J J.
Dupont et al. Chem. Soc. Rev. 2010, 39, (5), 1780-1804. 3 C.C. Santini, et. al J. Mater.
Chem. 2009, 19, 3624-3631 and. 2007, 17, 3290-3292. b)P.S. Campbell et al. , PCCP,
2010, 12, 4217-4223 4) G. Gorka, et.al. Dalton Trans., 2011, DOI:
10.1039/C0DT00596G.
COIL-4:411
Vapor Pressures and Activity Coefficients of N-Alcohols in Binary Mixtures with
1-Butyl-4-Methylpyridinium Tetrafluoroborate
Ismail Kul (1) , ikul@widener.edu, One University Place, Chester PA 19013, United
States ; Javid Safarov (2)(3) ; Waleed A El-Awady (3)(4) ; Astan Shahverdiyev (3) ; Egon
Hassel (2) . (1) Department of Chemistry & Biochemistry, , Widener University, Chester
PA 19013, United States (2) Institute of Technical Thermodynamics, University of
Rostock, Rostock D-18059, Germany (3) Department of Heat and Refrigeration
Techniques, Azerbaijan Technical University, Rostock D-18059, Germany (4)
Mechanical Power Engineering Department, Mansoura Univeristy, Baku AZ1073,
Azerbaijan
Ionic liquids (ILs) are salts that are liquids and have a very low vapor pressures at
ambient temperatures. They are excellent solvents for a broad range of polar organic
compounds and they show partial miscibility with aromatic hydrocarbons. By varying the
length and branching of the alkane chains of the cationic core and the anionic
precursor, the solvent properties of ILs can be tailored to meet the requirements of
specific applications to create an almost infinite set of "designer solvents". In this
context thermodynamic properties of liquid mixtures containing ILs are of large interest,
in particular a systematic study of mixture properties such as VLE data and activity
coefficients are required. In continuation of our recent work, vapor pressure
measurements of methanol or ethanol in the ionic liquid 1-Butyl-4-methylpyridinium
tetrafluoroborate [B4mpy][BF4] at T=(278.15 to 323.15) K have been performed using a
static method. From the vapor pressure data activity coefficients at different
temperatures have been obtained. The experimental vapor pressure results of
investigated solutions were fit to the Antoine equation. The activity of the solvent and
osmotic coefficients were calculated from the experimental vapor pressure values.
Binary mixtures of ILs with non-electrolyte components belong to the class of electrolyte
solutions covering the whole range of composition including the pure liquid electrolyte.
Since there exists no reliable theoretical models for the Gibbs energy of mixing of this

kind of mixtures we have tried to describe the results of activity coefficients using purely
empirical expressions well known in thermodynamics of non-electrolyte mixtures. After
the analysis of various methods for the fitting of measured values, it turned out that the
NRTL equation gives the best empirical description of the activity coefficients and it was
used to determine activity coefficients from experimental data of partial pressures
including the vapor pressure of the pure solutes.
COIL-4:412
Lipid-Inspired Ionic Liquids from Cationic Lipids (Transfection)
Arsalan Mirjafari (1) , mirjafari@usouthal.edu, 307 N University Blvd., Mobile Alabama
36688, United States ; James H Davis, Jr. (1)(2) ; Kevin N West (2) . (1) Department of
Chemistry, University of South Alabama, Mobile Alabama 36608, United States (2)
Department of Chemical and Biomolecular Engineering, University of South Alabama,
Mobile Alabama 36608, United States
A number of methods have been developed to facilitate the delivery of functional DNA
into the eukaryotic cells for the study of gene regulation and gene expression. One of
the most important of these is cationic liposome-mediated transfection (lipofection). N-
[1-(2,3-dioleyloxy)propyl)-N,N,N-trimethylammonium chloride (DOTMA), N-[1-(2,3dioleoyloxy)propyl)-N,N,N-trimethylammonium
chloride (DOTAP), and N-[1-(2,3diolyloxy)propyl)-N,N,N-trimethylammonium
chloride (sat-DOTAP), dimethyldioctadecyl
ammonium bromide (DDAB) and, 1,2-dioleoyl-sn-glycero-3 ethylphosphocholine
chloride (EPC) have been proven to be the highly efficient materials for the delivery of
DNA, RNA, oligonucleotides, ribonucleoproteins, proteins and also other therapeutic
payloads into cells. Significantly, the cations of each of these salts shares important
structural attributes with a family of low-melting, highly lipophilic 'lipid-inspired' ILs we
recently reported. In continuation of that previous work, we have now developed a
complimentary family of lipid-based ILs using gene transfection liposomes derived from
DOTMA and related species. As with our earlier lipid-like ILs, members of this new IL
family all have relatively low melting points (< 80 o C), with one of particular note having
a Tm of -44 o C.
COIL-4:413
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Hydrogen Bond Donating and Accepting Ability of Ionic Liquids Measured by
Means of UV/Vis, 1 H-NMR, And IR Spectroscopy
Ralf Lungwitz (1) , ralf.lungwitz@s2000.tu-chemnitz.de, Strasse der Nationen 62,
Chemnitz 09111, Germany ; Ingmar Polenz (1) ; Stefan Spange (1) . (1) Department of
Polymer Chemistry, Chemnitz University of Technology, Chemnitz 09111, Germany
Most of the relevant properties of Ionic Liquids (ILs) and their effect on catalysis are
determined by the hydrogen bond donating (HBD) and accepting (HBA) ability of the

ILs. Various UV/Vis and IR probe molecules were used to measure empirical HBD and
HBA strength parameter. 1-3 Two examples of them are presented below (R = n-alkyl, X
= 19 various anions). The imidazolium cation was utilised to serve both, as
cationic part of the IL and 1 H-NMR probe. 1-3 There are significant intercorrelations
between the HBD and HBA strength parameters determined by means of three different
spectroscopic methods. [1] R. Lungwitz, S. Spange, New J. Chem., 2008, 32, 392. [2]
R. Lungwitz, S. Spange, M. Friedrich, W. Linert, S. Spange, New J. Chem., 2008, 32,
1493. [3] R. Lungwitz, V. Strehmel, S. Spange, New J. Chem., 2010, 34, 1135.
COIL-4:414
X-ray Photoelectron Spectroscopy of Ionic Liquid-Based Catalytic Solutions
Shuang Men (1) , pcxsm4@nottingham.ac.uk, University Park, Nottingham
Nottinghamshire NG7 2RD, United Kingdom ; Ignacio J Villar-Garcia (2) ; Emily F Smith (3) ;
Peter Licence (1) ; Kevin RJ Lovelock (1) . (1) School of Chemistry, University of
Nottingham, Nottingham NG7 2RD, United Kingdom (2) School of Chemistry, Addis
Ababa University, Addis Ababa PO Box 1176, Ethiopia (3) Centre for Surface Chemical
Analysis, University of Nottingham, Nottingham NG7 2RD, United Kingdom
Ionic liquids (ILs) are salts with melting point lower than 100 o C. They have very low
vapour pressure and do not suffer significant evaporation even under high vacuum
conditions at room temperature. So it is possible to use X-ray Photoelectron
spectroscopy (XPS) to analyse ionic liquids and ionic liquid-based metal catalytic
solutions. 1 XPS is a highly sensitive technique able to provide the information about
both surface elemental composition of a sample and the electronic structure of different
elements within a compound. It can be applied to distinguish between atoms of the
same element situated in chemically distinct environments. 2 Ionic liquids have been
widely used in many homogenous catalytic reactions with great success. We have used
XPS to investigate key interactions associated with catalytic processes – the interaction
of catalyst with solvent or ligands and the stability of the ionic liquid towards imidazol-2ylidene
formation. We present early results on two catalytic systems, palladium
mediated Suzuki cross-coupling (Fig.1) 3 and rhodium catalysed hydroformylation
systems (Fig.2) 4 . Our research opened a new path to understand the key information
about the effect of ligand or solvent to the metal catalyst performance in solution and
will help for the design of catalytic systems for catalysis reactions in the future.
References [1] Chemical Reviews, 2010, 110, 5158-5190. [2] Phys. Chem. Chem.
Phys., 2011, 13, 2797-2808. [3] Organometallics, 2000, 19, 3818-3822. [4]
Organometallics, 2001, 20, 3848-3850.
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Multi Scale Dynamics of Ionic Liquids Confined in Monolithic Oxides Network.
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Jean Le Bideau (1) , jean.lebideau@cnrs-imn.fr, BP 32229, 2 rue de la Houssiniere,
Nantes cedex 3 44322, France ; Dominique Guyomard (1) ; Jean-Marc Zanotti (2) ; Jean-
Pierre Korb (3) ; Dominique Petit (3) ; Pierre Levitz (3) . (1) Institut des Materiaux Jean Rouxel,
Nantes 44322, France (2) Laboratoire Leon Brillouin, Saclay 91191, France (3) Ecole
Polytechnique, Palaiseau 91128, France
Ionogels provide nanometer scale confinement of an IL within an oxide network. ILs
feature interesting properties, but applications are hampered by the liquid state.
Nevertheless, the use of ionogels for all solid lithium batteries has now been evidenced.
More in depth understanding of the molecular dynamics of the confined ionic liquids was
achieved at different time and space scales by means of quasi elastic neutron scattering
(QENS) and nuclear magnetic relaxation dispersion (NMRD). QENS allows
concluding to a very small decrease at short time scale of the dynamic of confined ionic
liquid. The diffusion coefficients obtained by QUENS were compared to that obtained by
NMRD and PGSE, with relative values related to tortuosity. With NMRD, a translational
correlation time tm for the surface diffusion and a time of residence tesc over which the
ionic liquid stays correlated with the solid surface were measured. Besides the interest
for diffusion coefficients, these parameters allowed investigating phase transitions;
these transitions were also observed by QENS through mean square displacements as
a function of temperature. From their temperature dependence, all these results could
be related to an ion pairs to single ions transition. J. Le Bideau, L. Viau, A. Vioux,
"Ionogels, ionic liquid – based hybrid materials" Chem. Soc. Rev., 2011, 40, 907–925.
D. Petit, J.-P. Korb, P. Levitz, D. Brevet, J. Le Bideau, "Multi-scale Dynamics of 1H and
19F in Confined Ionic Liquids for Lithium Batteries." C.R. Chimie, 2010, 13, 409-411. J.
Le Bideau, D. Guyomard, J.-B. Ducros, P. Soudan, "High energy non-aqueous lithium
batteries based on ionic liquids gels." PATENT FR 2009/50936, WO 2010/092258,
CNRS-Université de Nantes. J. Le Bideau, P. Gaveau, S. Bellayer, M.-A. Néouze, A.
Vioux, "Effect of confinement on ionic liquids dynamics in monolithic silica ionogels : 1H
NMR study." Phys. Chem. Chem. Phys., 2007, 9, 5419-5422.
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Assessment of Interactions Between CO2 and Ionic Liquids Using ab initio
Methods,
R. Smith, J. Steckel *
COIL-4:417
New Ionic Liquids for Active Layers in Photovoltaics

R. M. Frazier (1) , rmfrazier@bama.ua.edu, The University of Alabama Aime Building,
Tuscaloosa Alabama 35487, United States ; D. T. Daly (1) ; W. L. Hough (1) ; S. K. Spear (1) ;
R. D. Rogers (2) . (1) Alabama Innovation and Mentoring of Entrepreneurs, The University
of Alabama, Tuscaloosa Alabama 35487, United States (2) Center for Green
Manufacturing and Department of Chemistry, The University of Alabama, Tuscaloosa
Alabama 35487, United States
Ionic liquids (ILs) play an important role in many electrical devices including dyesensitized
solar cells (DSSCs), organic light emitting diodes (OLEDs), batteries, and
supercapacitors. Currently, ILs are largely used to transport charge in these devices; a
passive role considering the potential ILs offer to actively participate in electrical
devices. The wide absorption range from 300nm to 900nm for common dye salts allows
flexibility in tailoring ILs to specific wavelengths which is useful for photovoltaic devices.
Current organic photovoltaic devices suffer from phase segregation in the active
polymer layers due to mismatch between the donors and acceptors. The dual nature of
ILs allows the engineering of new photovoltaic materials by combining donor and
acceptor molecules into a single compound without deleterious phase segregation.
Additionally, since ILs are lightweight flexible materials, they are easy to use and are
compatible with fabrication techniques such as spraying, screen-printing, and roll-to-roll
processing. These characteristics make ILs extremely amenable to active participation
in electrical devices and offer the potential for enhanced device performance and
functionality. This presentation will discuss UA's recent advances in the design and
implementation of ILs as the active layer in photovoltaics. These new ion pairs absorb in
the visible region of the electromagnetic spectrum and have been used as the light
absorbing and charge transporting materials in sandwich-type solar cells as opposed to
the conventional use of ILs as just the charge transport medium in DSSCs. The output
of devices strongly depends on the choice of cation and anion with improvements
achieved by simply changing one of the ions. These results suggest that ILs are wellsuited
as active layers in electrical devices and open up the opportunity for significant
device enhancement by optimizing ion pairs.
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From Tree Rosin to Chiral Ionic Liquids
Magdalena B. Foreiter (1) , K.Seddon@qub.ac.uk, QUILL Research Centre, Belfast
Northern Ireland, United Kingdom ; H. Q. Nimal Gunaratne (1) ; Tiina Laaksonen (1)(2) ;
Kenneth R. Seddon (1) ; Kristiina Wahala (2) . (1) QUILL Research Centre, The Queen’s
University of Belfast, Belfast Northern Ireland, United Kingdom (2) Laboratory of
Organic Chemistry, University of Helsinki, Belfast Northern Ireland, United Kingdom
We have synthesised several novel chiral ionic liquids from a chiral softwood rosinbased
compound. Our starting material, (+)-dehydroabietylamine, (A), is easily isolated
from a commercially available amine mixture derived from rosin. 1 Since (+)dehydroabietylamine
has been known to have chiral recognition abilities towards
carboxylic acids, 1 according to its magnificent backbone structure, it was considered

that it might be a useful substrate for creating novel chiral ionic liquids, which could be
utilised in an analytical application for chiral analytes, e.g. by NMR recognition. Our
attention was focussed on synthesising chiral ammonium, imidazolium or thiouronium 2
ionic liquids derived from (+)-dehydroabietylamine, (B), (C) and (D). We found S-alkylbis(dehydroabietyl)thiouronium
bis{(trifluoromethyl)sulfonyl}amide, (D), to be an
excellent enantio-discriminating agent for chiral carboxylates in NMR recognition,
representing a novel approach to the discrimination of chiral compounds by NMR
spectroscopy. References 1. W. J. Gottstein and L. C. Cheney, J. Org. Chem.,
1965, 30, 2072. 2. M. Abai, J. D. Holbrey, R. D. Rogers and G. Srinivasan, New J.
Chem., 2010, 34, 1981.