4th EucheMs chemistry congress

Poster Session 2
s1149
chem. Listy 106, s257–s1425 (2012)
Poster session 2 - Analytical Chemistry
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dynAMiC extrACtion of oiL ProduCtS froM
ContAMinAted SoiLS
e. SAvoninA 1 , P. fedotov 1 , A. Soin 1 ,
t. MAryutinA 1
1 Vernadsky Institute of Geochemistry and Analytical Chemistry
RAS, Department of Analytical Chemistry, Moscow, Russia
Control of oil content in contaminated soils is a very actual
task because of increasing development of oil industry. Existing
methods used for the determination of oil hydrocarbons in soils
are routine and time-consuming due to the necessity of laborious
sample pretreatment prior to instrumentation analysis. Hence, the
development of new methods for organic analysis of soils is
required.
The use of flow-through extraction systems (FTES) for
dynamic extraction of hydrocarbons from soils is very promising.
Microcolumns (MC) packed with a particulate sample are wellknow
FTES [1] . In the present work cylindrical MC were applied
to the analysis of spiked with oil hydrocarbons (OH) and
contaminated soil samples. Tetrachlormethane was used as solvent
for MC extraction of OH prior to the detection by
IR-spectrometry. The dependence of extraction efficiency on soil
type, eluent volume and extraction time was systematically
studied. Elution curves show that the eluent volume of 20–30 mL
is enough for extraction in MC. Results on OH content obtained
using extraction in MC, Soxhlet extraction and batch extraction
were comprared. It has been showm that the recovery of OH after
extraction using MC is 70–94%. No filtration step is required
before the determination of OH in the MC effluent. The technique
enables the extraction to be performed within 20–30 minutes
only.The proposed approach to the sample pretreatment in organic
soil analysis opens a new door into the development of new
analytical methods for the control of oil contaminated soils.
references:
1. M. Rosende, M. Miró, V. Cerda Analytica Chim Acta,
2008, 619, 192
Keywords: extraction; oil products; soil;
4 th EucheMs chemistry congress
P - 0 5 7 5
the inveStiGAtion of therMAL deCoMPoSition
of nitro-ChLoro-AzidoBenzeneS with
therMoAnALytiCAL And CoMPutAtionAL
MethodS
n. SenoCAK 1 , n. yiLMAz 2 , S. Öz 3 , i. SvoBodA 4 ,
o. AtAKoL 2
1 Police Criminal Labratory, Chemistry, Ankara, Turkey
2 Ankara University, Chemistry, Ankara, Turkey
3 Ahi Evran University, Chemistry, Kirsehir, Turkey
4 TU- Darmstadt, FB Materialwissenschaft, Darmstadt,
Germany
1,2-dichlorobenzene and 1,2,3-trichlorobenzene were
nitrated with HNO /H SO . The obtained mixtures were
3 2 4
converged into azido-chloro-nitrobenzenes via nucleophilic
subtitution reaction with NaN as described in the literature 3 [1] .
The components in the precipitate were seperated by fractional
crystallization and were investigated by TG. Benzofuroxan
formation after elimination of N at 100–120°C was observed from
2
IR, MS, and XRD results in case of nitro and azide groups are
next to each other in the aromatic ring (Fig.1). Additionally, the
released energies for exothermic reaction of o-nitroazidobenzenes
were measured by DSC. On the other hand an obvious detonation
reaction was observed for dinitrodiazidobenzenes at 130–150 °C.
All theoretical calculations were carried out using the
Gaussian G09W (revision B.01) program package. [2] DFT-based
structure optimizations and frequency analyses were performed
at the B3LYP/cc-pVDZ level of theory. [3] The enthalpies of
formation of both reactants and products were calculated using
complete basis set (CBS-4M) method of Petersson and coworkers
in order to obtain accurate energies. [4] From the calculated heat of
formations the enthalpies of decomposition were calculated
according to Hess’s Law and were compared with the
experimental values which were available from DSC analysis.
The good agreement between the experimentally observed
enthalpies of decomposition and the CBS-4M calculated values
gives credence to the accuracy of the applied CBS-4M method.
references:
1. A. S. Bailey, J.R. Case, Tetrahedron, 3, 113-131,1958
2. Gaussian 09 Software, Revision B01.2009
3. A. D. Becke, J. Chem. Phys., 88, 1053-1062, 1988
4. Jr. A. J. Montgomery, M. J. Frisch, J. W. Ochterski,
G. A. Petersson, J. Chem. Phys. 112, 6532-6553, 2000
Keywords: Benzofuroxan; CBS-4M; DFT; Nitroazidobenzene;
Thermal analysis;
AUGUst 26–30, 2012, PrAGUE, cZEcH rEPUbLIc