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General Introduction term is a Lennard-Jones that accounts simultaneously for the attractive and the repulsive term of the interaction potential. One of the main advantages of using a molecular based EoS as the soft-SAFT is that the parameters are physically meaningful and independent of the thermodynamic conditions. Also, contrarily to simple mean-field approaches it is possible to explicitly consider intramolecular as well as intermolecular interactions. Furthermore, and probably the most important feature, is that SAFT is an approach in which the different microscopic contributions that control the macroscopic properties of the fluid are explicitly considered when building the theory. In this sense, non-ideal contributions, such as molecular shape, polarity and association, can be introduced in the development of the equation according to the system in study originating a robust and versatile tool for the prediction of thermodynamic properties of complex systems. The systems studied include pure perfluoroalkanes, alkanes, gases as xenon, radon, oxygen and carbon dioxide and mixtures between them. The equation was used to correlate/predict vapour pressure and density data of the pure compounds, vapour-liquid equilibrium of gases and alkanes in perfluoroalkanes and liquidliquid equilibrium between perfluoroalkanes and alkanes. For all the properties studied, the results given by the sof-SAFT Eos are always compared with the results given by a cubic EoS, in this case the Peng-Robinson EoS. The solubility of oxygen in perfluoroalkanes was also modelled using the Regular Solution Theory in an entirely predictive manner in order to quantify the importance of the entropic contribution during the dissolution process. - 15 -
References General Introduction Banks, R. E. Fluorocarbons and Their Derivatives Macdonald Technical & Scientific: London, (1970) 7-69 Banks, R. E.; Tatlow, J. C., A Guide to Modern Organofluorine Chemistry, Journal of Fluorine Chemistry (1986) 33: 227 Betzemeier, B.; Knochel, P., Perfluorinated Solvents - a Novel Reaction Medium in Organic Chemistry, Top. Curr. Chem. (1999) 206: 61 Bonaventura, C.; Tesh, S.; Faulkner, K. M.; Kraiter, D.; Crumbliss, A. L., Conformational Fluctuations in Deoxy Hemoglobin Revealed as a Major Contributor to Anionic Modulation of Function Through Studies of the Oxygenation and Oxidation of Hemoglobins A(0) and Deer Lodge Beta 2(NA2)His -> Arg, Biochemistry (1998) 37: 496 Bonifácio, R. P.; Filipe, E. J. M.; McCabe, C.; Gomes, M. F. C.; Pádua, A H. A., Predicting the Solubility of Xenon in n-hexane and n-perfluorohexane: A Simulation and Theoretical Study, Molecular Physics (2002) 100: 2547 Calado, J. C.; McLure, I. M.; Soares, V., Surface Tension for Octafluorocyclobutane, nbutane and their Mixtures from 233 K to 254 K, and Vapour Pressure, Excess Gibbs Function and Excess Volume for the Mixture at 233 K, Fluid Phase Equilibria, (1978) 2: 199 Chandler, D., Structures of Molecular Liquids, Annu. Rev. Phys. Chem. (1978) 29: 441 Cho, M. H.; Wang, S. S., Enhancement of Oxygen-Transfer in Hybridoma Cell-Culture by Using a Perfluorocarbon as an Oxygen Carrier, Biotechnology Letters (1988) 10: 855 Clark, L. C. Gollan F., S u rvival of Mammals Breathing Organic Liquids Equilibrated with Oxygen at Atmospheric Pre s s u re, Science (1966) 152: 1755 Clark, E. S., The Molecular Conformations of Polytetrafluoroethylene: Forms II and IV, Polymer (1999) 40: 4659 Cohn SM., Blood Substitutes in Surgery, S u rgery (2000) 127: 599 Colina, C. M.; Galindo, A.; Blas, F. J.; Gubbins, K.E. Phase Behavior of Carbon Dioxide Mixtures with n-alkanes and n-perfluoroalkanes Fluid Phase Equilibria (2004) 222–223: 77 Colina, C. M.; Gubbins, K. E. Vapor-Liquid and Vapor-Liquid-Liquid Equilibria of Carbon Dioxide/n-perfluoroalkane/n-alkane Ternary Mixtures J. Phys. Chem. B (2005) 109: 2899 Cui, S. T.; Siepmann, J. I.; Cochran, H. D.; Cummings, P. T., Intermolecular Potentials and Vapor-Liquid Phase Equilibria of Perfluorinated Alkanes, Fluid Phase Equilibria (1998) 146: 51 - 16 -
Page 1 and 2: Ana Maria Antunes Dias Universidade
Page 3 and 4: o júri presidente Prof. Dr. Joaqui
Page 5 and 6: palavras-chave resumo perfluoroalca
Page 7 and 8: Contents Notation List of Tables Li
Page 9 and 10: Notation Abbreviations AAD EoS LCST
Page 11 and 12: List of Tables Table I.1 Average Bo
Page 13 and 14: Table III.6 Adjusted Binary Paramet
Page 15 and 16: Figure II.9 Comparison between corr
Page 17 and 18: Figure III.8 Temperature-density di
Page 19 and 20: Figure III.25 Vapor-phase mole frac
Page 21 and 22: I.1. Fluorine Properties General In
Page 23 and 24: Table I.2. Physicochemical Properti
Page 25 and 26: General Introduction order to compa
Page 27 and 28: General Introduction the numerous a
Page 29 and 30: General Introduction carbon dioxide
Page 31 and 32: General Introduction animals. That
Page 33: General Introduction Table I.3. Lit
Page 37 and 38: General Introduction Hildebrand, J.
Page 39 and 40: General Introduction Rowinsky EK. N
Page 41 and 42: II. Part EXPERIMENTAL METHODS, RESU
Page 43 and 44: Experimental Methods, Results and D
Page 49 and 50: Table II.3. (continued) T K ρexp g
Page 51 and 52: ρ / g.cm-3 1.750 1.730 1.710 1.690
Page 55 and 56: I. 3. Vapour pressure I.3.1. Biblio
Page 57 and 58: I.3.2. Apparatus and Procedure Expe
Page 59 and 60: I.3.3. Experimental Results and Dis
Page 63 and 64: Table II.8. (continued) T K Pexp kP
Page 67 and 68: ΔH vap = TΔS vap 2⎛ d ln P ⎞
Page 69 and 70: I.4. Solubility at atmospheric pres
Page 79 and 80: x2 (T,P2) 7.0E-03 6.0E-03 5.0E-03 4
Page 81 and 82: L 2,1 0.70 0.60 0.50 0.40 0.30 285
Page 85 and 86:
Experimental Methods, Results and D
Page 87 and 88:
Page 89 and 90:
Page 91 and 92:
Page 93 and 94:
P / MPa 6 5 4 3 2 1 0 P / MPa 14 12
Page 95 and 96:
II.6. Liquid - Liquid Equilibrium I
Page 97 and 98:
Page 99 and 100:
Page 101 and 102:
0 τ β Δ1 2Δ1 [ 1+ B τ + B τ +
Page 103 and 104:
References Experimental Methods, Re
Page 105 and 106:
Page 107 and 108:
Page 109 and 110:
Page 111 and 112:
III.1. Introduction Modeling Most c
Page 113 and 114:
Modeling The pioneering work of Wer
Page 115 and 116:
III.2. Soft-SAFT Model Modeling A S
Page 117 and 118:
Modeling The equation of state is w
Page 119 and 120:
Chain Term Modeling Originally Wert
Page 121 and 122:
Modeling The model is easily extend
Page 123 and 124:
( ) ( ) ∑∑∑ 3 2 2 2 2 qq 32π
Page 125 and 126:
Modeling HRT is a promising theory,
Page 127 and 128:
( ρ) ρ , 0 ≤ ρ ( ρ) 2 Modelin
Page 129 and 130:
III.3. Application to Pure Compound
Page 131 and 132:
Modeling From the optimised paramet
Page 133 and 134:
T / K 400 350 300 250 200 150 100 5
Page 135 and 136:
ln Pvap 1.0E+01 1.0E+00 1.0E-01 1.0
Page 137 and 138:
Modeling Table III.2. Absolute Aver
Page 139 and 140:
Modeling The correlation coefficien
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Pvap (MPa) 4.00 3.50 3.00 2.50 2.00
Page 143 and 144:
Modeling The mixture parameters a a
Page 145 and 146:
Modeling the assumptions made by th
Page 147 and 148:
Modeling between oxygen and perfluo
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xSolute 5.5E-03 5.0E-03 4.5E-03 4.0
Page 151 and 152:
Modeling previous work, dealing wit
Page 153 and 154:
Modeling These results confirm that
Page 155 and 156:
Modeling CO2 binary mixtures using
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Modeling average deviation (AAD) be
Page 159 and 160:
P / MPa 14 12 10 8 6 4 2 0 0 0.2 0.
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Modeling Figures III.16, III.17 and
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Modeling calculations from the orig
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Table III.9. References for VLE exp
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P / MPa 20 18 16 14 12 10 8 6 4 2 0
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Modeling Finally, Figure III.24 pre
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III.4.4. VLE and LLE of Alkane and
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Modeling number of perfluro-n-alkan
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y C6F14 1.0 0.8 0.6 0.4 0.2 0.0 0.0
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P / MPa 0.08 0.07 0.06 0.05 0.04 0.
Page 179 and 180:
P / MPa 0.12 0.10 0.08 0.06 0.04 0.
Page 181 and 182:
Modeling approach based on the meth
Page 183 and 184:
Modeling Blas, F. J.; Vega, L. F.,
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DIPPR, Thermophysical Properties Da
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Modeling Hildebrand, J. H.; Fisher,
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Modeling McCabe, C.; Jackson, SAFT-
Page 191 and 192:
Modeling Poling, B.; Prauznitz, J.;
Page 193 and 194:
Modeling Wertheim, M. S., Fluids wi
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