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Experimental Methods, Results and Discussion Comparison of the C-F and C-H Thermochemical Bond Energies, J. Am. Chem. Soc., (1959) 63: 1133 Goodwin, A.R.H.; Moldover, M.R. Phase Border and Density Determinations in the Critical Region of (carbon dioxide plus ethane) Determined from Dielectric Permittivity Measurements, J. Chem. Thermodyn. (1997) 29: 1481 Greer, S. C.; Moldover, M.R.; Hocken R., Differential Transformer as a Position Detector in a Magnetic Densimeter, Rev. Sci. Instrum. (1974) 45: 1462 Hales, J. L. Apparatus for Accurate Measurement of Liquid Densities Over an Extended Temperature Range, J. Phys. E (1970) 3: 855 Hales, J. L.; Townsend, R. Liquid Densities From 293 to 490 K of Eight Fluorinated Aromatic Compounds, J. Chem. Thermodynamics (1974) 111-116 Hales, J. L.; Gundry, H. A., An Apparatus for Accurate Measurement of Liquid and Vapor Densities on the Saturation Line, Up to the Critical-Temperature, J. Phys. E: Sci. Instrum. (1983) 16: 91 Haszeldine, R.; Smith, F., Organic Fluorides. Part VI. The Chemical and Physical Properties of Certain Fluorocarbons, J. Chem. Soc. (1951) 603-608 Hefter, G. T. Liquid-Liquid Solubilities in The Experimental Determination of Solubilities Edited by Hefter, G. T. and Tomkins, R. P. T., John Wiley & Sons, Ltd (2003) Hesse, P.; Battino, R.; Scharlin, P.; Wilhelm, E., Solubility of Gases in Liquids. 20. Solubility of He, Ne, Ar, Kr, N2, O2, CH4, CF4, and SF6 in n-Alkanes n-ClH2l+2 (6 l 16) at 298.15 K, J. Chem. Eng. Data, (1996) 41: 195 Hickman, J. B., Solubility of Isomeric Hexanes in Perfluoroheptane, J. Am. Chem. Soc. (1955) 77: 6154 Hildebrand, J. H.; Cochran, D. R. F., Liquid-Liquid Solubility of Perfluoromethylcyclohexane with Benzene, Carbon Tetrachloride, Clorobenzene, Chloroform and Toluene, J. Am. Chem. Soc. (1949) 71: 22 Hildebrand, J. H.; Fisher, B. B.; Benesi, H. A., Solubility of Perfluoro-n-heptane with Benzene, Carbon Tetrachloride, Chloroform, n-Heptane and 2,2,4-Trimethylpentane, J. Am. Chem. Soc. (1950) 72: 4348 Hildebrand J. H., Prausnitz, J. M., Scott, R. L., Regular and Related Solutions, Van Nostrand Reinhold, New York (1970) Chapter 8 Iezzi, A.; Bendale, P. ; Enick, R.; Turberg, M.; Brady, J., Gel Formation in Carbon Dioxide – Semifluorinated Alkane Mixtures and Phase Equilibria of a Carbon Dioxide – Perfluorinated Alkane Mixture, Fluid Phase Equilibria (1989) 52: 307 - 87 -
Experimental Methods, Results and Discussion IUPAC Recommended Reference Materials for the Realization of Physicochemical Properties. Marsh, K. N.; editor. Blackwell (for IUPAC): Oxford (1987) Kennan, R. P.; Pollack, G.L., Solubility of Xenon in Perfluoroalkanes: Temperature Dependence and Therodynamics, J. Chem. Phys, (1988) 89: 517 Koo, L.; Green, M. S. Revised and Extended Scaling for Coexisting Densities of SF6 Phys. Rev. A (1977) 16: 2483 Kreglewski, A., Determination of high-pressure liquid density for n-perfluorohexane and n-perfluorononane, Bulletin de L'academie Polonaise des Sciences, (1962) vol.X: 629 Knapp, H.; Döring, R.; Oellrich, L.; Plöcker, U.; Prausnitz, J.M., Vapor–Liquid Equilibria for Mixtures of Low-Boiling Substances, DECHEMA Chem. Data Series VI (1981) Lannung, A., The Solubilities of Helium, Neon and Argon in Water and Some Organic Solvents, J. Am. Chem. Soc. (1930) 52: 68 Lazzaroni, M. J.; Bush, D.; Brown, J. S.; Eckert, C. A., High-Pressure Vapor-Liquid Equilbria of Some Carbon Dioxide+Organic Binary Systems, J. Chem. Eng. Data (2005) 50: 60 Makranczy, J., Solubility of Gases in Normal-Alkanes, Hungarian Journal of Industrial Chemistry, (1976) 4: 269 Marteau, Ph.; Tobaly, P.; Ruffier-Meray, V.; Barreau, A., In Situ Determination of High Pressure Phase Diagrams of Methane-Heavy Hydrocarbon Mixtures Using an Infrared Absorption Method, Fluid Phase Equilib. (1996) 119: 213 Miguel, A. A. F.; Ferreira, A. G. M.; Fonseca, I. M. A, Solubilities of Refrigerants in water, Fluid Phase Equilibria (2000) 173: 97 Morrison, T. J.; Billett, F. The Measurement of Gas Solubilities J. Chem. Soc. (1948) 2033 Mousa, A. H. N. Study of Vapor Pressure and Critical Properties of Perfluoro-n-hexane J. Of Chemical and Engineering Data (1978) 23: 133 Nagahama, K. VLE Measurements at Elevated Pressures for Process Development, Fluid Phase Equilibria (1996) 116: 361 Nagarajan, N.; Kumar, A.; Gopal, E. S. R.; Greer, S. C. Liquid-Liquid Critical Phenomena. The Coexistence Curve of n-heptane –acetic anhydride, J. Phys. Chem. (1980) 84: 2883 Pádua, A. A. H., PhD Thesis (1994) Patrick, C. R.; Prosser, G. S. Vapour Pressures + Related Properties of Hexafluorobenzene Transactions of the Faraday Society (1964) 60: 700 Pauly, J.; Daridon, J-Luc; Coutinho, J. A. P. Fluid Phase Equilibria, 2005 submited - 88 -
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Ana Maria Antunes Dias Universidade
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o júri presidente Prof. Dr. Joaqui
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palavras-chave resumo perfluoroalca
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Contents Notation List of Tables Li
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Notation Abbreviations AAD EoS LCST
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List of Tables Table I.1 Average Bo
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Table III.6 Adjusted Binary Paramet
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Figure II.9 Comparison between corr
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Figure III.8 Temperature-density di
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Figure III.25 Vapor-phase mole frac
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I.1. Fluorine Properties General In
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Table I.2. Physicochemical Properti
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General Introduction order to compa
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General Introduction the numerous a
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General Introduction carbon dioxide
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General Introduction animals. That
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General Introduction Table I.3. Lit
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References General Introduction Ban
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General Introduction Hildebrand, J.
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General Introduction Rowinsky EK. N
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II. Part EXPERIMENTAL METHODS, RESU
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Experimental Methods, Results and D
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Page 47 and 48:
Page 49 and 50:
Table II.3. (continued) T K ρexp g
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ρ / g.cm-3 1.750 1.730 1.710 1.690
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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 61 and 62: Experimental Methods, Results and D
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 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 101 and 102: 0 τ β Δ1 2Δ1 [ 1+ B τ + B τ +
Page 103 and 104: References Experimental Methods, Re
Page 105: Experimental Methods, Results and D
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
Page 141 and 142: 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
Page 149 and 150: 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
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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.
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P / MPa 0.12 0.10 0.08 0.06 0.04 0.
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Modeling approach based on the meth
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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-
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Modeling Poling, B.; Prauznitz, J.;
Page 193 and 194:
Modeling Wertheim, M. S., Fluids wi
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