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P / MPa 14 12 10 8 6 4 2 0 0.0 0.2 0.4 0.6 0.8 1.0 x, y CO2 Modeling Figure III.13. Predictions of VLE of CO2/perfluobenzene system at 293.15, 323.15 and 353.15 K. Symbols represent experimental data measured in this work. Solid dark lines correspond to the soft-SAFT model including the polar term and dashed lines to the original soft-SAFT model. In both cases the size and the energy binary interaction parameters are set to one. The lighter solid lines are predictions given by the Peng Robinson EoS with kij=0. Results obtained for perfluorodecalin and perfluoromethylcyclohexane are similar to the ones obtained for perfluoro-n-octane, meaning that the introduction of the quadrupole effect in CO2 does not seem to noticeably influence the description of the phase equilibria for non aromatic perfluorocompounds. In a previous work, it was observed that binary parameters are needed for obtaining quantitative predictions if the lengths of the two molecules involved in the mixtures are different and/or their shape deviates from spherical (Kontogeorgis et al., 1996). Using other EoS the authors showed that for athermal mixtures the use of a size binary parameter could provide a better and more meaningful description of data and reduce the magnitude of the energy binary parameter in systems were energetic interactions are important. Thus, a good description of the phase diagrams of CO2/non-aromatic-perfluoroalkanes requires the use of two interaction parameters, as previously observed for oxygen/perfluoroalkanes mixtures. - 139 -
P / MPa 14 12 10 8 6 4 2 0 0 0.2 0.4 0.6 0.8 1 x, y CO2 Modeling Figure III.14. Predictions of the vapor-liquid equilibrium of CO2/perfluorotoluene system at 293.15K, 323.15K and 353.15K. Legend as in Figure III.13. P/MPa 14 12 10 8 6 4 2 0 0.0 0.2 0.4 0.6 0.8 1.0 x, y CO2 Figure III.15. Predictions of the vapor-liquid equilibrium of CO2/perfluoro-n-octane system at 293.15K, 323.15K and 353.15K. Legend as in Figure III.13. - 140 -
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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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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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I. 3. Vapour pressure I.3.1. Biblio
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I.3.2. Apparatus and Procedure Expe
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I.3.3. Experimental Results and Dis
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Table II.8. (continued) T K Pexp kP
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ΔH vap = TΔS vap 2⎛ d ln P ⎞
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I.4. Solubility at atmospheric pres
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x2 (T,P2) 7.0E-03 6.0E-03 5.0E-03 4
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L 2,1 0.70 0.60 0.50 0.40 0.30 285
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P / MPa 6 5 4 3 2 1 0 P / MPa 14 12
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II.6. Liquid - Liquid Equilibrium I
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0 τ β Δ1 2Δ1 [ 1+ B τ + B τ +
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References Experimental Methods, Re
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Page 107 and 108: Experimental Methods, Results and D
Page 109 and 110: 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
Page 157: Modeling average deviation (AAD) be
Page 161 and 162: Modeling Figures III.16, III.17 and
Page 163 and 164: Modeling calculations from the orig
Page 165 and 166: Table III.9. References for VLE exp
Page 167 and 168: P / MPa 20 18 16 14 12 10 8 6 4 2 0
Page 169 and 170: Modeling Finally, Figure III.24 pre
Page 171 and 172: III.4.4. VLE and LLE of Alkane and
Page 173 and 174: Modeling number of perfluro-n-alkan
Page 175 and 176: y C6F14 1.0 0.8 0.6 0.4 0.2 0.0 0.0
Page 177 and 178: 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.,
Page 185 and 186: DIPPR, Thermophysical Properties Da
Page 187 and 188: Modeling Hildebrand, J. H.; Fisher,
Page 189 and 190: 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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