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Modeling shown such wide and reliable applicability to the calculation of vapor-liquid equilibria (VLE) for systems containing light hydrocarbons, permanent gases, carbon dioxide, and as shown here, perfluoroalkanes. P / MPa 12 10 8 6 4 2 0 0 0.2 0.4 0.6 0.8 1 x, y CO2 Figure III.17. Vapor-liquid equilibrium of CO2/perfluoromethylcyclohexane system at 293.15K, 323.15K and 353.15K. Legend as in Figure III.16. As a further test of the reliability of the parameters provided here for the soft-SAFT EoS, the performance of the soft-SAFT equation was checked, without and with the quadrupolar term for the mixture CO2/perfluoro-n-hexane, for which there is available data in the literature (Iezzi et al, 1989). Figure III.19 shows predictions of the original and the polar soft-SAFT equation for this mixture. Figure III.19a depicts pure predictions from the two versions of the equation. Figure III.19b presents calculations from both versions of soft-SAFT with the size binary parameters taken from Table III.8, and binary size energy parameters equal to 0.807 and 0.916, respectively. The energy parameters were fitted at 314.65K and used in a transferred manner for the higher temperature, 353.25K. Regarding the pure predictions (Figure III.19a) it is interesting to see the effect the addition of the quadrupole has in accurately describing the behaviour of the mixture as compared to the original equation. The simulation results obtained by Cui et al. (1998) and also by Zhang and Siepmann (2005) from Monte Carlo simulations for this mixture lye between - 143 -
Modeling calculations from the original soft-SAFT equation and those provided from the polar soft- SAFT equation, being polar soft-SAFT superior than the simulations in this case. Note that in these simulations explicit charges were considered for the CO2 molecule. P / MPa 14 12 10 8 6 4 2 0 0 0.2 0.4 0.6 0.8 1 x, y CO2 Figure III.18. Vapor-liquid equilibrium of CO2/perfluorodecalin system at 293.15K, 323.15K and 353.15K. Legend as in Figure III.16 Excellent agreement is observed when both versions of the equation are used with binary parameters (Figure III.19b), as expected from the rest of the results shown here. A similar study was carried for CO2/alkane mixtures. The alkanes studied are the corresponding alkanes for the perfluoroalkanes studied in this work. Table III. 9 reports the references from where the VLE data for these mixtures was taken as well as the temperature range studied in each case and the intermediate temperature used in this work to adjust the binary interaction parameters. The main objective of this comparison is to observe the influence of fluorination on the solubility of carbon dioxide and to compare the influence of the electrostatic contributions for these mixtures, using as tool the soft-SAFT EoS. Experimentally, for all the systems studied in this work, the solubility of carbon dioxide is always higher in the fluorinated molecules. This effect is maximum for the CO2/perfluorodecalin vs CO2/decalin systems. At the thermodynamic conditions presented the CO2/decalin system presents a LL region for carbon dioxide mole fractions higher than - 144 -
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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 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 and 158: Modeling average deviation (AAD) be
Page 159 and 160: P / MPa 14 12 10 8 6 4 2 0 0 0.2 0.
Page 161: Modeling Figures III.16, III.17 and
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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