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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. …………………………………………………………………. Figure III.16 Vapor-liquid equilibrium of CO2/perfluoro-n-octane system at 293.15K, 323.15K and 353.15K. Symbols represent experimental data measured in this work. Solid lines corresponds to the soft-SAFT model including the polar term and black dashed lines to the original soft-SAFT model at optimised size and the energy binary interaction parameters from Table III.8. The lighter solid lines are predictions given by the Peng Robinson EoS with kij also from Table III.8……… Figure III.17 Vapor-liquid equilibrium of CO2/perfluoromethylcyclohexane system at 293.15K, 323.15K and 353.15K. Legend as in Figure IV.16……… Figure III.18 Vapor-liquid equilibrium of CO2/perfluorodecalin system at 293.15K, 323.15K and 353.15K. Legend as in Figure III.16…………………… Figure III.19 Vapor-liquid equilibrium of CO2/perfluoro-n-hexane system at 314.65, 353.25 K. Symbols represent experimental data measured by Iezzi et al. (1989) (a) Predictions given by the soft-SAFT model (b) soft-SAFT calculations with binary interaction parameters. Legend as in Figure III.16………………………………………………………... Figure III.20 Predictions of the vapor-liquid equilibrium of CO2/benzene system at 298, 313 and 353 and 393 K. Symbols represent experimental data. Solid lines correspond to the soft-SAFT model including the polar term and dashed lines to the original soft-SAFT model. (a) Size and the energy binary interaction parameters are set to one; (b) Size and the energy binary interaction parameters adjusted at 313 K………….. Figure III.21 Predictions of the vapor-liquid equilibrium of CO2/toluene system at 290.8, 323.17, 353.18 and 477.04 K. Legend as in Figure III.20. Binary parameters were adjusted at 323 K…………………………… Figure III.22 Predictions of the vapor-liquid equilibrium of CO2/n-octane system at 313.15, 328.15 and 348.15 K. Legend as in Figure III.21. Binary parameters were adjusted at 328 K…………………………………… Figure III.23 Predictions of the vapor-liquid equilibrium of CO2/methylcyclohexane system at 270, 311, 338.9 and 477 K. Legend as in Figure III.22. Binary parameters were adjusted at 311 K…………………………………………………………………. Figure III.24 Predictions of the vapor-liquid equilibrium of CO2/decalin system at 298, 348 and 423 K. Legend as in Figure III.23. Binary parameters were adjusted at 323 K. The star indicates the upper critical solution temperature of this mixture………..…………………………………. - xii - 140 142 143 144 145 147 148 149 149 150
Figure III.25 Vapor-phase mole fraction versus the liquid mole fraction for nperfluorohexane + n-alkane mixtures: n = 5 at 293.65 K (circles), n = 6 at 298.15 K (squares), n = 7 at 317.65 K (diamonds), and n = 8 at 313.15 K (triangles). Symbols represent experimental data (Duce et al., 2002) and lines correspond to the predictions from the soft-SAFT EoS……………………………………………………………………. Figure III.26 Vapor-phase mole fraction versus the liquid mole fraction for nhexane + n-perfluoroalkane mixtures: n = 5 at 293.15 K (circles), n = 6 at 298.15 K (squares), n = 7 at 303.15 K (diamonds), and n = 8 at 313.15 K (triangles). Symbols represent experimental data (Duce et al., 2002) and lines correspond to the predictions from the soft-SAFT EOS…………………………………………………………………… Figure III.27 P-x diagrams for C6F14 + CnH2n+2 mixtures. (a) n = 5 at 293.65 K (circles), n = 6 at 298.15 K (squares) and (b) n = 7 at 317.65 K (diamonds), and n = 8 at 313.15 K (triangles). Symbols represent experimental data (Duce et al., 2002) and lines correspond to the predictions from the soft-SAFT EoS…………………………………. Figure III.28 P-x diagrams for C6H14 + CnF2n+2 mixtures. (a) n = 5 at 293.65 K (circles), n = 6 at 298.15 K (squares) and (b) n = 7 at 317.65 K (diamonds), and n = 8 at 313.15 K (triangles). Symbols represent experimental data (Duce et al., 2002) and lines correspond to the predictions from the soft-SAFT EoS…………………………………. Figure III.29 P-x diagrams at 259.95 K, 253.62 K, 246.35 K and 238.45 K for C4F10 + C4H10 mixture compared with soft-SAFT predictions. The triangles describe the experimental data (Thorpe and Scott, 1956) and the solid curves the theoretical predictions…………………………… Figure III.30 P-x diagrams at 110.5 K, 108.5 K and 105.5 K for CF4 + CH4 mixture compared with soft-SAFT predictions. The circles describe the experimental data (Thorpe and Scott, 1956) and the solid curves the theoretical predictions…………………………………………….. Figure III.31 LLE of C6F14 + CnH2n+2 mixtures at 0.1 MPa: n = 6 (diamonds), n = 7 (squares) and n = 8 (triangles). Symbols represent experimental data (Duce et al., 2002). Solid lines correspond to the predictions from the soft-SAFT EoS……………………………………………… Figure III.32 LLE of C8F18 + CnH2n+2 mixtures at 0.1 MPa: n = 6 (diamonds), n = 7 (squares), n = 8 (triangles) and n = 9 (circles). Symbols represent experimental data (Duce et al., 2002). Solid lines correspond to the predictions from the soft-SAFT EoS. Stars represent the upper critical solution temperature for each mixture………………………………... 162 - xiii - 156 156 158 159 160 160 161
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: Figure III.8 Temperature-density di
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 and 34: General Introduction Table I.3. Lit
Page 35 and 36: References General Introduction Ban
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 71 and 72:
Experimental Methods, Results and D
Page 73 and 74:
Page 75 and 76:
Page 77 and 78:
Page 79 and 80:
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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Page 85 and 86:
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
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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
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Modeling The pioneering work of Wer
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III.2. Soft-SAFT Model Modeling A S
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Modeling The equation of state is w
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Chain Term Modeling Originally Wert
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Modeling The model is easily extend
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( ) ( ) ∑∑∑ 3 2 2 2 2 qq 32π
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Modeling HRT is a promising theory,
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( ρ) ρ , 0 ≤ ρ ( ρ) 2 Modelin
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III.3. Application to Pure Compound
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Modeling From the optimised paramet
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T / K 400 350 300 250 200 150 100 5
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ln Pvap 1.0E+01 1.0E+00 1.0E-01 1.0
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Modeling Table III.2. Absolute Aver
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Modeling The correlation coefficien
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Pvap (MPa) 4.00 3.50 3.00 2.50 2.00
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Modeling The mixture parameters a a
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Modeling the assumptions made by th
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Modeling between oxygen and perfluo
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xSolute 5.5E-03 5.0E-03 4.5E-03 4.0
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Modeling previous work, dealing wit
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Modeling These results confirm that
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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.;
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Modeling Wertheim, M. S., Fluids wi
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