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ρ / g.cm -3 1.840 1.820 1.800 1.780 1.760 1.740 Experimental Methods, Results and Discussion 280 290 300 310 320 T / K Figure II.3. Comparison between experimental density data for perfluoro-n-nonane measured in this work (■) and literature data measured by (*) Haszeldine et al. (1951) and (∆) Piñeiro et al. (2004). ρ / g.cm -3 1.700 1.680 1.660 1.640 1.620 1.600 1.580 1.560 1.540 280 290 300 310 320 330 T / K Figure II.4. Comparison between experimental density data for perfluorobenzene (*) and perfluorotoluene (x) measured in this work and literature data measured by (–) Hales et al. (1974). - 33 -
Experimental Methods, Results and Discussion Hales et al. (1974) measured the density of degassed samples of perfluorobenzene and perfluorotoluene by weighing with and without activation of a solenoid, which maintains a magnetically controlled float in the centre of the sample, according to a procedure described elsewhere (Hales et al, 1970). The densities measured for those compounds in the present work are in both cases systematically lower, by 1.2x10 -3 g/cm 3 , than those measured by these authors. The effect of dissolved air on the density of perfluoro-n-hexane and perfluorobenzene was studied by Dunlap et al. (1958) and Hales et al. (1974), respectively. In the case of perfluoro-n-hexane, densities of the degassed sample were about 2.0x10 -3 g/cm 3 higher than those of the air saturated sample. In the case of perfluorobenzene, differences between degassed and air saturated samples were about 7.5x10 -4 g/cm 3 . Those differences are related with the solvent’s capacity to dissolve components of the air which is higher in the case of perfluoro-n-hexane (Dias et al., 2004; Evans et al., 1971). This observation cannot entirely justify the differences between density data measured in this work and literature data. In fact, differences observed for perfluorobenzene and perfluorotoluene, around 1.2x10 -3 g/cm 3 , are higher than would be expected just from considering the effect of dissolved air in the sample. For perfluoro-n-hexane, data measured by Dunlap et al. (1958), for an air saturated sample, are lower than those obtained in this work. Also, the comparison between the data measured in this work and reported by Piñeiro et al. (2004), seems to indicate that the methods used in both works are not very sensitive to differences between densities of degassed and air saturated samples. The different methods used to measure the densities are probably the main reason for the differences observed. I.2.4. Derived properties At the thermodynamic conditions used to measure density data in this work it is possible to calculate the isobaric thermal expansion coefficient αP along the saturation curve at 298.15 K, using Equation II.6. Values obtained for the fluorinated compounds studied in this work are reported in Table II.5. P T ⎟ 1 ⎛ ∂ρ ⎞ α = − ⎜ ρ ⎝ ∂ ⎠ P - 34 - (II.6)
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 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: 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 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 and 106:
Experimental Methods, Results and D
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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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