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Experimental Methods, Results and Discussion pronounced than data measured by Gomes et al. (2004). The value reported by Skarts et al. (1978) at 310.15 K agrees with the temperature dependence obtained in this work. The values reported by Wesseler et al. (1977) and Riess et al. (2001) at 298.15 K are 14 % and 9 % respectively higher than the values measured in this work at the same temperature. In the case of perfluoro-n-heptane and perfluoro-n-nonane, only one value was found for comparison, one reported by Gjaldbaek (1952) for perfluoro-n-heptane and the other reported by Wesseler at al. (1977) for perfluoro-n-nonane. The deviations are of 10% and 2 % respectively, higher than the values measured in this work at the same temperature. The higher deviation found in the case of perfluoro-n-heptane can be due to the low purity of the sample used in this work. I.4.5. Derived properties The dissolution of a gas into a liquid is associated with changes in thermodynamic functions namely standard Gibbs energy (ΔG2 * ), standard enthalpy (ΔH2 * ) and standard entropy (ΔS2 * ) of solvation that can be calculated from experimental solubility results. These functions represent the changes that occur in the solute neighborhood during dissolution process due to the transference of one solute molecule from the pure perfect gas state to an infinitely dilute state in the solvent, at a given temperature T and so they can correctly describe the average intermolecular interaction between the solute and the solvent Ben-Naim and Marcus (1984) and Ben-Naim (2001). The thermodynamic functions were calculated from the temperature dependence of the molar fraction according to the following equations * ⎛ ⎞ 0 ⎜ RT G = Δ − ⎟ 2 G RT ln ⎜ ⎟ (II.21) ⎝ V1 ⎠ Δ 0 * 0 ΔH = ΔH − RT ( Tα −1) (II.22) 2 1 * ⎛ ⎞ 0 ln⎜ RT ΔS 2 = ΔS + R ⎟ ⎜ − ( 1 −1 0 ⎟ R Tα ) (II.23) ⎝ V1 ⎠ where R is the gas constant, α1 is the isobaric thermal expansibility of the solvent, calculated from density data, and ΔG 0 , ΔH 0 and ΔS 0 are the thermodynamic functions associated with the hypothetical changes that happen in the solute neighborhood when the - 63 -
Experimental Methods, Results and Discussion molecules are transferred from the gas phase to a hypothetical solution where the mole fraction of solute is equal to one, which are calculated from the temperature dependence of the experimental solubility data measured according to the following equations (Ben- Naim, 1980 and Ben-Naim and Marcus, 1984), 0 ( ln x ) p Δ G2 = −RT 2 (II.24) G T H ⎟ ⎛ ∂( Δ / ) ⎞ Δ 0 0 2 T ⎜ 2 = − ⎝ ∂T (II.25) ⎠ p G S T ⎟ 0 0 ⎛ ∂Δ ⎞ Δ = − ⎜ ⎝ ∂ ⎠ 2 (II.26) p The values for the thermodynamic functions of dissolution of oxygen in the different compounds at 298.15 K are listed in Table II.15. Table II.15. Thermodynamic properties of solvation for oxygen in different perfluoroalkanes at 298.15 K. Solvent ΔG2 * ΔH2 * ΔS2 * kJ.mol -1 kJ.mol -1 J.mol -1 K -1 C6F14 1.79 - 13.41 - 50.98 C7F16 1.81 - 9.66 - 38.47 C8F18 1.74 - 4.36 - 20.44 C9F20 1.80 - 4.40 - 20.81 1Br-C8F17 1.92 - 2. 06 - 13.36 1H-C8F17 1.94 - 1.64 - 12.00 1H,8H-C8F16 2.21 1.22 - 3.31 C10F18 2.17 0.05 - 7.09 - 64 -
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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
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 79 and 80: x2 (T,P2) 7.0E-03 6.0E-03 5.0E-03 4
Page 81: 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 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
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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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