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Experimental Methods, Results and Discussion Table II.6 compiles references where vapour pressure data for fluorinated compounds, higher then C6 could be found, reporting the methods and measuring conditions for each case. Comparison with data measured in this work will be performed in the following section. Table II.6. Compilation of the References Reporting Experimental Vapour Pressure Data for Fluorinated Compounds Method Sample purity (%) T range (K) Reference C6F14 Dynamic 96.5 284 - 343 Stiles et al. (1952) Static 99.98 303 - 331 Dunlap et al. (1958) Up to 1atm - Isoteniscope > 1 atm - Dynamic ≈ 100 256 - 448 Crowder et al. (1967) Static Purified* 524 - 452 Ermakov et al. (1967) P, V, T Measurements 98 433 - 449 Mousa (1978) C8F18 Dynamic Purified* 310 - 380 Kreglewski (1962) Static Purified* 368 - 502 Ermakov et al. (1967) C9F20 Static Purified* 387 - 524 Ermakov et al. (1967) C6F6 Dynamic 99.9 293 - 358 Patrick and Prosser (1964) Dynamic 99.97 310 - 362 Counsell et al. (1965) Dynamic 99.99 216 - 387 Douslin and Osborn (1965) Dynamic > 99.95 370 - 515 Evans and Tiley (1966) Static 99.995 398 - 516 Douslin et al. (1969) Dynamic 99.995 290 - 378 Ambrose (1981) Dynamic 99.95 318 - 377 Ambrose et al. (1990) C7F8 Dynamic 99.89 290 - 400 Ambrose et al. (1981) C7F14 Not reported Purified* 272 - 314 Glew et al. (1956) Dynamic 98 311 - 384 Good et al. (1959) * The authors purified the samples used but do not state the final purity. - 37 -
I.3.2. Apparatus and Procedure Experimental Methods, Results and Discussion In this work, an apparatus based on the static method was built to measure the vapour pressures of the compounds under study. A scheme of the set-up is depicted in Figure II.5. It consists mainly of a glass sample cell (A), a thermostatic bath (B), a temperature measurement system, pressure measuring system (C) and a temperature controlled glass vacuum line interconnecting the sample cell to the degassing system and to the pressure sensor. J N B E M C A F L Figure II.5. Scheme of the vapor pressure apparatus: A, Cell; B, water bath; C, pressure transducer; D, liquid nitrogen trap; E, hot water jacket protected tube; F, condenser; G, vacuum pump; H, datalogger; I, computer; J, temperature controller; L, cell temperature sensor (Pt100); M, hot-block box for the pressure sensor; N, PID temperature controller; V, high vacuum Teflon valves. For the studied temperature range, water was used as thermostatic bath fluid. The temperature in the bath was controlled with a digitally controlled immersion thermostat, Digiterm 100 (J). For temperatures below 298 K a refrigerated immersion cooling coil was used. The stability and uniformity of the temperature in the working area of the thermostatic bath was better than ± 0.01 K. - 38 - D H G I V
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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 and 52: ρ / g.cm-3 1.750 1.730 1.710 1.690
Page 55: I. 3. Vapour pressure I.3.1. Biblio
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
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Experimental Methods, Results and D
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Experimental Methods, Results and D
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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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