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Experimental Methods, Results and Discussion Table II.5. Derived Coefficients of Thermal Expansion at 298.15 K, αP, of the Studied Compounds. Compound αP ×10 3 (K -1 ) C6F14 C8F18 C9F20 1Br-C8F17 1H-C8F17 1H,8H-C8F16 C10F18 C6F6 C7F8 - 35 - 1.87 ± 0.05 1.47 ± 0.04 1.38 ± 0.04 1.26 ± 0.03 1.38 ± 0.03 1.27 ± 0.02 1.12 ± 0.03 1.43 ± 0.02 1.29 ± 0.02
I. 3. Vapour pressure I.3.1. Bibliographic revision Experimental Methods, Results and Discussion There are essentially five different methods that can be used to measure vapour pressure data. The choice between them is mainly due to the different thermodynamic ranges of application of each as well as with the accuracy required for the measurements. A brief overview of the main features of each of those methods follows. Dynamic method – also called ebulliometric method, measures the boiling temperature, which pertains to a specific pressure. The recommended range of application is from 10 3 Pa up to 10 5 Pa, between 20ºC and 100ºC with an estimated repeatability up to 25% between 10 3 and 2x10 3 Pa and 1-5% between 2x10 3 and 10 5 Pa. This method has also been recommended for boiling point determination and is useful for that purpose up to 350ºC. Static method - measures, at thermodynamic equilibrium, the vapour pressure established in a closed system at a specified temperature. This method is suitable for onecomponent and multicomponent solids and liquids. The recommended range of application is from 10 Pa up to 10 5 Pa, between 0ºC and 100ºC, with an estimated repeatability of 5- 10%. Isoteniscope - this standardized method is also a static method but is usually not suitable for multicomponent systems. The recommended range of application is from 100 Pa up to10 5 Pa, between 0ºC and 100ºC, with an estimated repeatability of 5-10%. Vapour pressure balance - the quantity of substance leaving a cell per unit time through an apparatus of known size is determined under vacuum conditions in such a way that return of the substance into the cell is negligible (by measuring the pulse generated on a sensitive balance by a vapour jet or by measuring the weight loss). The recommended range of application is from 10 -3 Pa up to 1 Pa, between 0ºC and 100ºC, with an estimated repeatability of 5-20%. Gas saturation method - a stream of inert carrier gas is passed over the substance in such a way that it becomes saturated with its vapour and the vapour is then collected in a suitable trap. Measurement of the amount of material transported by a known amount of carrier gas is used to calculate the vapour pressure at a given temperature. The recommended range of application is up to 1 Pa, with an estimated repeatability of 10-30%. - 36 -
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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 53: Experimental Methods, Results and D
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
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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