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General Introduction paramagnetic species (Hamza et al., 1981 and Serratrice et al., 1985). The results were rationalized on the basis of the easiness of formation of cavities within the liquid rather than the existence of any specific interaction again indicating that the cavities opened by these solutes in perfluoroalkanes are significantly larger than in alkanes. Oxygen solubility depends somewhat on molecular structure. For similar molecular weight, the differences in O2 solubility can reach 20-25%. Linear perfluoroalkanes, including those that have a double bond, an oxygen atom, or a terminal bromine atom, have an advantage over the cyclic and polycyclic perfluoroalkanes (Riess, 1984). Terminal alkyl chain resulted in slightly reduced O2 solubility (Meinert and Knoblish, 1993). When perfluoroalkanes are mixed with alkanes, the deviations from ideality are positive and larger than those of nearly all other classes of mixtures containing only nonpolar and non-eletrolyte substances. The most striking consequences of the extent of the deviations are, in bulk properties, marked positive azeotopy (double azeotrope can even arise in the perfluorobenzene/benzeme system) and usually liquid-liquid immiscibility (Scott, 1958) and also in surface properties, negative aneotropy or surface azeotropy (McLure et al., 1973). Differences in chain flexibility of the two component molecules and the weak interaction energy interplay are most probably the main responsible for the occurrence of these phenomena (Calado et al., 1978). I.3. Applications The first fluorinated compounds were synthesised during the II World War, as part of the Manhattan project, when scientists were looking for a material that was able to resist to chemical attack and long-term thermal stability at high temperatures to serve as coating for volatile elements in radioactive isotope production. The importance of the inclusion of fluorine atoms in organic molecules is well documented from the number of publications/year regarding fluorinated compounds, which increased from ≈ 35 in 1960 to ≈ 910 in 2004. The first articles relating synthesis, purification and measurement of physical properties of highly fluorinated perfluoroalkanes were published in the fifties. Since then, a constant increase in the number of publications occurred till 1990. In the last fifteen years, the number of publications/year increased from ≈ 70 (in 1990) to ≈ 200 (in 2004). The increase in the number of publications verified in the last years is related with - 7 -
General Introduction the numerous applications that highly fluorinated compounds are finding in different areas including biomedical, industrial and environmental. I.3.1. Biomedical Purposes In 1966, Clark and Gollan showed that mice immersed in oxygenated silicone oil or liquid fluorocarbon could breathe (Clark and Gollan, 1966). Nowadays, the application of perfluoroalkanes for biomedical purposes is mainly being carried out using them as pure liquids for liquid ventilation or in the emulsified form, if they are to be injected. A neat fluorocarbon, C8F17Br or perflubron, is currently investigated in Phase II for treatment of acute respiratory failure by liquid ventilation (Kraft, 2001) and other liquid and gaseous perfluoroalkanes are being used as high-density intraoperative fluids for eye surgery (Miller et al., 1997). In the late 1970s, the first commercial perfluoroalkane emulsion, Fluosol-DA 20% was tested in humans. Presently at least five companies are developing a red blood cell substitute based on perfluorochemicals: Allience (Oxygent), HemoGen (Oxyfluor), Sanguine (PHERO 2), Synthetic Blood International (Oxycyte) and the Russian OJSC SPC Perftoran (Perftoran). Perfluoroalkane in water emulsions constitute safe and cost-effective vehicles for in vivo oxygen delivery. The release and uptake of gases by perfluoroalkane emulsions is facilitated once gases are dissolved in liquid perfluoroalkane and are not covalently bound to the perfluoroalkane molecules as in the case of hemoglobin. Furthermore, the perfluorochemical microdroplets that carry oxygen are 1/70 th of the size of red blood cells. They can, therefore, reach areas of the body virtually inaccessible to red blood cells and they can be easily eliminated from the organism. Phase III clinical trials conducted on such emulsions have shown that they can help in preventing the risk of oxygen deficiency in tissues, and reducing the need for donor blood transfusion during surgery. Cardiovascular, oncological and organ-preservation indications are under investigation. Potential applications of red cell blood substitute include all the situations of surgical anemia, some haemolytic anemias, ischemic disease, angioplasty, extracorporeal organ perfusion, cardioplegia (Cohn, 2000), radiotherapy of tumours (Rowinsky, 1999) and as an ultrasound contrast agent to detect myocardial perfusion abnormalities (Porter et al., 1995). The specific physicochemical properties of fluoroalkanes mentioned previously have triggered numerous applications of these compounds in the field of oxygen delivery. - 8 -
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: General Introduction order to compa
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 77 and 78:
Experimental Methods, Results and D
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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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P / MPa 6 5 4 3 2 1 0 P / MPa 14 12
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II.6. Liquid - Liquid Equilibrium I
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0 τ β Δ1 2Δ1 [ 1+ B τ + B τ +
Page 103 and 104:
References Experimental Methods, Re
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Page 107 and 108:
Page 109 and 110:
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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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