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GAS SOLUBILITY OF HFCs IN ORGANIC SOLVENTS J.P.B. Almeida 1, H.C. Fachada 2, I. M. A. Fonseca 1* 1 Chemical Engineering Department, University of Coimbra, Pólo II, Pinhal de Marrocos, 3030–290 Coimbra, Portugal. 2 Electrical Engineering Department, Institute Polytechnique of Coimbra, 3030-199 Coimbra, Portugal. * e-mail: fonseca@eq.uc.pt The solubilities of HFCs in the alcohols decrease in the order: CHF 3 > CH 2 F 2 > CH 3 F > CF 4. This is corroborated by the values of Gº 2 in Table 1. This can be explained by the formation of a complex between solute/solvent molecules by means of hydrogen-bonding. Actually the presence of the strongly electron-attracting halogen atom(s) on the carbon of the solute molecule looses the hydrogen(s) and makes it available for coordination to the donor atom (of the solvent molecule). For each HFC the solubility increases with the C- content of the alcohol increases. This is related to H-bonding or association in the alcohol; i.e. solvents with strong H-bonding tendencies dissolve less the same gas those with weaker H-bonding tendencies. The comparison of the solubility with literature values in Table 2 shows a satisfactory agreement. [1] J.M. Prausnitz, R.N. Lichtenthaler, E.G. Azevedo, Molecular Thermodynamics of Fluid-Phase Equilibria, 3rd ed., Prentice Hall, Englewood Cliffs, 1999. [2] I.M.A Fonseca, J.P.B. Almeida, H.C. Fachada, Automated apparatus for gas solubility measurements, J. Chem. Thermodynamics 39 (2007) 1407-1411. [3] H.L. Clever, R. Battino, The Experimental Determination of Solubilities, edited by G.T. Hefter and R.P.T. Tomkins, Wiley, 2003, pp. 101-150. [4] M. Takenouchi, R. Kato, H. Nishiumi, J. Chem. Eng. Data 46 (2001) 746-749. [5] S. Bo, R. Battino, E. Wilhelm, J. Chem. Eng. Data 38 (1993) 611-616. [6] J. Pardo, M.C. Lopez, J. Santafe, F.M. Royo, J.S. Urieta, Fluid Phase Equilibria 109 (1995) 29-37. This work is inserted in a research program that consists mainly in the experimental and theoretical study of the effect of association [1] between solute and solvent molecules in the solubility of gases in liquids. To measure the solubility of gases in liquids an automated apparatus based on Ben-Naim-Baer and Tominaga et al designs has been implemented [2]. The accuracy of the experimental method was checked by measuring the solubility of carbon dioxide and nitrous oxide in water, being found to be 0.6%. The solubilities of hydrofluorocarbons, HFCs, (CH 3 F, CH 2 F 2, CHF 3 and CF 4 ) in lower alcohols (methanol, ethanol, 1-propanol, 1-butanol) have been determined in the temperature range [285, 310] K, at atmospheric pressure. To represent the temperature dependence of the mole fraction solubilities, the equation Rlnx 2 = A + B/T + ClnT was used. From this equation the experimental Gibbs energies, enthalpies and entropies of solution at 298 K were calculated [3]. Solubility apparatus: TB, thermostated bath; TC, temperature controller; T, thermometer; PT, pressure transducer; LA, linear actuator; PC, pressure controller; PE, Penning gauge; DIF, diffusion oil pump; TRAP, liquid N 2 trap; EQ, equilibrium vessel with connector; GB, gas burette; V1,…V6, high vacuum Teflon stopcocks; AGIT, magnetic stirrer; E, elevator. Experimental Automated apparatus [2,3] (which embodies a volumetric method) Results Calculations SystemAAD (%)Ref. CH 2 F 2 / Methanol3.9[4] CH 2 F 2 / Ethanol3.2[4] CF 4 / 1-Butanol1.9[5],[6] Table 2 Comparison of solubility results with literature values Table 1 Thermodynamic functions (J mol -1 ) obtained from Rlnx 2 = A + B/T + ClnT, at 298 K. Gas (2)Solvent (1) G20G20 H20H20 S20S20 CHF 3 Methanol9254.09-7168.81-55.11 Ethanol8884.89-11726.59-69.17 1-Propanol8250.34-9517.25-59.62 1-Butanol7720.77-13872.79-72.46 CH 3 F Methanol20486.50-244659.00-889.75 Ethanol15920.76-57274.00-245.62 1-Propanol14628.30-8124.00-76.35 1-Butanol14330.02-19192.00-112.49 CH 2 F 2 Methanol10196.86-11570.75-73.05 Ethanol9639.87-18034.80-92.87 1-Propanol8869.65-9407.77-61.33 1-Butanol8390.15-7527.62-53.42 CF 4 1-Propanol18622.35-1211.84-66.56 1-Butanol18480.83-1636.01-67.51 Abstract Conclusions AAD = (1 / N) 100 ( x 2 - x 2lit / x 2lit ) References Acknowledgements This work was carried out under Research Project POCI/EQU 44056/2002 financed by FCT – Fundação para a Ciência e Tecnologia (Portugal) and FEDER
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