Vapor-liquid Equilibrium Of Polymer + Solvent Systems: Experimental Data And Thermodynamic Modeling

In this work, experimental vapor-liquid equilibrium (VLE) data for binary systems polymer + solvent were obtained using a gravimetric sorption apparatus. The studied systems were benzene + polystyrene, hexane + polystyrene, benzene + poly(methyl methacrylate), benzene + poly(ethyl methacrylate), hexane + poly(vinyl chlorate) and water + poly(vinyl chlorate), in the range of 30-40 °C. The experimental data were modeled with two group contribution models for the activity coefficient, Elbro-FV and UNIFAC-Zhong; the latter method considers the free-volume of molecules of high molecular weight, such as polymers. UNIFAC groups in the literature as well as new groups that were proposed for the monomers were used. The necessary energy interaction parameters between these groups were estimated. There were observed mean deviations between experimental and calculated mass fractions of about 8.5% with Elbro-FV, and about 17% with UNIFAC-Zhong when original groups were used, while there were observed mean deviations of about 7% with Elbro-FV and about 16% with UNIFAC-Zhong when new groups were used. The Elbro-FV model represents the experimental data with better precision in both cases; on the other hand, the data were better correlated with both models when new groups were used. © 2007 Elsevier Ltd. All rights reserved.481956465652Ballantine, D.S., Wohltjen, H., (1989) Anal Chem, 61, pp. 704-751Grate, J.W., Klusty, M., McGill, R.A., Abraham, M.H., Whiting, G., Andonian-Haftvan, J., (1992) Anal Chem, 64, pp. 610-624Napper, D.M., (1983) Polymeric stabilization of colloidal dispersions, , Academic Press, LondonFornasiero, F., Krull, F., Prausnitz, J.M., Radke, C.J., (2005) Biomaterials, 26, pp. 5704-5716High, M.S., Danner, R.P., (1990) Fluid Phase Equilib, 55, pp. 1-15Baker, R.W., Yoshiok, N., Mohr, J.M., Kahn, A.J., (1987) J Memb Sci, 31, pp. 259-271Verbrugge, M.W., Hill, R.F., Schneider, E.W., (1992) AIChE J, 38, pp. 93-100Kubota, H., Yoshino, N., Ogiwara, Y., (1990) J Appl Polym Sci, 39, pp. 1231-1239Maeda, Y., Tsuyumoto, M., Karakane, H., Tsugaya, H., (1991) Polym J, 23, pp. 501-511Wolfarth, C., (1993) Makromol Chem Theory Simul, 2, pp. 605-635Panayiotou, C.P., Vera, J.H., (1984) Polym J, 16, pp. 89-102Iwai, Y., Miyamoto, S., Nakano, K., Arai, Y., (1990) J Chem Eng Jpn, 23, pp. 508-510Wolfarth, C., (1994) Vapour-liquid equilibrium data of binary polymer solutions, vapour-liquid, Henry-constants and segment-molar excess Gibbs energies, , Elsevier, AmsterdamWang, K., Hu, Y., Wu, D.T., (1994) J Chem Eng Data, 39, pp. 916-919Gupta, R.B., Prausnitz, J.M., (1995) J Chem Eng Data, 40, pp. 784-791Gupta, R.B., Prausnitz, J.M., (1996) Fluid Phase Equilib, 117, pp. 77-83Tanbonliong, J.O., Prausnitz, J.M., (1997) Polymer, 38, pp. 5775-5783Mio, C., Jayachandran, K.N., Prausnitz, J.M., (1997) Fluid Phase Equilib, 141, pp. 165-178Mio, C., Kiritsov, S., Thio, Y., Brafman, R., Prausnitz, J.M., Hawker, C., (1998) J Chem Eng Data, 43, pp. 541-550Jayachandran, K.N., Chatterji, P.R., Prausnitz, J.M., (1998) Macromolecules, 31, pp. 2375-2377Lieu, J.G., Prausnitz, J.M., (1999) Polymer, 40, pp. 5865-5871Striolo, A., Prausnitz, J.M., (2000) Polymer, 41, pp. 1109-1117Lieu, J.G., Prausnitz, J.M., Gauthier, M., (2000) Polymer, 41, pp. 219-224Fornasiero, F., Halim, M., Prausnitz, J.M., (2000) Macromolecules, 33, pp. 8435-8442Kruger, K.M., Pfohl, O., Dohrn, R., Sadowski, G., (2006) Fluid Phase Equilib, 241, pp. 138-146Danner, R.P., High, M.S., (1993) Handbook of polymer solution thermodynamics, , DIPPR-AIChE, New YorkMio, C., Prausnitz, J.M., (1998) Polymer, 39, pp. 6401-6405Kim, J., Joung, K.C., Yoo, K.P., Bae, S.Y., (1998) Fluid Phase Equilib, 150-151, pp. 679-686Kim, J., Choi, E., Yoo, K.P., Lee, C.S., (1999) Fluid Phase Equilib, 161, pp. 283-293Elbro, H.S., Fredenslund, A., Rasmussen, P., (1990) Macromolecules, 23, pp. 4707-4714Oishi, T., Prausnitz, J.M., (1978) Ind Eng Chem Process Des Dev, 17, pp. 333-339Bondi, A., (1968) Physical properties of molecular crystals, liquids and glasses, , Wiley, New YorkZhong, C., Sato, Y., Masuoka, H., Chen, X., (1996) Fluid Phase Equilib, 123, pp. 97-106Hansen, H.K., Rasmussen, P., Fredenslund, A., Schiller, M., Gmehling, J., (1991) Ind Eng Chem Res, 30, pp. 2352-2355Fredenslund, A., Gmehling, J., Rasmussen, P., (1977) Vapour-liquid equilibria using UNIFAC, , Elsevier, AmsterdamGmehling, J., Li, J., Schiller, M., (1993) Ind Eng Chem Res, 32, pp. 178-193Nelder, J.A., Mead, R., (1965) Comput J, 7, pp. 308-313Stragevitch, L., d'Ávila, S.G., (1997) Braz J Chem Eng, 14, pp. 41-5