Finitely Concentrated Partial Molar Excess Properties of Solvent/Polymer [poly(4-methylstyrene) (PMS), poly(vinylbenzyl chloride) (PVBC)] Systems

Sang Soon Park; Joong So Choi

Korean Journal of Chemical Engineering, Vol.20, No.4, 745-754, July, 2003

Sang Soon Park, and Joong So Choi^{1, †}

Institute of Technology, Chementech, Inc., Kwangwoon University Business Incubating Center, 447-1,Wolgyedong, Nowonku, Seoul 139-701, Korea
¹Department of Chemical Engineering, Kwangwoon University, 447-1, Walgyedong, Nowonku, Seoul 139-701, Korea

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The finitely concentrated activity coefficients and partial molar excess properties of solvents were measured with inverse gas chromatography (IGC) in polymer solutions containing a poly(4-methylstyrene) (PMS) or a poly(vinylbenzyl chloride) (PVBC). The experimental temperature ranges were 373.15 K to 413.15 K for PMS and 353.15 K to 393.15 K for PVBC. They were over melting point or glass transition temperature of each polymer. Ten kinds of solvents (Acetone, n-Heptane, Cyclohexane, Chloroform, Methylisobutylketone, Trichlorobenzene, Benzene, Toluene, Ethylbenzene, Chlorobenzene) that are important in the chemical engineering field were arbitrarily chosen for binary polymer solutions. The external degree of freedom of original UNIFAC-FV model was empirically modified to give flexibility to itself as a C1=A+BT from the experimental data in finite concentration. The UNIFAC-FV model included a new external degree of freedom as a function of temperature. The parameters (A, B) were estimated by correlating the activities of solvent with the modified model and extended to predict the partial molar excess properties of solvents in the finite-concentrated polymer solutions. The predicted values were compared with them by original UNIFAC-FV as well as the experimental data. The results obtained with the revised model using the new parameter showed the higher quality than the results obtained by original model.

Keywords:Inverse Gas Chromatography;Activity Coefficient;Partial Molar Excess Properties;External Degree of Freedom;UNIFAC-FV

[References]

Brockmeier NF, McCoy RW, Meyer JA, Macromolecules, 5, 464 (1972)
Beret S, Prausnitz JM, AIChE J., 21, 1123 (1975)
Bondi A, "Physical Properties of Molecular Crystals Liquids and Glasses," John Wiley & Sons, New York, London, Sydney, 225 (1968)
Brandrup J, Immergut EH, "Polymer Handbook," 3rd ed., VII-526-539 (1989)
Conder JR, Purnell JH, Trans. Faraday Soc., 64, 1505 (1968)
Conder JR, Purnell JH, Trans. Faraday Soc., 64, 3100 (1968)
Conder JR, Purnell JH, Trans. Faraday Soc., 65, 824 (1969)
Conder JR, Purnell JH, Trans. Faraday Soc., 65, 839 (1969)
Choi JS, Tochigi K, Kojima K, Fluid Phase Equilib., 111(1), 143 (1995)
Chang YH, Bonner DC, J. Appl. Polym. Sci., 19, 2457 (1975)
Chen F, Fredenslund A, Rasmussen P, Ind. Eng. Chem. Res., 29, 875 (1990)
Elbro HS, Fredenslund A, Rasmussen P, Ind. Eng. Chem. Res., 30, 2576 (1991)
Gmehling J, Rasmussen P, Fredenslund A, Ind. Eng. Chem. Process Des. Dev., 32, 118 (1982)
Holten-Anderson J, Rasmussen P, Fredenslund A, Ind. Eng. Chem. Res., 26, 1382 (1987)
High M, Danner RP, Fluid Phase Equilib., 55, 1 (1990)
Kim NH, Choi BG, Choi JS, Korean J. Chem. Eng., 13(2), 129 (1996)
Kim NH, Won YS, Choi JS, Fluid Phase Equilib., 146(1-2), 223 (1998)
Oishi T, Prausnitz JM, Ind. Eng. Chem. Process Des. Dev., 17, 333 (1978)
Patterson O, Macromolecules, 2, 672 (1962)
Patterson D, Tewari YB, Schreiber HP, Guillet JE, Macromolecules, 4, 865 (1983)
Reid RC, Prausnitz JM, Poling BE, "The Properties of Gases and Liquids," 4th ed., McGraw-Hill, New York, U.S.A., 67 (1987)
Schuster RH, Grater H, Cantow HJ, Macromolecules, 17, 619 (1984)
Tsonopoulos C, AIChE J., 20, 263 (1974)

[Related Articles]

[1] Brockmeier NF, McCoy RW, Meyer JA, Macromolecules, 5, 464 (1972)

[2] Beret S, Prausnitz JM, AIChE J., 21, 1123 (1975)

[3] Bondi A, "Physical Properties of Molecular Crystals Liquids and Glasses," John Wiley & Sons, New York, London, Sydney, 225 (1968)

[4] Brandrup J, Immergut EH, "Polymer Handbook," 3rd ed., VII-526-539 (1989)

[5] Conder JR, Purnell JH, Trans. Faraday Soc., 64, 1505 (1968)

[6] Conder JR, Purnell JH, Trans. Faraday Soc., 64, 3100 (1968)

[7] Conder JR, Purnell JH, Trans. Faraday Soc., 65, 824 (1969)

[8] Conder JR, Purnell JH, Trans. Faraday Soc., 65, 839 (1969)

[9] Choi JS, Tochigi K, Kojima K, Fluid Phase Equilib., 111(1), 143 (1995)

[10] Chang YH, Bonner DC, J. Appl. Polym. Sci., 19, 2457 (1975)

[11] Chen F, Fredenslund A, Rasmussen P, Ind. Eng. Chem. Res., 29, 875 (1990)

[12] Elbro HS, Fredenslund A, Rasmussen P, Ind. Eng. Chem. Res., 30, 2576 (1991)

[13] Gmehling J, Rasmussen P, Fredenslund A, Ind. Eng. Chem. Process Des. Dev., 32, 118 (1982)

[14] Holten-Anderson J, Rasmussen P, Fredenslund A, Ind. Eng. Chem. Res., 26, 1382 (1987)

[15] High M, Danner RP, Fluid Phase Equilib., 55, 1 (1990)

[16] Kim NH, Choi BG, Choi JS, Korean J. Chem. Eng., 13(2), 129 (1996)

[17] Kim NH, Won YS, Choi JS, Fluid Phase Equilib., 146(1-2), 223 (1998)

[18] Oishi T, Prausnitz JM, Ind. Eng. Chem. Process Des. Dev., 17, 333 (1978)

[19] Patterson O, Macromolecules, 2, 672 (1962)

[20] Patterson D, Tewari YB, Schreiber HP, Guillet JE, Macromolecules, 4, 865 (1983)

[21] Reid RC, Prausnitz JM, Poling BE, "The Properties of Gases and Liquids," 4th ed., McGraw-Hill, New York, U.S.A., 67 (1987)

[22] Schuster RH, Grater H, Cantow HJ, Macromolecules, 17, 619 (1984)

[23] Tsonopoulos C, AIChE J., 20, 263 (1974)