Distribution of Solutes Between Polymer and Supercritical Fluid by Inverse Supercritical Fluid Chromatography

Jae-Jin Shim

Korean Journal of Chemical Engineering, Vol.19, No.1, 146-152, January, 2002

DOI10.1007/BF02706888 Export Citation

Distribution of Solutes Between Polymer and Supercritical Fluid by Inverse Supercritical Fluid Chromatography

Jae-Jin Shim^†

School of Chemical Engineering and Technology, Yeungnam University, 214-1 Tae-dong, Kyongsan, Kyongbuk 712-749, Korea

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Two methods of inverse supercritical fluid chromatography (ISFC), frontal analysis supercritical fluid chromatography (SFC) and elution SFC, have been compared for the determination of distribution coefficients of solutes between a polymer and a supercritical CO2. The logarithm of the distribution coefficient showed monotonic decrease with the density of the supercritical fluid (SF). The abnormal-maximum behavior of solute sorption in the polymer phase was explained by the fluid and solute properties, f2P/P2 sat. Interesting open-elliptic shapes of sorption and volumefraction curves were obtained and explained with the fugacity coefficient. Correction to the capacity factor was employed to eliminate the retention due to the adsorption on the surface of the silica support. A model based on the Flory equation and the Peng-Robinson equation of state (EOS) successfully predicted the phase behavior of the ternary solutesupercritical fluid-polymer systems using only interaction parameters obtained from the binary systems. The solute distribution coefficient at infinite dilution was used to calculate the phase equilibrium at finite concentration using a ternary-phase diagram.

Keywords:Distribution Coefficient;Supercritical Fluid;Polymer;Solute;Sorption;Supercritical Fluid Chromatography;Phase Equilibrium

[References]

Bartle KD, "Theory and Principles of Supercritical Fluid Chromatography," in Supercritical Fluid Chromatography-(RSC Chromatography Monographs), Smith, R.M., Ed., The Royal Society of Chemistry, London, chap. 1 (1988)
Berens AR, Huvard GS, "Interaction of Polymers with Near-Critical Carbon Dioxide," in Supercritical Fluid Science and Technology,Johnston, K.P. and Penninger, J.M.L., eds., ACS Symposium Series 406, American Chemical Society, Washington, D.C., 207 (1989)
Berens AR, Huvard GS, Korsmeyer RW, "Application of Compressed Carbon Dioxide in the Incorporation of Additive into Polymers," Paper No. 48b, AIChE Meet., Washington, DC (1988)
Chang KH, Bae HK, Shim JJ, Korean J. Chem. Eng., 13(3), 310 (1996)
Chang SH, Park SC, Shim JJ, J. Supercrit. Fluids, 13(1), 113 (1998)
Card TW, Al-Saigh ZY, Munk P, Macromolecules, 18, 1030 (1985)
Conder JR, Young CL, "Physicochemical Measurement by Gas Chromatography," John Wiley & Sons, Chichester (1979)
Eckert CA, Ziger DH, Johnston KP, Kim S, J. Phys. Chem., 90, 2738 (1986)
Flory PJ, "Principles of Polymer Chemistry," Cornell University Press, Ithaca, NY (1969)
Kuwahara N, Okazawa T, Kaneko M, J. Polym. Sci. C: Polym. Lett., 23, 543 (1968)
McHugh MA, Krukonis VJ, "Supercritical Fluid Extraction: Principles and Practice," 2nd, Butterworths-Heinemann, Boston (1994)
Ng HJ, Robinson DB, J. Chem. Eng. Data, 23(4), 325 (1978)
Olesik SV, Steger JL, Kiba N, Roth M, Novotny MV, J. Chromatogr., 392, 165 (1987)
Paulaitis ME, Krukonis VJ, Reid RC, Rev. Chem. Eng., 1(2), 179 (1983)
Peng DY, Robinson DB, Ind. Eng. Chem. Fundam., 15(1), 59 (1976)
Prausnitz JM, Lichtenthaler RN, de Azevedo EG, "Molecular Thermodynamics of Fluid-Phase Equilibria," 3rd ed., Prentice-Hall, Upper Saddle River, NJ (1999)
Sand ML, "Method for Impregnating a Thermoplastic Polymer," U.S. Patent, 4,598,006 (1986)
Saus W, Knittel D, Schollmeyer E, Textile Res. J., 63(3), 135 (1993)
Shim JJ, "Thermodynamics and Phase Equilibria of Polymer-Solute-Supercritical Fluid Systems by Supercritical Fluid Chromatography," Ph.D. Dissertation, University of Texas at Austin, Austin, Texas (1990)
Shim JJ, Johnston KP, AIChE J., 35(7), 1097 (1989)
Shim JJ, Johnston KP, J. Phys. Chem., 95(1), 353 (1991)
Shim JJ, Johnston KP, AIChE J., 37(4), 607 (1991)
Shim JJ, Yates MZ, Johnston KP, Ind. Eng. Chem. Res., 38(10), 3655 (1999)
Shim JJ, Yates MZ, Johnston KP, Ind. Eng. Chem. Res., 40(2), 536 (2001)
van Wasen U, Swaid I, Schneider GM, Angew. Chem.-Int. Edit., 19, 575 (1980)
Yonker CR, Smith RD, J. Phys. Chem., 92, 1664 (1988)

[Related Articles]

[1] Bartle KD, "Theory and Principles of Supercritical Fluid Chromatography," in Supercritical Fluid Chromatography-(RSC Chromatography Monographs), Smith, R.M., Ed., The Royal Society of Chemistry, London, chap. 1 (1988)

[2] Berens AR, Huvard GS, "Interaction of Polymers with Near-Critical Carbon Dioxide," in Supercritical Fluid Science and Technology,Johnston, K.P. and Penninger, J.M.L., eds., ACS Symposium Series 406, American Chemical Society, Washington, D.C., 207 (1989)

[3] Berens AR, Huvard GS, Korsmeyer RW, "Application of Compressed Carbon Dioxide in the Incorporation of Additive into Polymers," Paper No. 48b, AIChE Meet., Washington, DC (1988)

[4] Chang KH, Bae HK, Shim JJ, Korean J. Chem. Eng., 13(3), 310 (1996)

[5] Chang SH, Park SC, Shim JJ, J. Supercrit. Fluids, 13(1), 113 (1998)

[6] Card TW, Al-Saigh ZY, Munk P, Macromolecules, 18, 1030 (1985)

[7] Conder JR, Young CL, "Physicochemical Measurement by Gas Chromatography," John Wiley & Sons, Chichester (1979)

[8] Eckert CA, Ziger DH, Johnston KP, Kim S, J. Phys. Chem., 90, 2738 (1986)

[9] Flory PJ, "Principles of Polymer Chemistry," Cornell University Press, Ithaca, NY (1969)

[10] Kuwahara N, Okazawa T, Kaneko M, J. Polym. Sci. C: Polym. Lett., 23, 543 (1968)

[11] McHugh MA, Krukonis VJ, "Supercritical Fluid Extraction: Principles and Practice," 2nd, Butterworths-Heinemann, Boston (1994)

[12] Ng HJ, Robinson DB, J. Chem. Eng. Data, 23(4), 325 (1978)

[13] Olesik SV, Steger JL, Kiba N, Roth M, Novotny MV, J. Chromatogr., 392, 165 (1987)

[14] Paulaitis ME, Krukonis VJ, Reid RC, Rev. Chem. Eng., 1(2), 179 (1983)

[15] Peng DY, Robinson DB, Ind. Eng. Chem. Fundam., 15(1), 59 (1976)

[16] Prausnitz JM, Lichtenthaler RN, de Azevedo EG, "Molecular Thermodynamics of Fluid-Phase Equilibria," 3rd ed., Prentice-Hall, Upper Saddle River, NJ (1999)

[17] Sand ML, "Method for Impregnating a Thermoplastic Polymer," U.S. Patent, 4,598,006 (1986)

[18] Saus W, Knittel D, Schollmeyer E, Textile Res. J., 63(3), 135 (1993)

[19] Shim JJ, "Thermodynamics and Phase Equilibria of Polymer-Solute-Supercritical Fluid Systems by Supercritical Fluid Chromatography," Ph.D. Dissertation, University of Texas at Austin, Austin, Texas (1990)

[20] Shim JJ, Johnston KP, AIChE J., 35(7), 1097 (1989)

[21] Shim JJ, Johnston KP, J. Phys. Chem., 95(1), 353 (1991)

[22] Shim JJ, Johnston KP, AIChE J., 37(4), 607 (1991)

[23] Shim JJ, Yates MZ, Johnston KP, Ind. Eng. Chem. Res., 38(10), 3655 (1999)

[24] Shim JJ, Yates MZ, Johnston KP, Ind. Eng. Chem. Res., 40(2), 536 (2001)

[25] van Wasen U, Swaid I, Schneider GM, Angew. Chem.-Int. Edit., 19, 575 (1980)

[26] Yonker CR, Smith RD, J. Phys. Chem., 92, 1664 (1988)