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Received June 22, 2001
Accepted July 18, 2001
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Distribution of Solutes Between Polymer and Supercritical Fluid by Inverse Supercritical Fluid Chromatography
School of Chemical Engineering and Technology, Yeungnam University, 214-1 Tae-dong, Kyongsan, Kyongbuk 712-749, Korea
Korean Journal of Chemical Engineering, January 2002, 19(1), 146-152(7), 10.1007/BF02706888
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Abstract
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_x000D_
distribution coefficient at infinite dilution was used to calculate the phase equilibrium at finite concentration using a ternary-phase diagram.
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References
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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)
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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)