Abstract
This contribution reviews the study of polymer thermodiffusion in convectionless cells. First, the development of thermodiffusion theory is summarized. Next, the apparent independence of thermodiffusion and degree of polymerization in polymers is discussed. Thermodiffusion coefficients (D T) measured by thermal field-flow fractionation on several polymer-solvent mixtures are then summarized. Polymers include a variety of different molecular weight samples of polystyrene, poly(á-methyl styrene), polyisoprene, and polymethylmethacrylate, as well as copolymers of styrene and isoprene. Solvents include benzene, toluene, ethylbenzene, tetrahydrofuran, 2-butanone, ethyl acetate, and cyclohexane. Measured values of D T do not correlate with predictive models of thermodiffusion, but are found to correlate with polymer density and solvent viscosity. Finally, using a hydrodynamic model of polymer thermodiffusion in nonpolar solvents, an expression is derived that expresses D T in terms of physicochemical parameters that can be estimated or measured independently. These parameters include the thermal expansion coefficient, molar volume and viscosity of the solvent, the radius of a polymer repeat unit, and the Hamaker constants. The model predicts general trends in the thermodiffusion of polymethylmethacrylate and polystyrene in solvents where such parameters are available, but overestimates the values of D T by a factor of 2–4.
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References
M. E. Schimpf: ‘Thermal Field-Flow Fractionation’. In: Field-Flow Fractionation Handbook, ed. by M. E. Schimpf, K. D. Caldwell, J. C. Giddings (Wiley, New York 2000) pp. 239–256
D. Enskog: Physik Z. 12, 533 (1911)
S. Chapman: Proc. Roy. Soc. Lond. A93, 1 (1916)
K. Wirtz: Naturwissenschaften 27, 369 (1939)
K. Wirtz, J. W. Hiby: Z. Physik 44, 369 (1943)
I. Prigogine, L. de Broukere, R. Amand: Physica 16, 851 (1950)
S. Prager, H. Eyring: J. Chem. Phys. 21, 1347 (1953)
S. R. de Groot: The Thermodynamics of Irreversible Processes (Interscience, New York, 1950)
K. G. Denbigh: Trans. Faraday Soc. 48, 1 (1952)
R. J. Bearman, J. G. Kirkwood, M. Fixman: Advanc. Chem. Phys. 1, 1 (1958)
W. M. Rutherford, H. G. Drickamer: J. Chem. Phys. 22, 1157 (1954)
E. L. Doughergy, H. G. Drickamer: J. Phys. Chem. 59, 443 (1955)
A. H. Emery, H. G. Drickamer: J. Chem. Phys. 23, 2252 (1955)
T. N. Khazanovich: J. Polym. Sci. Part C 16, 2463 (1967)
P. Debye, A. M. Bueche: High Polymer Physics (Chemical Publishing, New York, 1948) pp. 497–527
F. S. Gaeta: Phs. Rev. 182, 289 (1969)
J. C. Giddings, ‘The Field-Flow Fractionation Family: Underlying Principles. In: M. E. Schimpf, K. D. Caldwell, and J. C. Giddings, Eds., Field-Flow Fractionation Handbook (Wiley, New York, 2000) pp. 3–30.
M. Martin, C. Van Batten, M. Hoyos: Anal. Chem. 69, 1339 (1997)
A. C. van Asten, G. F. M. Boelens, W. Th. Kok, P. S. Williams, J. C. Giddings: Sep. Sci. Technol. 29, 513 (1994)
M. E. Schimpf, J. C. Giddings: Macromol. 20, 1561 (1987)
M. E. Schimpf, J. C. Giddings: J. Polym. Sci., Polym. Phys. Ed. 17, 1317 (1989)
R. Sisson, J. C. Giddings: Anal. Chem. 66, 4043 (1994)
A. C. van Asten, W. Th. Kok, R. Tijssen, H. Poppe: J. Polym. Sci. B: Polym. Phys. 34, 283 (1996)
C. A. Rue, M. E. Schimpf: Anal. Chem. 66, 4054 (1994)
G. Thomaes: Physica 17, 885 (1951)
J. Xu, C. A. Rue, M. E. Schimpf: J. Liq. Chrom. & Rel. Technol. 20, 2703 (1997)
M. E. Schimpf, J. C. Giddings: J. Polym. Sci., Polym. Phys. Ed. 28, 2673 (1990)
M. E. Schimpf, L. M. Wheeler, P. F. Romeo: ACS Symp. Ser. 521, 63 (1992)
S. L. Brimhall, M. N. Myers, K. D. Caldwell, J. C. Giddings: J. Polym. Sci., Polym. Phys. 23, 2443 (1985)
J. M. Prausnitz, Moleclar Thermodynamics of Fluid Phase Equilibria. (Prentice-Hall, Englewood Cliffs, 1969)
J. Brandrup, E. H. Immergut, ed.: Polymer Handbook (Wiley, New York, 1989)
F. S. Gaeta, G. Perna, G. Scala: J. Poly. Sci. Polym. Phys. Ed. 13, 203 (1975)
M. E. Schimpf, S. M. Semenov: J. Phys. Chem. B 104, 9935 (2000)
S. Ross, I. D. Morrison: Colloidal Systems and Interfaces. (Wiley, New York, 1988)
M. Teubner: J. Chem. Phys. 76, 5564 (1982)
J. A. Riddik, W. B. Bunger, T. K. Sakano, eds.: Organic Solvents. Physical Properties and Methods of Purification (Wiley, New York, 1986)
K. S. Birdi, ed.: Handbook of Surface and Colloid Chemistry (CRC Press, New York, 1997)
J. van Oss: Interfacial Forces in Aqueous Media (Dekker, New York, 1994)
E. M. Lifshitz: Zh. Teor. Fiz. 29, 94 (1955)
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Schimpf, M.E. (2002). Thermodiffusion of Polymer Solutions in Convectionless Cells. In: Köhler, W., Wiegand, S. (eds) Thermal Nonequilibrium Phenomena in Fluid Mixtures. Lecture Notes in Physics, vol 584. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3-540-45791-7_14
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DOI: https://doi.org/10.1007/3-540-45791-7_14
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