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Mixing properties of model polymer/solvent systems

J. Chem. Phys. 103, 10315 (1995); doi:10.1063/1.469869

Issue Date: 15 December 1995

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Y.-J. Sheng and A. Z. Panagiotopoulos
School of Chemical Engineering, Cornell University, Ithaca, New York 14850-5201

S. K. Kumar
Department of Materials Science and Engineering, Pennsylvania State University, University Park, Pennsylvania 16802
Monte Carlo calculations have been performed on two nominally athermal polymer/solvent mixtures to test molecular theories of mixing properties for these systems. We first used the incremental chemical potential concept to derive an equation of state in the spirit of the generalized Flory dimer theory, without resorting to the concept of excluded volume. The resulting generalized Flory dimer-like theory and a related model, statistical associating fluid theory, were tested against simulation results for the excess volume, excess Gibbs free energy and component activity coefficients. Good agreement was obtained between the statistical associating fluid theory and computer simulations for all properties studied. The generalized Flory dimer theory, when applied self-consistently, was also able to provide quantitative predictions for the thermodynamic properties of these mixtures. An important result that emerges from our calculations is that these polymer solutions behave ideally when examined on the basis of a ``Flory-like'' reference state augmented by density effects. This asserts that the effects of molecular size disparity on system thermodynamics are properly captured by this approach. By contrast, the incompressible Flory approach fails to capture the dependence of activity coefficients on composition. ©1995 American Institute of Physics.
History: Received 12 June 1995; accepted 11 September 1995
Permalink: http://link.aip.org/link/?JCPSA6/103/10315/1
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KEYWORDS and PACS

Keywords
PACS
  • 02.70.Lq
    Mathematical methods in physics Computational techniques Monte Carlo and statistical methods
  • 36.20.Cw
    Studies of special atoms, molecules, and their ions; clusters Macromolecules and polymer molecules Molecular weights, dispersity
  • 64.75.+g
    Equations of state, phase equilibria, and phase transitions Solubility, segregation, and mixing
  • 82.60.Lf
    Physical chemistry Chemical thermodynamics Thermodynamics of solutions
  • YEAR: 1995

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PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
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