Sorption and diffusion of ethanol, 1,1,1-trichloroethane (TCA), and trichloroethylene (TCE) were investigated in polydimethylsiloxane (PDMS) membranes using a gravimetric technique. The thermodynamic equilibrium and kinetic properties were evaluated at temperatures of 25, 100, and 150ЊC. The sorption isotherms for TCA and TCE can be correlated well using the Flory-Huggins model. However, a three parameter Koningsveld-Kleinjtens variation to the Flory-Huggins equation is required for correlation of the ethanol isotherm. The solubility coefficients of TCA and TCE increase with activity, but it remains almost constant for ethanol. The calculated sorption energies reveal high positive heat of mixing for ethanol. TCA and TCE sorption in PDMS decreases strongly with temperature as opposed to ethanol. Clustering function analysis is used to explain the anomalous ethanol sorption and diffusion behavior in PDMS. TCA and TCE diffusivities do not exhibit large variations with volatile organic compound activity. However, ethanol demonstrates a maxima in its diffusivity at activities where it has minimum clustering tendencies.

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