Excess volume of polymer/solvent mixtures and proposed model for prediction of activity of solvents based on excess volume data

Density measurements were used to evaluate the excess volume of binary mixtures of poly(ethylene glycol) in water and ethanol solvents, poly(propylene glycol) in water and ethanol solvents, and poly(vinyl alcohol) in water solvent at different temperatures for various molecular weights of polymers. The excess volumes were correlated and expressed by a polynomial in terms of the weight fraction of the polymer. The activity of the solvent was expressed in terms of three parts: excess internal energy, excess entropy, and excess volume. The excess volume was derived from the expression obtained in this work, the excess entropy was derived from Flory's lattice model, and the excess internal energy was used as a weight average of the excess volume and entropy parts. The results indicated good agreement between the activity of the solvent calculated by the proposed model and the experimental data. The proposed model has the advantage that using only simple density measurements the activity values that are necessary in the calculation of thermodynamic properties can be evaluated. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1219–1227, 2005