Abstract
AbstractExcess heat capacities are given as functions of composition and temperature for non‐dilute aqueous solutions of poly(oxyethylene) and its oligomeric models, i. e. from the glycol monomer to tetramer and dimethyl ethers of these compounds. A theoretical model based on the concept of association equilibria was used to predict the excess heat capacities of aqueous mixtures of dimethyl ethers at 298K and 350K. Numerical values of parameters of the model were obtained by treatment of the heats of mixing reported in the first part of this study. It was sufficient to adjust two parameters of self‐association of water, and for each system also the parameter characterizing hydration of ether groups in oligomers. The agreement between theory and experiment was very good for both enthalpy and heat‐capacity data, with the exception of the concentration range rich in water, where the interaction scheme is probably more complicated.
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