Thermodynamics of polyether solutions

Abstract

Abstract Measurements are reported of the vapor pressures and the heats and volumes of mixing of solutions of poly(ethylene glycol dimethyl ether) in chloroform and in carbon tetrachloride. The measurements have been used to calculate the thermodynamic mixing functions for mixing with zero volume change. These values have been compared with the predictions of the lattice theory of mixtures at three different levels of approximation, viz., the generalized “first approximation” theory of Barker, the “zeroth approximation” theory, and the Flory theory. In the hydrogen‐bonding chloroform solutions the Barker theory is more successful than the other forms of the lattice theory. The results have also been used, in conjunction with those for solutions of poly(propylene glycol dimethyl ether) in the same two solvents, to test the ability of the Barker theory to correlate the properties of related systems. Good correlation is found between the two carbon tetrachloride solutions but not between the chloroform solutions. It is probable that the side‐chain methyl groups in the propylene oxide repeating unit cause the hydrogen‐bonding interaction to be weaker in this polymer than it is in the polymer with the ethylene oxide repeating unit.