Chemical thermodynamics of polymerization of formaldehyde in an aqueous environment

Abstract

A self‐consistent set of chemical thermodynamic values for the polymerization of formaldehyde in the gas phase and in aqueous solution is obtained with the aid of recent experimental thermochemical results and the use of selected methods of calculation of data not otherwise available. Enthalpies, entropies, and Gibbs free energies of formation are derived for the various intermediates and products, including the first six hydroxyl‐terminated oligomers. Simple equations for the logarithm of the equilibrium constant as a function of temperature are presented for a number of polymerization reactions, permitting comparison with experimental results. Reasonable agreement is obtained in almost all cases, even though ideal solutions are assumed.