Electrochemical properties of hydrophilic weak-acid membranes from hydrolysed polyacrylonitrile—I. Effect of cross-linking and chemical composition

Abstract

Gels cross-linked to various degrees and containing various amounts of nitrile, amide and carboxylic groups were prepared by polymerizing acrylonitrile at various concentrations in aqueous 70 per cent ZnCl 2 solution and by hydrolysis of polymers for various times in HCl vapours. Chemical characteristics of gels, concentration membrane potentials, membrane functions and permselectivities in KCl solutions were determined. It was proved that under the conditions used (pH close to 7, content of acrylic acid in the copolymer only 1·4–3·9 mole %). cross-linking is the decisive factor for permselectivity and ideality of the membrane functions. Cross-linking yielded almost 100 per cent permselectivity values and a slope of the membrane function of about 55 mV/decade. Further hydrolysis impairs the ideality of membranes, since the increase in swelling outweighs the effect of the increase in concentration of the active groups. Variability of the density of the ionizable groups is not sufficient to explain differences in the behaviour of the membranes under investigation.