Abstract
The viscosity‐average molecular weights w of [Na4Ca(PO3)6]n and [Na4Ba(PO3)6]n polymers determined by Staudinger's equation in 0.0035N NaCl solution were found to be lower than their number‐average molecular weights n determined by endgroup titration. The above anomaly has been shown to be owing to the effect of bivalent cations liberated in equilibria of the type: This has been further confirmed by measurments of w by the light scattering method. In aqueous solutions the greater change in viscosity of [Na4Ca(PO3)6]n solution with dilution is also ascribed to the secondary dissociation of the polymeric anions at lower concentrations.