Aqueous Solutions of Polyvinylsulfonic Acid: Phase Separation and Specific. Interactions with Ions, Viscosity, Conductance and Potentiometry

Abstract

SEPARATION AND SPECIFIC INTERACTION WITH IONS,Aqueous solutions of polyvinylsulfonic acid and its salts with various monovalent cations, separate into two liquid phases at high concentrations of added monovalent electrolytes. The hase separation has been studied as a function of temperature, polymer and added electrolyte concentration. The pgenomenon is high1 s ecific with res ect to the monovalent electrolytes investigated. In the alkali halide series the order of s ecificity is d C f < KCl > R b d a n d KI > KBr > KC1; no phase separation occurs under similar conditions with HCl, IWl, CsCl and NH4C1. Partial se aration of K + from Na+, K + from "I+, R b + from NH4+ and Na+ from H + in mixtures containing the chlorides of %oth res ective cations has been achieved. From potentiometric and conductimetric titrations polyvinylsulfonic acid is shown to gehave as a fully ionized polyelectrolyte. Specific effects with alkali cations are shown, from viscosity and conductivity measurements, to exist also in dilute solutions of the polymer, both in the absence and in the presence of added monovalent electrolytes; they are correlated to the order of specificity of the same cations in phase separation.

Electrolytic conductivity of poly(1,3-propylene phosphate) solutions containing mono- and divalent-counterions

“…Similar behaviour was found earlier for different monovalent salts of poly(styrene sulfonic acid) [11,14,[22][23] and poly(vinyl sulfonic acid) [24]. For PPP salts of a different degree of polymerization, both the equivalent conductivity at infinite dilution (A ~ and at defined concentration C (A c) diminishes with the increase of PPP molecular weight, although this effect is rather small.…”

“…(4), has been calculated by several authors [21][22][23][24][26][27][28]. For the majority of studied polymers, this paramter was found to be dependent on polyelectrolyte concentration and the nature of the counterion pair for which it was calculated.…”

Precision Sulfonic Acid Ester Copolymers

“…Although homopolymers of vinyl sulfonic acid and vinyl sulfonate have been produced by radical polymerization, copolymer synthesis by radical chemistry is limited. [8][9][10] Additionally, most sulfonated polystyrene copolymers are produced by random post-polymerization sulfonation chemistry. [1,7] Experimental Part…”

What conjugated polyelectrolytes tell us about aggregation in polyelectrolyte/surfactant systems

“…An alternative approach is to calculate a "limiting equivalent conductivity", which characterises the conductivity in a concentration range where the interionic interactions are limited to interactions between the polyion and its counter-ion atmosphere. However, other effects, such as polarizability [69] of the PE, Onsager relaxation [70] and the molecular weight [71,72] also cannot be neglected in an overall interpretation of electrical conductivity data.…”