Voltammetric Studies of Transport of Thallium(I) Counterions in Solutions of Polyelectrolytes in Mixed Solvents

Malgorzata Ciszkowska and Janet G. Osteryoung
Department of Chemistry North Carolina State University Raleigh, North Carolina 27695-8204

Abstract:

Transport of thallium(I) counterions was studied in solutions of poly(styrenesulfonic acid), PSSA, in mixed solvents by steady-state voltammetry at mercury microelectrodes. The diffusion coefficient values of Tl^I obtained in polyelectrolyte solutions were compared to those from solutions of p-toluenesulfonic acid, p-TSA, the simple acid, monomer analogue of PSSA. The dependence of the transport of Tl^I counterions on the dielectric constant, , of the solvent was investigated for such solvents as ethanol-, methanol-, and 1,4-dioxane-water mixtures over a wide range of -values. The diffusion coefficient of thallium(I) counterions in PSSA normalized by the diffusion coefficient in solution of the simple acid, p-TSA, was found to change proportionally to the change in the dielectric constant value of the solvent. This dependence is close to that predicted by Manning's theory. The results were obtained over a wide range of concentrations of counterions and over a wide range of concentrations of various supporting electrolytes.