
%0 Journal Article
%A Berne, A 
%A Popovych, O 
%T A New Method for the Estimation of Transfer Activity Coefficients of Ions From the E.M.F. of Cells With Liquid Junction
%J Australian Journal of Chemistry
%D 1988/10/01
%V 41
%N 10
%P 1523-1532
%K 
%R https://doi.org/10.1071/CH9881523
%U https://www.publish.csiro.au/paper/CH9881523 
%X Transfer activity coefficients of the tetraalkylammonium ions, logm&#947;R, where R+ = Me4N+, Et4N+, Pr4N+ and Bu4N+, and of the picrate ion, logm&#947;Pic, between pairs of dipolar aprotic solvents, S1 &#8594; S2, were evaluated by combining the e.m.f . of cells Ag(cryst.)|AgClO4|RX|AgClO4|Ag( cryst .)                                 S1        S2with the calculated liquid-junction potentials, Ej. The salt-bridge electrolyte RX was RClO4 and R Pic for the determinations of logm&#947;R and logm&#947;Pic, respectively, and the solvents were: acetonitrile ( MeCN ), N,N- dimethylformamide (HCONMe2), dimethyl  sulfoxide (Me2SO) and propylene carbonate ( pcar ). The logm&#947;R values showed a systematic variation with the AgClO4 concentration, apparently caused by the concentration dependence of the solvent component of the liquid-junction potential, Ej,s, neglected in the calculations. However, the above concentration dependence was virtually eliminated from the values of logm&#947;Pic when they were calculated with the aid of our concentration-dependent logm&#947;R data. For a number of our cells it was possible to evaluate the Ej,s, with the aid of literature data. The solvent component of Ej was found to be appreciable and varied both with the AgClO4 and the RX concentration. The Ej,s, was particularly large for cells containing pcar , with a maximum of -172 mV for the pcar | MeCN junction. 
