Ion pair formation effects in the reversible electroreduction of nitrobenzene in N,N-dimethylformamide

Summary From polarographic measurements pKass values of ion pairs formed by the nitrobenzene radical anion N− and cations M+ have been estimated. Application of the function (R+δ)−1 distinctly improved the empirical relation between E1/2ipf and ionic potentials verifying the assumption of the considerable influence of solvation effects on ion pair formation. This is also supported by a thermocycle treatment of solvation and association of ions and ion pairs.