Non-specific Salt Effects in Polarographic Reductions¹

Polarographic Reduction of the Phenyl-Substituted Ethenes

“…It is of value, however, to consider the conclusions set forth for the general case of an irreversible electrochemical reaction (21) as an indication of the probable effect of the double layer structure on an electrochemical reaction. The situation is complicated by the fact that most of the theories evolved have not yet been rigorously tested experimentally.…”

“…Ox ~ > Ox Red [21] The predicted log plot slopes are easily derived by equivalent reaction pair treatment.…”

Chronopotentiometric Potential-Time Curves and Their Interpretation

“…To reduce complication to a minimum the only possibility discussed here will be that in which the deposited species has unit activity. With this restriction, the analog of Equation 1becomes io/nF = ksQa (Cos -1/ ) (7) Again the value of Cos can be substituted from the Sand equation and the analog of Equation 2 becomes [t[r)1/2 = 1 -(ttDy!i/2ksQ°F^-nF (^/))'V2f"eT1,2 (8) The Nernst equation is obeyed when the second term on the right-hand side becomes negligible, while irreversibility is achieved when the third term on the right-hand side is negligible. Conditions under which these simplifications are justified can be derived by analogy with the preceding section.…”

“…Meites, L., Meites, T., Anal. Chem.20,984(1948) (8). Reilley, C. X., Cooke, W. D., Furman, X. H., Ibid., 23,1030 (1951).…”

Polarographic Theory, Instrumentation, and Methodology

“…Marcus (119) has developed a theory of electron transfer processes which takes into account the effect of the double layer on electrode reactions, and brings out the parallelism of solution and electrode reactions. Reinmuth, Rogers, and Hummelstedt (156) have examined the implication of Marcus' theory for polarographic processes. The importance* of double layer structure is pointed out, and changing electrolyte composition so as to favor increased absorption of either anions or cations has been demonstrated to affect electrode behavior in a predictable way.…”