COMPARED SELECTIVITIES OF REDOX-CATALYZED AND DIRECT ELECTROCHEMICAL PROCESSES .1. REACTIONS IN WHICH PRODUCT SELECTION INVOLVES COMPETITION BETWEEN DIMERIZATION AND FIRST-ORDER REACTIONS

In reactions where product selection involves competition between dime rization and first-order steps, selectivity may change on going from d irect electrolysis to redox-catalyzed electrolysis. The variation of p roduct distribution with pertinent competition parameters is rigorousl y and quantitatively established in each case. The physical reasons un derlying this prediction are discussed. They are shown to derive from the development of a space-dependent concentration profile of the prod uct selection intermediate. The particular form that this profile take s in each case is a function of the nature and rate of the step that p roduces the key intermediate and of the rates of the follow-up steps.