ELECTROANALYTICAL SIMULATIONS .16. SIMULATION OF CONTROLLED CURRENT BULK ELECTROLYSIS EXPERIMENTS BY ORTHOGONAL COLLOCATION - GENERAL-MODELAND SIMPLE CHARGE-TRANSFER MECHANISMS

A physico-chemical model, not making assumptions about the relative ra tes of reaction steps is formulated for galvanostatic electrolysis exp eriments in either the exhaustive or the constant concentration mode. The mathematical formulation (partial differential equations with init ial and, in some cases non-linear, boundary conditions) is solved by m eans of the orthogonal collocation technique and subsequent integratio n of the ordinary differential equation system in the time domain. The approach is applied to several electrode reaction mechanisms consisti ng of one or two charge transfer steps. The principal behavior of the simulation program is demonstrated. Electrode reactions are simulated under galvanostatic conditions and results of simulation experiments f or the exhaustive and constant concentration modes of the electrolysis are discussed and compared.