THEORY OF POLAROGRAPHIC KINETIC CURRENTS FOR SECOND-ORDER REGENERATION REACTIONS AT SPHERICAL ELECTRODES .2. NUMERICAL SOLUTION OF INTEGRAL EQUATIONS FOR STEADY-STATE BEHAVIOR

A numerical method is described for solving the nonlinear, steady-state integral equation which arises in treating the second-order, one-half regeneration mechanism for large potential-step electrochemical experiments at stationary spherical electrodes. Computational procedures employed for efficiently obtaining results used in the preparation of working curves are discussed. These results demonstrate that for spherical diffusion the upper limit of the kinetic-to-diffusion current ratio is less than two and is highly dependent on the effective electrode sphericity. This numerical method is readily adaptable to first-order mechanisms which are difficult to solve analytically. © 1969, American Chemical Society. All rights reserved.