Publications

An alternative approach to classical methods of electrochemical data analysis is presented. This alternative method is based on nonlinear parameter estimation and model discrimination techniques. The method is used to obtain the relevant kinetic and transport parameters and to elucidate the kinetic mechanism of 02 reduction at carbon and silver electrodes in alkaline electrolytes. © 1988, The Electrochemical Society, Inc. All rights reserved.

Ni‐P alloys were prepared by electrodeposition under different conditions on a rotating disk electrode. A variety of alloys were prepared ranging from Ni‐15P to Ni‐25P. An indirect reduction of species in solution involving several steps appears to be favored over the direct reduction at the electrode based on the low P content in the alloy. Energy dispersion x‐ray microanalysis was used to determine composition of the alloy. Transmission electron microscopy and x‐ray diffraction corroborated the amorphous nature of the structure. The physical and chemical homogeneity of the metallic glasses produced electrochemically is substantiated by the absence of electrochemical localized attack. Thus, a passivation mechanism is proposed which explains the formation of a broad range passive film in alkaline medium and also explains the narrow range of the passive film in acid and neutral media.

A general multiple electrode reaction model for electrodeposition of alloys on a rotating disk electrode is presented. Included in the model are mass transport equations with the effect of ionic migration, Butler-Volmer kinetic rate expressions, and the mole fractions of the individual components in the solid state. The model shows that the effect of ionic migration is important and that plating variables such as applied potential, pH, and bulk concentration can be included. Two examples (Ni-P and Ru-Ni-P) are used to illustrate the predictions of the model. © 1988, The Electrochemical Society, Inc. All rights reserved.

A two-dimensional mathematical model is presented for a lead dioxide electrode in a lead-acid cell. It is used to simulate the time dependent behavior of the electrode during discharge. The model contains six dependent variables: the concentration of the acid electrolyte; the porosity; the electrical potentials of the solid and solution phases; and the two directional components of the current density in the electrolyte. The effect of the electrode grid was included by varying the conductivity of the solid. Parameters such as electrode conductivity, electrode dimensions, and temperature are investigated to understand their effects on electrode discharge performance.

A mathematical model is presented for the initial corrosion rate of a porous layer on a rotating disk electrode. The model is used to predict the corrosion potential and corrosion current density for a porous electrode made of pure iron in aerated caustic solutions. The dependence of these predictions on some of the properties of the porous layer is presented. It is shown that the corrosion rate depends significantly on the specific surface area of the porous electrode.

A general mathematical model for studying the kinetics of electrochemical reactions at a rotating disk electrode under steady-state potentiostatic conditions is presented. The model, apart from predicting the net and partial current densities at given values of the applied potential, the ohmic potential drop, and the concentration and potential profiles in the solution, also accounts for homogeneous reactions of any order in the solution and noncharge transfer reactions at the electrode surface. The versatility of the model is demonstrated by the application of the model to a variety of complex reaction schemes. © 1987, The Electrochemical Society, Inc. All rights reserved.

The $\backslash$n$\backslash$nelectrode reaction with tribromide complex formation reaction in the solution, a chemical‐electrochemical (C‐E) type reaction, has been investigated in order to determine the effect of the chemical reaction on the electrode kinetics. It is shown that the chemical reaction has little effect on the electrode kinetics at very slow homogeneous reaction rates, but has a more drastic effect on the electrode kinetics at faster homogeneous reaction rates. Also, the kinetics at the electrode are affected by changes in the concentrations of the active species ($\backslash$n$\backslash$n, Br−, and$\backslash$n$\backslash$n) in the bulk solution as a consequence of the coupling effect of the chemical reaction on the electrode kinetics.

An extensive survey of the Docktor-Ingenieur Dissertationen of Jakob J6rissen and Klaus-R. Menschig, both originally from the Universitfit Dortmund, is presented in regard to the empirical modeling of membrane chlor-alkali cells and how it can be applied to a combined zero gap/attached porous electrode layer membrane cell. Particular emphasis is placed on Mensehig s work on zero gap (ZG) and attached porous electrode layer (APEL) membrane chlor-alkali cells, the first such research to appear in the open literature. Menschig developed various computer programs to characterize these ZG and APEL membrane chlor-alkali cells. He characterized these cells by using the following parameters: the current density distribution over the membrane, the species concentrations on the membrane surfaces, equivalent diffusion layer thicknesses for the mesh electrodes/current collectors and attached porous electrode layers, and the electrode overpoten-tials and equilibrium potentials using the \~urface concentrations for the ZG and APEL cell configurations. He used empirical equations first presented by J6rissen for gap membrane cells combined with his own experimental observations for a cell which used Nation TM 390, a bilayer perfluorosulfonic acid membrane, to determine values for these parameters. His empirical relations describe the dependence of the flux of OH from catholyte to anolyte as a function of catholyte caustic concentration (Cc:NaO.) and the membrane potential drop as a function of catholyte caustic (ec:N\~,,,,) and anolyte salt concentrations (Ca:N\~, \~)-By using the experimental values for total cell potential, current density, and cell outlet concentrations with the empirical equations, Menschig calculated values for the characterizing parameters mentioned above. He used these values and other information (e.g., membrane and porous electrode layer conductivity) to predict the total cell potential for the ZG configuration. With prior knowledge of total cell potential and current efficiency for corresponding APEL and ZG cell configurations, membrane surface concentrations were derived and used in the prediction of total cell potential for a combined zero gap/attached electrode cell.

A finite difference procedure is presented for solving coupled sets of partial differential equations. For one dependent variable, the procedure consists of replacing the concept of a single unknown at multiple grid points with the concept of a line of node points with multiple unknowns at each node point. The procedure is illustrated first for a second order, linear elliptic partial differential equation and then for a coupled set of non-linear elliptic partial differential equations. The method is easier to use and requires less computer storage than a banded solver method such as IMSL s routine LEQT1B. The procedure could be extended to include three spatial coordinates and time. © 1987.