Scheme of squares: Part I. Systems formalism for potentiostatic studies

Seralathan, M. ; Rangarajan, S. K. (1985) Scheme of squares: Part I. Systems formalism for potentiostatic studies Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, 191 (2). pp. 209-228. ISSN 0022-0728

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The so-called "Scheme of Squares", displaying an interconnectivity of heterogeneous electron transfer and homogeneous (e.g., proton transfer) reactions, is analysed. Explicit expressions for the various partial currents under potentiostatic conditions are given. The formalism is applicable to several electrode geometries and models (e.g., semi-infinite linear diffusion, rotating disk electrodes, spherical or cylindrical systems) and the analysis is exact. The steady-state (t→∞) expressions for the current are directly given in terms of constant matrices whereas the transients are obtained as Laplace transforms that need to be inverted by approximation of numerical methods. The methodology employs a systems approach which replaces a system of partial differential equations (governing the concentrations of the several electroactive species) by an equivalent set of difference equations obeyed by the various partial currents.

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ID Code:81238
Deposited On:04 Feb 2012 12:35
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