A simple analytical expression for the current function has been formulated for irreversible electron transfer processes in linear sweep voltammetry (LSV). The equations pertaining to the surface concentrations of the reactants and products have been obtained using the current function. The parametric dependence of the diffusion layer thickness has also been derived and its significance pointed out. The reductive cleavage of carbon tetrachloride in N,N′-dimethylformamide (DMF) at glassy carbon electrodes is investigated for verifying the theoretical expressions. © 2004 Elsevier Ltd. All rights reserved.

M. V. Sangaranarayanan

Department Of Chemistry

Carbon tetrachloride

Computer simulation

Computer software

Diffusion

electric conductivity

Electric currents

CURRENT FUNCTION

DIFFUSION LAYER THICKNESS

IRREVERSIBLE ELECTRON TRANSFER

Linear sweep voltammetry

Surface concentration

Electron transitions

IIT Madras is a public technical and research university located in Chennai, Tamil Nadu. Founded in 1959, it is recognised as an Institute of National Importance.

IIT Madras has been ranked as the top engineering institute in India for four years in a row by the National Institutional Ranking Framework of the MHRD

It currently offers undergraduate, postgraduate and research degrees across 16 disciplines in Engineering, Sciences, Humanities and Management. About 596 faculty belonging to science and engineering departments and centres of the Institute are engaged in teaching, research and industrial consultancy.

IIT Madras

Electrochimica Acta

A systematic way of distinguishing stepwise and concerted mechanisms in reductive cleavage reactions has been formulated involving current function analysis of the voltammetric data. The electrochemical reductive cleavage of the carbon-iodine bond in 1,3-dichloro-2-iodobenzene has been analyzed from a mechanistic point of view to illustrate the methodology. 1,3-Dichloro-2- iodobenzene undergoes an initial stepwise electron transfer obeying quadratic activation-driving force relationship. The current function analysis yields the reorganization energy for the reduction of 1,3-dichloro-2-iodobenzene and the results have been verified independently using convolution potential sweep voltammetry. © 2004 Elsevier Ltd. All rights reserved.

Tetrahedron

Distinction between stepwise and concerted mechanisms in reductive cleavage reactions - Use of voltammetric current function in the analysis of non-linear kinetic laws

Russian Journal of Electrochemistry

Interfacial Catalysis, Volkov, A.G., Ed., New York: Marcel Dekker, 2003

Journal of the American Chemical Society

Reductive Cleavage of Carbon Tetrachloride in a Polar Solvent. An Example of a Dissociative Electron Transfer with Significant Attractive Interaction between the Caged Product Fragments

Journal of Electroanalytical Chemistry

Ohmic drop compensation in cyclic voltammetry at scan rates in the megavolt per second range: access to nanometric diffusion layers via transient electrochemistry

Convolutive modelling of electrochemical processes based on the relationship between the current and the surface concentration

Tables of semiintegrals

Formulation of a simple analytical expression for irreversible electron transfer processes in linear sweep voltammetry and its experimental verification

Journal	Electrochimica Acta
ISSN	00134686
Open Access	No