الفهرس 
Electrochemical measurementsOnly 14 pages are availabe for public view
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Abstract
The purpose of this work has been to generate a better understanding of the nature of electrochemical reaction mechanisms. It is made apparent that the determination of both kinetic and thermodynamic parameters of electrode reactions is considerably improved by the application of the convolution transform methods. These methods have clear application in mechanisms involving’c~cre actions (C is a chemical reaction, E is an electron transfer step) or fragments of this and their applications have been utilised in thz deduction of the mechanistic pathways within this framework that occur upon oxidation and reduction of various metallo-borane and carbonyl phosphinecomplexes in dichloromethane 1 tetrabutylarnmonium perchlorate electrolyte. It should be stressed however that even in complex mechanistic schemes the II convolution and its derivative the deconvolution can provide a very useful treatment in data analysis. For example a continuously rising ’plateau’ value in I1 can indicate that some form of regenerative process is operating. If, on cyclic sweeping, the I1 does not return to the initial value then there is possibly a following chemical reaction removing the product. The sluggishness of electron transfer in the electrode reaction is emphasised in the deconvolution where the position of the peaks have clear mechanistic implication in terms of rate of electron transfer. Deconvolutions can, in situations where there is no observed reverse peak in a cyclic voltammogram, show a clear reverse peak.