Solvent effect on the electrochemical reductive cleavage of carbon tetrachloride – a novel example of the deviation from the quadratic activation-driving force relationship

Electrochemical reductive cleavage of carbon tetrachloride at glassy carbon electrodes in various non-aqueous solvents follows a quadratic activation-driving force dynamics whereas the Butler-Volmer kinetics is observed in the case of benzonitrile. A relatively higher transfer coefficient value has been noticed in benzonitrile, while in rest of the solvents, the transfer coefficients are less than 0.5. In benzonitrile, both the electron transfer and bond cleavage occur in a single step with a linear activation-driving force relationship, as deduced from the low temperature voltammetric studies in conjunction with the convolution analysis.