The reduction of l-cystine hydrochloride at lead using static and rotating disc electrodes

Ralph, T.R., Hitchman, M.L., Millington, J.P. and Walsh, F.C. , Walsh, F.C. (ed.) (2005) The reduction of l-cystine hydrochloride at lead using static and rotating disc electrodes. Journal of Electroanalytical Chemistry, 583 (2), 260-272. (doi:10.1016/j.jelechem.2005.06.009).

Abstract

The reduction of the disulphide, l-cystine hydrochloride to the l-cysteine hydrochloride thiol, in 0.1 mol dm?3 HCl at 298 K, has been studied at pre-treated, circular, 0.50 cm2 lead disc electrodes using steady state linear sweep voltammetry, non-steady state voltammetry and controlled potential coulometry. The diffusion coefficient for l-cystine hydrochloride was approximately 4.8 × 10?10 m2 s?1 from the three techniques. Reduction of the disulphide was irreversible and hydrogen evolution occurred as a competitive reaction at approximately ?1.35 V vs. SCE. Analysis of the mixed control kinetics, using a Koutecky–Levich approach, allowed the relative roles of charge transfer and mass transport to be resolved. Anomalously high Tafel slopes, of typically ?183 mV, were observed due to disulphide adsorption. The charge transfer kinetics are consistent with the first electron gain being rate determining while reaction orders are +1 with respect to both the disulphide and proton concentrations. The mechanism of l-cystine hydrochloride reduction has been critically discussed.

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