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New Aspects of the Brdička Reaction of Low‐Molecular Thiols; Voltammetry at Low Rate of Potential Scan
Author(s) -
Heyrovský Michael
Publication year - 2000
Publication title -
electroanalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.574
H-Index - 128
eISSN - 1521-4109
pISSN - 1040-0397
DOI - 10.1002/1521-4109(200008)12:12<935::aid-elan935>3.0.co;2-f
Subject(s) - chemistry , catalysis , horizontal scan rate , thiol , cobalt , adsorption , inorganic chemistry , electrolysis , ligand (biochemistry) , dropping mercury electrode , cyclic voltammetry , photochemistry , electrode , electrochemistry , organic chemistry , biochemistry , receptor , electrolyte
The catalytic evolution of hydrogen on mercury electrodes from solutions of thiols containing cobalt(II) ions can proceed in different ways according to the conditions of electrolysis: in the classical Brdička current at –1.7 V, at HMDE in the “P” peak, especially with low rate of potential scan, around –1.25 V, or at HMDE at –1.5 V after preelectrolysis at the foot of the Co(II) reduction step. The occurrence of the “P” peak is due to reaction in the adsorbed state, preceded by ligand catalytic reduction of the cobalt thiol complex; evolution of hydrogen is catalyzed by unstable intermediates of the surface process.