Journal
JOURNAL OF APPLIED ELECTROCHEMISTRY
Volume 32, Issue 6, Pages 611-620Publisher
KLUWER ACADEMIC PUBL
DOI: 10.1023/A:1020168529893
Keywords
adsorbates; adsorption isotherms; adsorption kinetics; dimethyl thiourea; methyl thiourea; platinum; tetramethyl thiourea; thiourea
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The electrochemical response of adsorbates produced on polycrystalline Pt from thiourea, methyl thiourea, 1,3 dimethyl thiourea and tetramethyl thiourea dissolved in aqueous 0.5 M sulfuric acid are comparatively studied using electrochemical routines. The adsorption kinetics of thioureas on Pt follows an Elovich-type equation. Their saturation coverage, measured from the decrease in the H-atom electrosorption charge after correction for molecular size for steric effects, decreases as the size of the molecule producing adsorbates increases. Adsorption data fulfill the empirical Frumkin isotherm with a repulsive adsorbate-adsorbate lateral interaction term. Adsorbate electrooxidation starts at about 0.65 V vs SHE. The deprotonation of hydrogen-containing thioureas yields soluble products, their electrochemical behaviour being to some extent similar to that of formamidine disulfide. For E > 0.65 V vs SHE, the oxidation of thioureas can be described as complex processes in which intermediates compete with oxide layer formation on platinum.
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