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The reduction of cupric salts in aqueous solutions by carbon monoxide. Byerley, John Joseph

Abstract

The kinetics of the carbon monoxide reduction of Cu(II) to Cu(I) in aqueous solutions were studied at 120°C and carbon monoxide pressures up to 1360 atm. The reduction was followed spectrophoto-metrically in a high pressure titanium cell specifically developed for studying reactions between transition metal ions and gaseous reducing agents. The observed kinetics in acetate-buffered solutions yield a rate law of the form [ Formula omitted ] The rate law describes a reaction that occurs by two parallel paths, one of which is effectively independent of pressure and is accounted for by a stable carbon monoxide complex, described by Cu(CO)+. The pressure-dependent path contains both a pH-dependent and pH-independent reaction. The observed kinetics are consistent with the following mechanism which includes the insertion of a carbon monoxide molecule between a copper ion and a co-ordinated water molecule. [ Formulas omitted ] The effect of complexing was found to be quite minor. This was further verified by studies in sulphate and perchlorate solutions.

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