Kinetics and mechanisms of the reaction between carbon monoxide and copper(II) in aqueous solution

Abstract

The kinetics of the reduction of copper(II) to copper(I) by carbon monoxide in aqueous solutions have been investigated at 120 °C and carbon monoxide pressures up to 1360 atm. The reaction is homogeneous and proceeds by two paths, one of which is virtually independent of carbon monoxide pressure due to the formation of a stable cuprous carbonyl complex Cu(CO)+. The second reaction path contains both a pH-dependent and pH-independent component. The rate-determining step in both paths appears to be the decomposition of a carbon monoxide insertion complex by a cupric ion. Complexing ligands such as acetate were observed to have a minor inhibiting effect on the overall reaction.