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Kinetics of the Cu(II) catalysed reduction of Dichrmoate by hydrogen in aqueous solutions Hahn, Edmund Alexander

Abstract

The kinetics of the Cu⁺⁺ catalysed reduction of dichromate by hydrogen in aqueous perchlorate solutions were investigated between 160° and 200°C. A significant dependence of rates on Cr[superscript](VI) was observed. The mechanism proposed to account for the kinetics gave rise to a rate law of the form [formula omitted] where the rate constant for the hydrogen activation step, k₁, is given by [formula omitted]. The rate constant ratios k₋₁/k₂ and k₋₁/k₃ are believed to be temperature independent in the temperature range under consideration, and have approximate values of 0.38 and 0.02 respectively. As a consequence of these studies a similar mechanism was proposed for the Cu⁺⁺ catalysed hydrogen-oxygen recombination reaction investigated by McDuffie and co-workers. According to this mechanism an apparent discrepancy between the observations of Halpern et al and those of the former workers can be explained.

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