Abstract
The rapid oxidation of hydrogen peroxide by CoIII has been investigated with initial [CoIII]6 × 10–4 M using stopped-flow spectrophotometry. The oscilloscope traces and the kinetics show that two intermediate complexes related by a protonation equilibrium are involved, and the decomposition of CoIIIHO 2 dominates over that of CoIIIH2O2. Heats and entropies of formation of the complexes and energies and entropies of activation for their decompositions are calculated : these differ markedly from similar quantities derived from conventional experiments with [CoIII]7 × 10–5 M, and this is discussed in terms of CoIII dimers.

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