Canadian Journal of Chemistry · 1966 · 35 citations · 2 references
Natural SciencesBiochemistryChemistryCatalysisChemical KineticsInorganic ChemistryCatalytic Reaction KineticsOxidation-reduction ReactionsRedox CatalysisRedox ChemistryRedox ProcessesRedox ReactionsIron CatalysisIron Redox ChemistryIron-catalyzed OxidationIsotopic Exchange ProcessesMechanismsMetal Ion Redox ChemistryRate-determining StepRate-determining Step Analysis
The prediction, based on earlier studies of the ruthenium(III) chloride catalyzed oxidation of H 2 by iron(III), that in the absence of iron(III) or other oxidants ruthenium(III) chloride should catalyze homogeneously the isotopic exchange between D 2 and H 2 O has been confirmed. A kinetic study was made of this exchange reaction in which the dependence of the exchange rate and of the exchange product distribution (HD:H 2 ratio) on the concentrations of ruthenium(III), hydrogen ion, and chloride ion were determined. The results, and in particular the observation that the HD:H 2 ratio of the exchange product increases with the concentrations cf H + and Cl − , support the view that the ruthenium (III)-catalyzed oxidation of D 2 by iron(III) and the D 2 –H 2 O exchange reaction proceed through related mechanisms involving a common rate-determining step in which D 2 is split heterolytically and a deuteridoruthenium(III) complex is formed.
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