Speciation of rhodium(III) in different acidic media has been studied by capillary zone electrophoresis (CZE). Depending on the nature of the acid, rhodium was shown to occur in the form of positive, neutral and/or negatively charged complexes. The relationship between the distribution of rhodium forms and its catalytic action on the oxidation of N-methyldiphenylamine-4-sulfonic acid by periodate ions has been investigated. It was found that only positively charged complexes of rhodium, such as those dominating in perchloric acid solutions, catalyzed a given reaction to form a colored oxidation product. The rate of the catalyzed reaction was optimized with respect to the pH, reagent and oxidant concentration levels, ionic strength, concentration of the catalyst, as well as the presence of interfering ions. The developed kinetic spectrophotometric method features rather high sensitivity (limit of determination 10 mug l(-1)) and tolerance for most platinum metals and was applied to a complex industrial sample of a platinum concentrate.
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