Abstract
The rate of oxidation of formic acid by CoIIIaq has been measured in aqueous perchlorate media over a wide range of conditions using conventional and stopped-flow spectrophotometry. The order in [CoIII] is unity and the order in [HCOOH] lies between zero and unity; the rate decreases with increasing acidity in a complex manner. The mechanism is resolved into two rate determining processes, each involving an intermediate CoIII—HCOOH complex. These two complexes have an acid–base relationship involving two protons. Values for ΔH* and ΔS* together with the ratio of rates of oxidation of HCOOH and DCOOH are compared for a range of oxidizing ions.
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Schedule a callMore From: Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases
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