The Reliability of Standard Rate Constants for Rapid Electrochemical Reactions.
PURDUE UNIV LAFAYETTE IN DEPT OF CHEMISTRY
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A method is outlined for testing the reliability of standard rate constants for rapid electrode reactions evaluated using electrochemical perturbation techniques. This entails monitoring the response of the apparent values of rate constants to systematic alterations of the double-layer structure caused by the addition of specifically adsorbed anions. These rate responses are compared with those observed at the same potential for structurally similar, yet irreversible, reactions for which reliable rate constant - potential data can be obtained using conventional d.c. methods. The procedure is applied to rate data obtained for RuIIIII ammine redox couples by comparing the measured rate increases resulting from the addition of para toluenesulfonate anions with the corresponding rate increases seen for the irreversible reduction of CoIII ammines.
- Physical Chemistry