Abstract
The kinetics and thermodynamics of the reversible outer-sphere electron-transfer reaction between Co(terpy) 2 2+/3+ (terpy=2,2′:6′,2″-terpyridine) and horse-heart cytochrome c III/II was studied as a function of temperature and pressure. The activation volumes for the reduction of Co(terpy) 2 3+ and oxidation of Co(terpy) 2 2+ were found to be +18.4±1.3 and −18.0±1.4 cm 3 mol −1, respectively. The overall reaction volume for the reduction of Co(terpy) 2 3+ was determined to be +33±3 cm 3 mol −1. These data are used to construct a volume profile, from which it follows that the transition state lies exactly halfway between the reactant and product states on a volume basis. The experimental results are in good agreement with the rate constant and activation volume calculated from the Marcus-Hush-Stranks-Swaddle relationships.
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