✦ LIBER ✦
Anomalously large effects of pressure on electron transfer kinetics in solution: The aqueous manganate(VI)-permanganate(VII) system
✍ Scribed by T.W. Swaddle; L. Spiccia
- Publisher
- Elsevier Science
- Year
- 1986
- Weight
- 254 KB
- Volume
- 139-140
- Category
- Article
- ISSN
- 0378-4363
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✦ Synopsis
The classical Stranks-Hush-Marcus theory of pressure effects on the rates of outer-sphere electron transfer reaction rates in solution underestimates IzaV*[; specifically, for the MnO4/MnO24 (aq) exchange, zaV*=-21.2 (observed) vs. -6.6cm 3 mol 1 (calculated). This discrepancy can best be resolved by conceding that the Mn-Mn separation ~ in the transition state is variable and pressure-sensitive in the context of non-adiabatic electron transfer within an ellipsoidal cavity with ~ -550 pm.