Outer-sphere electron-transfer reactions of ascorbate anions

Abstract
Rate constants for the one-electron oxidation of ascorbate dianion (A2-) by bis(terpyridine)cobalt(III)ion (8.5 × 106 dm3 mol-1 s-1) and pentaammine(pyridine)ruthenium(III) ion (6.0 × 109 dm3 mol-1 s-1), and of the monoanion (HA-) by tetraammine (bipyridine)ruthenium(III)ion (2.1 × 105 dm3 mol-1s-1) have been determined in aqueous solution at 25ºC and ionic strength 0.1 (NaNO3 or NaClO4). It is shown that these rate constants, and other published rate constants for oxidation of HA- and A2-, are consistent with the Marcus cross relation, on the assumption that the self-exchange rate constants for both the HA-/HA and A2-/A-couples are 106 dm3 mol-1 s-1. One electron redox potentials for the ascorbate/dehydroascorbate system have been derived from scattered literature data.