Abstract
The Co(EDTA) − complex in aqueous solution gives rise to a specific interaction with I − ions as evidenced by a new, relatively intense band formed at 290–300 nm. This specific interaction is attributed to the formation of an ion-pair between Co(EDTA) − and I −, even though they are like charged ions. Irradiation of this ion-pair in air- equilibrated solutions with 313 nm light, causes the reduction of the Co(EDTA) − to Co(EDTA) 2− and the oxidation of the I − ion to I 3 −. The results obtained are interpreted on the basis of a mechanism in which Co(EDTA) 2− and I · are the primary photoproducts. The I · radical is then scavenged by I − to yield I 2 −, which subsequently disproportionates to I 3 − and I − and reoxidizes Co(EDTA) 2− to Co(EDTA) −. At the beginning of the photoreaction, the I 2 − decay is equally distributed on the two reaction pathways. It was possible to determine a value of 0.2 ± 0.05 for the photoreaction quantum yield and an efficiency of the primary photochemical step almost unitary. A schematic representation of the energetics of the overall reaction is reported.
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