Abstract
The oxidation of ascorbic acid (AH 2) by octacyanomolybdate(V) in a buffered acidic aqueous methanolic medium has been studied and compared with that of hexacyanoferrate(III) and octacyanotungstate(V). The reaction has been found to be first-order with respect to both oxidant concentration and ascorbic acid concentration. The dependence on acidity suggested a rate law of the form: −d[OX]/2d t = ( k a+ k b/[H +])[OX][AH 2], where k a is the rate constant of the reaction with molecular ascorbic acid and approximately equals zero for [Fe(CN) 6] 3− and [W(CN) 8] 3− and k b is the rate constant of the reaction with the ascorbate anion. The rate measurements for the three oxidants were used to calculate the entropies and enthalpies of activation. The differences in the rates of oxidation of ascorbic acid by the three oxidants, which are in the order Mo V > Fe III > W v, are discussed.
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