Abstract
The kinetics of chromic acid oxidation of phenylphosphinic acid to phenylphosphonic acid has indicated the formation of an anhydride between HCrO4− and phenylphosphinic acid in its active PhP(OH)2 and inactive PhPH(O)OH forms. The ambiguity about the reactive form of phenylphosphinic acid arises from the fact that protonation of the anhydride leads to the same transition state which disproportionates in the rate-determining step to phosphonium ion and chromium(IV). These, through different reactions in the fast step, yield phenylphosphonic acid and chromium(III) as the final products. That HCrO4− is the reactive species of chromium(VI) is confirmed by the fact that k0 is independent of the inital [CrVI] where k0 is defined by the Equation k0=kobs[CrVI]/[HCrO4−]; kobs is the pseudo first-order rate constant with respect to chromium(VI) ([Phenyl-phosphinic acid]≫[CrVI]).
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