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1 Polish Journal of Chemistry

1 2001

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Kinetic Studies on Perborate Oxidation in Non-aqueous Media. Oxidation of Diphenylamine

Karunakaran C., Reshmi S. L., Kamalam R.

Polish Journal of Chemistry

2001

Vol. 75, nr 7

1019-1029

Solution of perborate in glacial acetic acid generates peracetic acid on aging and the peracetic acid oxidation of diphenylamine is fast. Hydrogen peroxide in glacial acetic acid does not yield peracetic acid on standing; also, the hydrogen peroxide oxidation rate is only two-third of perborate. The aging effect was overcome by dissolving perborate in 1,2-diols. The oxidation in 1,2-diols-acetic acid is zero order in the oxidizing agent, whereas the same oxidation with fresh solution of perborate in acetic acid is first order with respect to the oxidizing agent. However, the rate of the former and the specific rate of the latter show first order dependence on [perborate]0. The reactions proceed via two paths, one is first order and the other is zero order in diphenylamine. In 1,2-diols-acetic acid, the perborate oxidation is slower than hydrogen peroxide. The reaction mechanism is discussed and the rate laws derived.