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Kinetics and Mechanism of Perborate Oxidation of Aromatic Aldehydes

Mediaen A.

Polish Journal of Chemistry

2004

Vol. 78 / nr 3

437-445

The kinetics of oxidation of benzaldehyde by sodium perborate in an acetic acid medium have been studied. The reaction is first order with respect to both oxidant concentration and to the substrate. Hydrogen ion accelerates the rate of reaction. Amechanism involving the formation of an unstable perborate ester, which decomposes to the reaction products, has been suggested. The activation parameters associated with the rate-determining step have been calculated. The effects of various functional groups on the ring at the meta, and para positions of benzaldehyde have also been examined.

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.

Generation of peracetic acid on aging of perborate solution in acetic acid: kinetics of oxidation of N-methylaniline and N,N-dimethylaniline

Karunkaran C., Palanisamy P. N.

Bulletin of the Polish Academy of Sciences. Chemistry

2001

Vol. 49, No. 1

17-26

Perborate solution in glacial acetic acid generates peracetic acid on aging, and the peracetic acid oxidation of N-methylaniline and N,N-dimethylaniline is fast. But perborate dissolved in ethylene glycol does not show the aging effect and the oxidation is smooth. The oxidation of N-methylaniline exhibits Michaelis-Menten dependence on the famine] and is apparent zero order in the oxidizing agent but the rate increases linearly with the initial concentration of perborate ([perboratejo). On the other hand, the oxidation of N,N-dimethylaniline is first order in the amine and the oxidizing agent but the rate shows Michaelis-Menten dependence on [perboratejo. The mechanism of oxidation is discussed and the rate law derived.