Kinetic of oxidation of phenyl hydrazine, hydroxy ethyl hydrazine, hydrazine hydrate, ethyl carbazate and 2,4-dinitro phenyl hydrazine by 2,6-dichloroquinone-4-chloro-imide has been investigated in aqueous acetic acid-perchloric acid and aqueous acetic acid-sodium acetate mixtures. Reaction are found to be first order in oxidant and in substrate. The reactions are decelerated with the increase in the concentration of perchloric acid in acetic acid - perchloric acid mixtures. The reactions are accelerated with the increase in sodium acetate concentration in acetic acid - sodium acetate mixtures. The order of reactivity has been found to be phenyl hydrazine > hydroxy ethyl hydrazine > hydrazine hydrate > 2,4-dinitro phenyl hydrazine > ethyl carbazate. It appears that this reagent functions as an oxidizing agent it two stages: the first stage is the oxidation by hydrolytic product HOCl and the second by the other hydrolytic product 2,6-dichloroquinone. A suitable mechanism is postulated to explain the observations.

Oxidation of toluene, o-xylene, p-xylene, m-xylene naphthalene and anthracene with phenyl iodosylacetate follows second order kinetics. The reactions are strongly dependent on the permitivity of the solvent medium. The activation parameters have been computed. Side chain acetoxylation is the major reaction in the case of toluene, o-xylene and p-xylene while nuclear acetoxylation has been encountered in the case of m-xylene, naphthalene and anthracene. The mechanisms of side chain and nuclear acetoxylations are proposed, which satisfy the kinetic data obtained.

AbstractThe kinetics of the reaction between some enolizable ketones and trichloroisocyanuric acid (Z) in aqueous acid‐acetic acid medium at 35 °C show pseudo‐zero‐order and pseudo‐first‐order disappearance of (Z) in the absence and the presence of added Cl‐, respectively.

Kinetics of the Ru(I1I) and Os(VIII) catalysed oxidations of benzilic acid by Tl(OAch in aqueous acetic acid ~perchloric acid medium over the temperature range 50' -70C follow a pseudo-first order disappearance of TI(I II). In the Ru(III)-catalysed reaction the apparent pseudo-first order rate constant decreases with increase in [TI(III)]o and shows a linear dependence in [benzilic acid]o, attaining almost limiting value at higher relative [benzilic acid]o. The ratt! constant remains almost unchanged with change in [H +]. The reaction also shows an almost linear dependence in [Ru(lIl)]o and more than unit dependence on [Ru(III)]o at higher relative [Ru(lIl)]o. On the other hand, the Os(VIII)-catalysed reaction exhibits a unit order dependence each in [benzilic acid]o, [TI(III)]o and [Os(VIII)]o. Plausible mechanisms consistent with observed facts have been proposed.

Title reactions are acid catalyzed and strongly dependent on the permittivity of the medium. With Cr(VI) indene reacts faster than trans-stilbene, but with V(V), trans-stilbene reacts faster than indene. The mechanism is discussed.

The title reaction is fractional each in substrate and acid, first order in oxidant. The effec of acetic acid is marginal. The products of oxidation were identified as quinones.