Kinetics and mechanism of uncatalyzed and silver(I) catalyzed oxidation of lysine by cerium(IV) in acid perchlorate medium

Yadav, M. B.; Devra, Vijay; Rani, Ashu

doi:10.5281/zenodo.5811769

2009

DOI: 10.5281/zenodo.5811769

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Kinetics and mechanism of uncatalyzed and silver(I) catalyzed oxidation of lysine by cerium(IV) in acid perchlorate medium

M. B. Yadav¹,

Vijay Devra²,

Ashu Rani³

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Oxidation of Formamidines by Cerium(IV) in Aqueous Perchlorate Solutions: A Kinetics and Mechanistic Approach

Fawzy

Zaafarany

Althagafi

et al. 2016

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The kinetics of oxidation of one of the formamidine derivatives, namely, methylaminopyrazole formamidine (MAPF) by cerium(IV) has been investigated in aqueous perchlorate solutions at a constant ionic strength of 1.2 mol dm-3 and at 25°C. The progress of the reaction was followed spectrophotometrically. The reaction exhibited a first order kinetics with respect to [Ce(IV)], whereas the order with respect to [MAPF] was found to be less than unity. The reaction rate decreased with the increase in acid concentration with a negative less than unit order. The rate of reaction was not affected by increasing either ionic strength or dielectric constant of the medium. Furthermore, addition of cerium(III) product did not affect the reaction rate. The plausible oxidation mechanism involves formation of an intermediate complex between MAPF substrate and the kinetically active species of cerium(IV) in a pre-equilibrium step which decomposes in the slow step to give free radical derived from the substrate and Ce(III). The free radical is attacked by another Ce(IV) species to yield the final oxidation products which were identified by spectral and chemical analyses as methylaminopyrazole, dimethylamine and carbon dioxide. The activation parameters have been evaluated and discussed. The rate law associated with the reaction mechanism was derived.

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Oxidation of Formamidines by Cerium(IV) in Aqueous Perchlorate Solutions: A Kinetics and Mechanistic Approach

Fawzy

Zaafarany

Althagafi

et al. 2016

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Kinetics and Mechanistic Study of Oxidation of Pyridine Derivative by Cerium(IV) in Aqueous Perchloric Acid

Fawzy¹,

Zaafarany

Tirkistani³

et al. 2016

AJPC

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The kinetics of oxidation of N, N-dimethyl-N'-(pyridin-2-yl) formamidine (Py-F) by cerium(IV) was studied spectrophotometrically in aqueous perchloric acid solutions at a constant ionic strength of 1.0 mol dm-3 and at 20°C. The reaction showed first order dependence with respect to [Ce(IV)] and less than unit order with respect to [Py-F]. The reaction exhibited negative fractional-first order kinetics with respect to [H + ]. The rate of reaction was not significantly affected by variation of either ionic strength or dielectric constant of the reaction medium. Addition of cerium(III) product did not affect the reaction rate. A suitable mechanistic scheme for the oxidation reaction has been proposed. The final oxidation products were identified as 2-aminopyridine, dimethylamine and carbon dioxide. The activation parameters have been evaluated and discussed. The rate law associated with the reaction mechanism was derived.

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Silver-Catalyzed Oxidation of Atropine Drug by Cerium(IV) in Aqueous Perchlorate Solutions: A Kinetics and Mechanistic Approach

Fawzy¹,

Zaafaray

Althagafi

et al. 2016

JDDMC

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The kinetics of oxidation of atropine drug (ATR) by cerium(IV) in aqueous perchlorate solutions in the presence of silver(I) catalyst has been studied spectrophotometrically at a constant ionic strength and temperature. The reaction showed first order dependence with respect to each [Ce(IV)] and [Ag(I)], and less than unit order kinetics with respect to [ATR]. The reaction exhibited negative fractional-first order kinetics with respect to [H + ]. Increasing ionic strength and dielectric constant of the medium increased the reaction rate. In the present work, the kinetically active species of cerium(IV) was found to be Ce(OH) 3+. Addition of Ce(III) product had no significant effect on the oxidation rate. The oxidation products of atropine were identified by spectral and chemical analyses as tropine, benzaldehyde, methanol and carbon dioxide. A plausible mechanistic scheme for the catalyzed oxidation was proposed. The activation parameters of the second order rate constant were calculated and the rate law associated with the reaction mechanism was derived.

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Kinetics and mechanism of uncatalyzed and silver(I) catalyzed oxidation of lysine by cerium(IV) in acid perchlorate medium

Cited by 4 publications

References 0 publications

Oxidation of Formamidines by Cerium(IV) in Aqueous Perchlorate Solutions: A Kinetics and Mechanistic Approach

Oxidation of Formamidines by Cerium(IV) in Aqueous Perchlorate Solutions: A Kinetics and Mechanistic Approach

Kinetics and Mechanistic Study of Oxidation of Pyridine Derivative by Cerium(IV) in Aqueous Perchloric Acid

Silver-Catalyzed Oxidation of Atropine Drug by Cerium(IV) in Aqueous Perchlorate Solutions: A Kinetics and Mechanistic Approach

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