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Silver(I) and Copper(II) Catalysis for Oxidation of Histidine by Cerium(IV) in Acid Medium: A Comparative Kinetic Study
Author(s) -
Fawzy Ahmed,
Althagafi Ismail I.,
Altass Hatem M.
Publication year - 2017
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.21063
Subject(s) - chemistry , catalysis , inorganic chemistry , cerium , ionic strength , reaction rate constant , acetaldehyde , copper , histidine , sulfuric acid , aqueous solution , kinetics , organic chemistry , ethanol , physics , quantum mechanics , enzyme
The catalytic effect of silver(I) and copper(II) ions on the oxidation of histidine by cerium(IV) in aqueous sulfuric acid solutions was studied spectrophotometrically at a constant ionic strength of 3.0 mol dm −3 and at 25°C. In both uncatalyzed and metal ions‐catalyzed paths, the reactions exhibited first‐order kinetics with respect to [Ce(IV)] and [catalyst], and fractional first‐order dependences with respect to [His] and [H + ]. The oxidation rates increased as the ionic strength and dielectric constant of the reactions media increased. The catalytic efficiency of Ag(I) was higher than that of Cu(II). Plausible mechanistic schemes for both uncatalyzed and catalyzed reactions were proposed, and the rate laws associated with the suggested mechanisms were derived. In both cases, the final oxidation products of histidine were identified as 2‐imidazole acetaldehyde, ammonium ion, and carbon dioxide. The activation parameters associated with the second‐order rate constants were evaluated.