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Kinetics and mechanism of the oxidation of halotoluenes by acidic hexacyanoferrate(III)
Author(s) -
Bhattacharjee A. K.,
Mahanti M. K.
Publication year - 1982
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.550141005
Subject(s) - chemistry , perchloric acid , acetic acid , aldehyde , kinetic isotope effect , aqueous solution , hammett equation , kinetics , substrate (aquarium) , inorganic chemistry , reaction rate , reaction mechanism , photochemistry , organic chemistry , catalysis , reaction rate constant , deuterium , physics , oceanography , quantum mechanics , geology
The oxidation of halotoluenes by hexacyanoferrate(III) in aqueous acetic acid containing perchloric acid (0.5 M ) at 50°C gave the corresponding aldehyde as the major product, and a small amount of polymeric material. The order with respect to each of the reactants—substrate, oxidant, and acid—was found to be unity. Increasing proportions of acetic acid increased the rate of the reaction. The reaction was influenced by changes in temperature, and the activation parameters have been evaluated. The Hammett plot yielded a ρ + value of −1.8. A kinetic isotope effect k H / k D = 6.0 has been observed. The pathway for the conversion of the halotoluenes to the products has been mechanistically visualized as proceeding through the benzylic radical intermediate, formed in the rate‐determining step of the reaction. The radical undergoes rapid conversion to the products.