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Kinetics and mechanism of osmium (VIII) and ruthenium(III) catalyzed oxidation of aliphatic amines by chloramine‐T in alkaline and perchloric acid media
Author(s) -
Gupta Sushma,
Ali Vazid,
Upadhyay Santosh K.
Publication year - 1989
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.550210503
Subject(s) - chemistry , ruthenium , osmium , diethylamine , perchloric acid , triethylamine , catalysis , amine gas treating , ethylamine , chloramine t , inorganic chemistry , medicinal chemistry , photochemistry , organic chemistry
The kinetics of oxidation of aliphatic amines viz., ethylamine, n ‐butylamine, isopropylamine (primary amines), diethylamine (secondary amine), and triethylamine (tertiary amine) by chloramine‐T have been studied in NaOH medium catalyzed by osmium (VIII) and in perchloric acid medium with ruthenium(III) as catalyst. The order of reaction in [Chloramine‐T] is always found to be unity. A zero order dependence of rate with respect to each [OH − ] and [Amine] has been observed during the osmium(VIII) catalyzed oxidation of diethylamine and triethylamine while a retarding effect of [OH − ] or [Amine] on the rate of oxidation is observed in case of osmium(VIII) catalyzed oxidation of primary aliphatic amines. The ruthenium(III) catalyzed oxidation of amines follow almost similar kinetics. The order of reactions in [Amine] or [Acid] decreases from unity at higher amine or acid concentrations. The rate of oxidation is proportional to { k ′ and k ″ [Ruthenium(III)] or [Osmium(VIII)]} where k ′ and k ″ (having different values in case of ruthenium(III) and osmium(VIII)) are the rate constants for uncatalyzed and catalyzed path respectively. The suitable mechanism consisting with the kinetic data is proposed in each case and discussed.