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Kinetics and mechanism of Rh(III) catalyzed oxidation of styrene, stilbene and phenylacetylene by acid periodate
Author(s) -
Radhakrishnamurti P. S.,
Misra S. A.
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.550140605
Subject(s) - phenylacetylene , chemistry , styrene , catalysis , periodate , sodium periodate , kinetics , solvent , photochemistry , reaction mechanism , aqueous solution , medicinal chemistry , polymer chemistry , organic chemistry , copolymer , physics , quantum mechanics , polymer
Abstract The kinetics of Rh(III) catalyzed oxidative cleavage of styrene, stilbene, and phenylacetylene by periodate have been investigated in the presence of HClO 4 in aqueous acetic acid medium. The kinetic orders are completely dependent on the nature of unsaturation. In the cases of styrene and stilbene the reactions are first order in the oxidant and Rh(III), zero order with respect to the substrate, and independent of [H + ], whereas in the case of phenyl acetylene the reaction is zero order with respect to the oxidant and first order with respect to the substrate and Rh(III). The reaction is independent of [H + ] in the range of 0.01−0.05 M studied. A mechanism involving higher Rh(V) species has been postulated in the case of styrene as well as stilbene, and metal ion catalyzed hydration has been postulated in case of phenylacetylene. The influence of the solvent has been investigated, and a comparative analysis of the kinetic orders of styrene and stilbene is made with those of phenylacetylene.