The Mechanism and Kinetic Models of the Catalytic Oxidation of Ethylene by p-Benzoquinone in Aqueous–Acetonitrile Solutions of Pd(II) Cationic Complexes

A kinetic study of ethylene oxidation to acetaldehyde by p -benzoquinone in the Pd(OAc) 2 –HClO 4 −LiClO 4 –CH 3 CN–H 2 O system has been carried out under conditions when palladium(II) cationic complexes exist at a molar fraction of water of 0.67 and 30°С. For a reaction that mostly lead to the for...

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Bibliographic Details
Published in:Kinetics and catalysis 2018-07, Vol.59 (4), p.436-443
Main Authors: Martynov, I. V., Efremov, G. E., Bovyrina, E. A., Katsman, E. A., Temkin, O. N.
Format: Article
Language:English
Subjects:
Acetaldehyde
Acetonitrile
Catalysis
Catalytic oxidation
Cations
Chemistry
Chemistry and Materials Science
Dependence
Ethylene
Isotopes
Oxidation
Palladium
Physical Chemistry
Quinones
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Summary:A kinetic study of ethylene oxidation to acetaldehyde by p -benzoquinone in the Pd(OAc) 2 –HClO 4 −LiClO 4 –CH 3 CN–H 2 O system has been carried out under conditions when palladium(II) cationic complexes exist at a molar fraction of water of 0.67 and 30°С. For a reaction that mostly lead to the formation ofPd(CH 3 CN)(H 2 O) 3 2+ two-route mechanism and a kinetic model have been proposed that describe adequately the experimental dependence of the reaction initial rate on the concentration of p -benzoquinone, HClO 4 , and palladium. The model takes into account previous findings on the H 2 O/D 2 O and C 2 H 4 /C 2 D 4 kinetic isotope effects and the important role of Pd(0) quinone complexes.
ISSN:0023-1584
1608-3210
DOI:10.1134/S0023158418040079