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


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Abstract

A kinetic study of ethylene oxidation to acetaldehyde by p-benzoquinone in the Pd(OAc)2–HClO4−LiClO4–CH3CN–H2O 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(CH3CN)(H2O)32+ 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, HClO4, and palladium. The model takes into account previous findings on the H2O/D2O and C2H4/C2D4 kinetic isotope effects and the important role of Pd(0) quinone complexes.

About the authors

I. V. Martynov

Lomonosov Institute of Fine Chemical Technologies

Email: olegtemkin@mail.ru
Russian Federation, Moscow, 119571

G. E. Efremov

Lomonosov Institute of Fine Chemical Technologies

Email: olegtemkin@mail.ru
Russian Federation, Moscow, 119571

E. A. Bovyrina

Lomonosov Institute of Fine Chemical Technologies

Email: olegtemkin@mail.ru
Russian Federation, Moscow, 119571

E. A. Katsman

Lomonosov Institute of Fine Chemical Technologies

Email: olegtemkin@mail.ru
Russian Federation, Moscow, 119571

O. N. Temkin

Lomonosov Institute of Fine Chemical Technologies

Author for correspondence.
Email: olegtemkin@mail.ru
Russian Federation, Moscow, 119571

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