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Let us consider kinetics in the studied system in
p. 4627.
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comparison with standard aqueous solutions of palla-
dium chloride complexes. Taking into account kinetic
data, ethylene oxidation occurs more slowly in the
chloride system than the oxidation of palladium(0)
complexes by quinone (with proton). Therefore, the
main contribution to material balance of the catalyst is
2−
p. 415.
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PdCl4 , PdCl3
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Therefore, in pseudo-steady state conditions (when
the concentrations of quinone and acetaldehyde,
which is the product of reaction, are much higher than
the catalyst concentration), the rates of all steps of pal-
ladium π complex transformations to form Pd(0) are
equal. The rate of a step when Pd(0) is formed is equal
to the sum of rates of its oxidation (which is regenera-
tion of the oxidized states of palladium). In aqueous
acidic solutions of palladium sulfate and perchlorate
[2–4], the steps of oxidation of Pd(0) quinone com-
plexes were considered “rate-limiting”. It has been
assumed that all of the Pd(II) rapidly transforms into
Pd(0) quinone complexes, which interact with eth-
ylene (before and after quinone protonation) and are
the main participants of the catalytic cycle. Initially,
the system does not show the complete transfer of Pd2+
into Pd(0) quinone complexes, but the steps of oxida-
tion of the latter to the corresponding hydroquinolate
complexes noticeably affect the reaction kinetics.
Note also that, in the acetonitrile system, the turnover
frequency in ethylene oxidation in the presence of pal-
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ladium cationic complexes (
= 0.87 atm,
Р
С2Н4
[HClO4] = 0.2 mol/L, [Pd]∑ = 0.0005 mol/L, [Q]0 =
0.2 mol/L) is approximately 130 times higher, than in
the solutions of chloride complexes (
= 0.87 atm,
Р
С2Н4
[HCl] = 0.05 mol/L, [Pd]∑ = 0.02 mol/L, [Q]0 =
0.1 mol/L).
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ACKNOWLEDGMENTS
This work was supported by the Russian Science
Foundation (project. 16-19-10632, G.E. Efremov).
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okislenii (π-Complexes of Olephines in Liquid-phase
Oxidation), Moscow: Nauka, 1970.
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KINETICS AND CATALYSIS
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No. 4
2018