SATURATION KINETICS AND RELATIVE REACTIVITY OF THE DOUBLE BONDS
261
Hinshelwood equation relating the surface coverage (Θ) vation energy have been determined, and the mecha-
to the concentration of reagents (С) appears as
nism of the process has been discussed. The kinetic
parameters determined indicate that the reaction
examined is a type III hydrogenization reaction. The
cyclic diene hydrogenation kinetics obeys the Lang-
muir–Hinshelwood equation.
bDCPDСDCPD
b С
Н2 Н2
ΘDCPD
=
, ΘН2
=
, (2)
1
+ bDCPDСDCPD
1 + b С
Н2 Н2
where bDCPD and bH2 are the equilibrium constants of
dicyclopentadiene and hydrogen adsorption processes,
respectively.
REFERENCES
The reaction is zeroth-orders with respect to cyclo-
diene and hydrogen at the highest cyclodiene and
hydrogen coverages on the catalyst surface, i.e., when
their adsorption equilibrium constant (b) is sufficiently
large. At large values of the adsorption equilibrium con-
stant, bC @ 1. In this case, Θ becomes unity 1 for both
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ef
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cat
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CONCLUSIONS
When a finely dispersed palladium catalyst
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hydrogenation of cyclodienes, such as 1,5-cis,cis-
2,6
cyclooctadiene and endo-tricyclo[5.2.1.0 ]decadi-
ene-3,8 (dicyclopentadiene), at atmospheric pressure,
successive saturation of the double bonds of their mol-
ecules takes place. In the dicyclopentadiene molecule,
the double bond of the bicycloheptene moiety is
hydrogenated first. Cyclooctadiene hydrogenation to
cyclooctene proceeds via the formation of a conju-
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1
1
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bonds of the bicycloheptene and cyclopentene moieties
of the dicyclopentadiene molecule is solvent-depen-
dent. This ratio is 7–9 : 1 for aromatic solvents (toluene
and xylenes), which exert the strongest differentiating
effect. The ratio of the hydrogenation rates of cyclooct-
adiene double bonds is 10.6 for the process carried out
both in a solution and in the absence of a solvent. This
makes it possible to obtain target cyclooctene, as well as
dicyclopentene, in 98.5–99% yield at the complete
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1
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1
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Translated by E. Boltukhina
KINETICS AND CATALYSIS Vol. 58 No. 3 2017