Complex Catalytic Processes by C.H. Bamford and C.F.H. Tipper (Eds.)

By C.H. Bamford and C.F.H. Tipper (Eds.)

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5 . HYDROGENATION OF ETHYLENE The hydrogenation of ethylene has been extensively studied over a wide variety of metal catalysts. In this section we review some of the results obtained for the kinetics and activation energies and from the use of deuterium as a tracer. Table 5 summarises the kinetics and activation energies observed for the hydrogenation of ethylene over a variety of metals. From these results it can be seen that, although there is some considerable variation in the precise values of the orders with respect to hydrogen and ethylene, in general the order with respect to hydrogen is commonly approximately unity and that for ethylene is zero or slightly negative.

Furthermore, the amounts of acetylene retained by “clean” and ethylene-precovered sur- 51 10101 molecules in gas pnose t x iu ") on equilibrium equilibrium with Fig. 21. Adsorption isotherm and composition of the gas phase on 2OoC. 0, 0, Total molethe surface for the adsorption of acetylene o n rhodiumsilica at 2OoC. Total cules adsorbed; s ~gas , phase acetylene; ethane. *, faces is identical. The results have been interpreted as showing that the adsorbed states of acetylene involved in retention and hydrogenation are different and that the sites involved in acetylene and ethylene adsorption are different.

This preferential loss of the 0-hydrogen atom has also been noted in propene-deuterium exchange [ 1431 on nickel catalysts, where propene-2-d, is the most favoured product. As with iron, it was concluded that a + /3 double bond migration occurred by an intramolecular hydrogen transfer, although both a /3 isomerisation and the /3 a migration were thought t o occur on the same sites with nickel. Cis-trans isomerisation was claimed t o occur by both a direct route and via a nonrepetitive olefin-alkyl interconversion.

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