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

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There are several possibilities. (a) Dissociative adsorption of molecular hydrogen, which may occur either competitively o r non-competitively with the olefin. H2(gas)+ 2 [ * ] + H + H I I (7) * * (b) Interaction of molecular hydrogen with chemisorbed olefin. RCH=CHR’ + H2 = RCH2-€HR’ + H I * References pp. 1 1 4-1 21 I * I * 26 But-l-ene (g) 11 H,C=CH. CH:! IC\ H3C * CH, H It 11 cis-but-2-ene (g) trans-but-2-ene (g) Fig. 10. Mechanism for the isomerisation of t he n-butenes involving n-allylic intermediates.

Attempts t o interpret the mechanism of ethylene hydrogenation over nickel [96-991 and over platinum catalysts [100,101] in terms of a statistical mechanical approach have not met with any substantial success, partly due t o the limitations of the model which must be assumed in order to perform the calculations and partly due t o the complexity of the calculations themselves. Results obtained from the reaction of ethylene with deuterium have been used t o obtain information regarding the probabilities of the various changes which the adsorbed hydrocarbon species may undergo.

1 1 4-1 21 'oo 80 - - *c v 0 - 60 - 40 I f 1 I Fig. 13. Variation of the percentage chance of adsorbed ethyl reverting to adsorbed ethylene ( r * ) with temperature for various alumina-supported metals [ 1051. probability of alkyl reversal and of olefin desorption. A more quantitative interpretation would require a knowledge of the actual surface eoverages of H and D atoms during the reaction. The parameters q and s give some indication of the origins and fates of the H and D atoms. There appears to be an inverse relationship between TABLE 8 Distribution of products from the reaction of propene with deuterium Conversion a Propenes Catalyst Temp.

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