Molybdenum metal catalyzed reaction of ethylene

被引:7
作者
Bartlett, BF
Tysoe, WT
机构
[1] UNIV WISCONSIN, DEPT CHEM, MILWAUKEE, WI 53201 USA
[2] UNIV WISCONSIN, SURFACE STUDIES LAB, MILWAUKEE, WI 53201 USA
关键词
molybdenum; ethylene; model catalyst; product distribution; kinetic measurements;
D O I
10.1023/A:1018935916385
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The reaction of ethylene catalyzed by clean molybdenum foil is examined between 800 and 880 K. Products up to C-7 are detected in measurable quantities and hydrocarbons up to C-8 are observed. The product distribution is well described by a Schulz-Flory function where a plot of In(W-n/n) versus n, where W-n is the yield of each C-n hydrocarbon, is a good straight line. Analysis of the slope and intercept of the distribution shows that the slope has a zero-order ethylene pressure dependence and varies with temperature with an activation energy of 4.6 +/- 0.6 kcal/mol, while the intercept has a pressure dependence of 1.3 +/- 0.3 and an activation energy of 46 +/- 4 kcal/mol. A kinetic model is proposed that successfully accounts for these pressure dependences. These data suggest that the activation energy for degenerate ethylene metathesis should be 55 +/- 5 kcal/mol and that the reaction should be first order in ethylene. These kinetic parameters are in good agreement with those found experimentally for the non-degenerate metathesis of propylene.
引用
收藏
页码:37 / 42
页数:6
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