Advances in Catalysis and Related Subjects, Volume 4 by W G Frankenberg

By W G Frankenberg

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If a chain mechanism is involved in the reactions of saturated hydrocarbons, the question of the initiating step is not completely answered, although the evidence points strongly to the formation of a polarized catalyst complex from unsaturated hydrocarbons, present as impurities or formed by thermal cracking or oxidation. This complex may initiate the formation of a propagating complex by extracting a hydride ion from the saturated hydrocarbon (hydrogen transfer). It is not clear why the catalyst-hydrocarbon complex is more effective in extracting hydride ions than the catalyst, itself, but the experimental evidence from some of the work on deuterium exchange (43) indicates that this is the case.

36 37 37 ..................... 43 2. Active Intermediates. . . . . . . . . . . . . . . . . . . . . . . . . 62 VI. Copper Compounds.. . . . . . . . . . . . . . 71 VII. ,. . . . . . . 75 I. INTRODUCTION It is a measure of the complexity and variety of the chemical reactions in which hydrogen peroxide participates that they have attracted the attention of chemical kineticists for almost a hundred years, and that many of the earliest reactions to be investigated still provide matter for further investigations.

Similarly, Greensfelder and his co-workers (48) came t o substantially the same general conclusions, The papers by Thomas and by Greensfelder, Voge, and Good have given an excellent treatment of the general mechanism involved in the cracking of hydrocarbons over silica-alumina catalysts. Essentially, the mechanism postulated by the writer and by these authors is based op the formation, reaction, and stabilization of cationic or carbonium ion intermediates. The formation of a carbonium ion from a paraffin or cycloparaffin mayebe brought about by the extraction of a negative hydrogen or hydride ion : iLl H H H H H H ....

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