Isotopic tracers in catalysis

Isotopic Tracers in Catalysis Aromatics from / Para Ils over Te-NaX Zeolite... 

A large fraction of Emmett s research centered around iron catalysts and the application of both radioactive and stable isotopic tracers in catalysis. His studies of the iron-synthetic ammonia system led to conclusions that remain unchallenged to this day. 

Consequent to the work of many and employing such techniques as structure variation, isotopic tracers, and stereochemistry, a large number of different adsorbed hydro bon firagments have been identified as key intermediates in various reactions of hydrocarbons. Correlation of these spedes with similar polynuclear organometallic spedes has been of interest. However, the author feels that mechanistic understanding has lagged behind some other aspects of catalysis. 

In recent years, considerable progress has been made in the elucidation of the reaction mechanism using such tools as infrared spectroscopy 34), electric conductivity 35, 36) isotopic tracer 37-39) and adsorption measurements during surface catalysis 21, 40). 

In some doublet reactions the same products may be obtained from the same reactants but in different ways. Such reactions were referred to as olistomeric and the structural conditions of their appearance were determined on the basis of the multiplet theory (348). Thus, theoretically two cases of bond fission can take place in esterification, HO—COR + H—OR and H—OCOR HO—R. The tracer method shows that the first case is realized as a rule. The half-doublet scheme expresses such experiments. The doublet indexes for the reactions in solutions disintegrate into such schemes see Balandin (37). A complete system of doublet reactions for C, H, N, 0, S, and Cl (without their isotopes) has been obtained by the author (345). It is much more detailed than Table VII and amounts to 1500 types. It was obtained by exhaustive variation of atoms and bonds in the index by means of a specially developed method based on matrix algebra and combinatorial analysis. The significance of the obtained classification for organic catalysis is similar to that of the complete system of forms in crystallography, which was derived from the groups of symmetry by Fedorov and covers all possible forms (349). 

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