Hydrogenation, adsorbed hydrocarbons

Od-fumace blacks used by the mbber iadustry contain over 97% elemental carbon. Thermal and acetylene black consist of over 99% carbon. The ultimate analysis of mbber-grade blacks is shown ia Table 2. The elements other than carbon ia furnace black are hydrogen, oxygen, and sulfur, and there are mineral oxides and salts and traces of adsorbed hydrocarbons. The oxygen content is located on the surface of the aggregates as C O complexes. The... 

Helium [7440-59-7] M 4.0. Dried by passage through a column of Linde 5A molecular sieves and CaS04, then passed through an activated-charcoal trap cooled in liquid N2, to adsorb N2, argon, xenon and krypton. Passed over CuO pellets at 300° to remove hydrogen and hydrocarbons, over Ca chips at 600° to remove oxygen, and then over titanium chips at 700° to remove N2 [Arnold and Smith 7 Chem Soc, Faraday Trans 2 77 861 1981]. 

In discussing the reaction pathways, we believe that the general evidence leads to the conclusion that hydrogenolysis proceeds via adsorbed hydrocarbon species formed by the loss of more than one hydrogen atom from from the parent molecule, and that in these adsorbed species more than one carbon atom is, in some way, involved in bonding to the catalyst surface. In the case of ethane, this adsorption criterion is met via a 1-2 mode or a v-olefin mode. Mechanistically it is difficult to see how the latter could be involved in C—C bond rupture in ethane. With molecules larger than ethane, other reaction paths are possible One is via adsorption into the 1-3 mode, and another involves adsorption as a ir-allylic species. 

Figure 8.10 shows the application of SFG on adsorbed hydrocarbons [35], Ethylene was adsorbed on the (111) surface of platinum at 240 K, and subsequently heated to different temperatures. The spectra monitor the conversion of di-G bonded ethylene to ethylidyne (=C-CH3), via an intermediate characterized by a frequency of 2957 cm-1 attributed to the asymmetic C-H stretch of a CH3 group in the ethylidene (=CH-CH3) fragment. Somoijai and coworkers have demonstrated the usefulness of the SFG technique for in situ work with studies of ethylene hydrogenation and CO oxidation at atmospheric pressure [36]. 

According to Farkas and Farkas exchange and hydrogenation occur by two unrelated mechanisms hydrogenation involves the simultaneous addition of two chemisorbed hydrogen atoms to the physically adsorbed hydrocarbon in the van der Waals layer. 

The beginning formation of small volatile hydrocarbons is associated with the formation of about the same amount of non volatile compounds retained on the catalyst. These adsorbed hydrogen deficient hydrocarbons increase the rate of methanol consumption. They are part of the reacting system. 

We have already noted (p. 16) that the interaction of an olefin with hydrogen or deuterium may lead to the occurrence of any of a number of processes. There is much evidence to suggest that each of these processes may be accounted for by considering a number of elementary steps in which a hydrogen atom, from a meantime unspecified source, is added to or removed from an adsorbed hydrocarbon species. 

It is generally agreed that the kinetics and the distributions of deuter-ated products from the reactions of alkynes or alkadienes with deuterium are satisfactorily interpreted in terms of the consecutive addition of two hydrogen atoms, of unspecified origin, to the adsorbed hydrocarbon to yield the monoolefin. The identity of the distributions of deuteroethyl-enes from the reaction of acetylene with equilibrated and non-equil-ibrated hydrogen—deuterium mixtures also provides strong evidence for such a mechanism [91]. 

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