Hydrogenation of. ethylene

The hydrogenation of ethylene has been extensively studied over a wide variety of metal catalysts. In this section we review some of the results obtained for the kinetics and activation energies and from the use of deuterium as a tracer. 

Kinetics and activation energies for ethylene hydrogenation Rate = k Ph2 po1ua 

One of the earliest studies of the reaction of C2H4 with D2, in which a full mass spectrometric analysis of the products was performed, used a nickel wire as catalyst [115,116]. Some typical results are shown in Fig. 11. These results showed that ethylene exchange was rapid and the deutero-ethylenes are probably formed in a stepwise process in which only one deuterium atom is introduced during each residence of the ethylene molecule on the surface, that is there is a high probability of ethylene desorption from the surface. From Fig. 11(a) it can also be seen that the major initial products are ethane-d0 and ethane-d,. This is consistent with a mechanism in which hydrogen transfer occurs by the reaction 

As the reaction proceeds, the ethylene becomes progressively more deuter-ated [Fig. 11(b)] and this is reflected in a progressive growth of the more heavily deuterated ethanes in the latter stages of the reaction. These conclusions are in general agreement with those subsequently obtained for the reaction over nickel films [102] (see Table 7). 

A systemmatic study of the reaction of ethylene with deuterium over alumina-supported Group VIII metals has been reported by Bond et al. [103—105], Table 7 shows a selection of typical results together with theoretical distributions calculated as discussed in Sect. 3.4. 

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The catalytic hydrogenation of ethylene occurs on various metal catalysts, such as nickel, including active or skeletal forms produced by dissolving out... 

Figure 5-4 Enthalpy Diagram for Hydrogenation of Ethylene. The values were...

What is the average energy release per bond on breaking bonds in cubane Compare this with the energy released on hydrogenation of ethylene. 

The next simplest group of linear polymers is the vinylidcnc group. Now two of the hydrogens of ethylene are replaced by radicals. Polymethylmethacrylate (alias PMMA,... 

The Hydrogenation of ethylene ean be written as C2H4 + Hj = C2H6. It is suggested that the reaetion sequenee is ... 

Not only cationic, but also anionic, species can be retained without addition of specially designed ligands. The anionic active [FFPt(SnCl3)4] complex has been isolated from the [NEt4][SnCl3] solvent after hydrogenation of ethylene [27]. The PtCl2 precursor used in this reaction is stabilized by the ionic salt (liquid at the reaction temperature) since no metal deposition occurs at 160 °C and 100 bar. The catalytic solution can be used repeatedly without apparent loss of catalytic activity. 

Fig. 2. Pressure fall —AP (Torr) against time t (arbitrary units) in hydrogenation of acetylene on Pt/AhOa catalyst at 110°C and Pst/Pctnt 2. In the initial slow period of the reaction the main product is ethylene, and after the acceleration, further hydrogenation of ethylene to ethane predominates. From G. C. Bond and P. B. Wells, J. CaM. 4, 211 (1965).

Purely parallel reactions are e.g. competitive reactions which are frequently carried out purposefully, with the aim of estimating relative reactivities of reactants these will be discussed elsewhere (Section IV.E). Several kinetic studies have been made of noncompetitive parallel reactions. The examples may be parallel formation of benzene and methylcyclo-pentane by simultaneous dehydrogenation and isomerization of cyclohexane on rhenium-paladium or on platinum catalysts on suitable supports (88, 89), parallel formation of mesityl oxide, acetone, and phorone from diacetone alcohol on an acidic ion exchanger (41), disproportionation of amines on alumina, accompanied by olefin-forming elimination (20), dehydrogenation of butane coupled with hydrogenation of ethylene or propylene on a chromia-alumina catalyst (24), or parallel formation of ethyl-, methylethyl-, and vinylethylbenzene from diethylbenzene on faujasite (89a). 

From the results of other authors should be mentioned the observation of a similar effect, e.g. in the oxidation of olefins on nickel oxide (118), where the retardation of the reaction of 1-butene by cis-2-butene was greater than the effect of 1-butene on the reaction of m-2-butene the ratio of the adsorption coefficients Kcia h/Kwas 1.45. In a study on hydrogenation over C03O4 it was reported (109) that the reactivities of ethylene and propylene were nearly the same (1.17 in favor of propylene), when measured separately, whereas the ratio of adsorption coefficients was 8.4 in favor of ethylene. This led in the competitive arrangement to preferential hydrogenation of ethylene. A similar phenomenon occurs in the catalytic reduction of nitric oxide and sulfur dioxide by carbon monoxide (120a). 

The catalysts thus prepared were active in the hydrogenation of ethylene and nitrogen (145a). 

A similar reaction was studied by Kowaka Jfi) who investigated the catalytic activity of palladium and its alloys with silver in the hydrogenation of ethylene. The author alluded to the poisoning effect of hydrogen pretreatment of the palladium catalyst. 

On the basis of information on the properties of the nickel-hydrogen and nickel-copper-hydrogen systems available in 1966 studies on the catalytic activity of nickel hydride as compared with nickel itself were undertaken. As test reactions the heterogeneous recombination of atomic hydrogen, the para-ortho conversion of hydrogen, and the hydrogenation of ethylene were chosen. 

Kolbel and Maennig (K11, K18, Ml) studied the hydrogenation of ethylene catalyzed by Raney-nickel suspended in hydrogenated Kogasin II. A... 

Slesser and Highet (SI5) have reported on a theoretical and experimental study of hydrogenation of ethylene catalyzed by Raney-nickel. 

Ciebien J.F., Cohen R.E., and Duran A., Catal3ftic properties of palladium nanoclusters synthesized within diblock copolymer films Hydrogenation of ethylene and propylene, Supramol. Sci., 5, 31, 1998. 

Mixed-valence Ru"-Ru" paddlewheel carboxylate complexes also have potential for oxidation reactions after incorporation in a microporous lattice with porphyrinic ligands. This MOF can be used for oxidation of alcohols and for hydrogenation of ethylene. Both the porosity of the lattice and the abihty of the diruthenium centers to chemisorb dioxygen are essential for the performance of the catalyst [62, 64]. 

Figure 6.38. Potential energy diagram for the hydrogenation of ethylene to the ethyl (C2H5) intermediate on a palladium(m) surface. The zero of energy has been set at that of an adsorbed H atom, (a) Situation at low coverage ethylene adsorbed in the relatively stable di-cr bonded mode, in which the two carbon atoms bind to two metal atoms. In the three-centered transition state, hydrogen and carbon bind to the same metal atom, which leads to a considerable increase in the energy...

Except for support effects, structure sensitivity has usually appeared in one of two aspects, variation of rate with svirface crystal face or with particle size. In ICC 1 Gwathmey reported in one of the first experiments with single crystal faces that different faces machined fi om Ni single crystal spheres catalyzed the hydrogenation of ethylene at different rates (ICC 1 paper 5). 

The kinetics of ethylene hydrogenation on small Pt crystallites has been studied by a number of researchers. The reaction rate is invariant with the size of the metal nanoparticle, and a structure-sensitive reaction according to the classification proposed by Boudart [39]. Hydrogenation of ethylene is directly proportional to the exposed surface area and is utilized as an additional characterization of Cl and NE catalysts. Ethylene hydrogenation reaction rates and kinetic parameters for the Cl catalyst series are summarized in Table 3. The turnover rate is 0.7 s for all particle sizes these rates are lower in some cases than those measured on other types of supported Pt catalysts [40]. The lower activity per surface... 

In the foregoing it has been discus.sed how a metal can dissociate H2. Fig. 3.6 explains the principle of catalysis with an example of the hydrogenation of ethylene, for which dissociative chemisorption of hydrogen is an elementary step in the catalytic cycle. The adsorption of alkenes, on the other hand, is non-dissociative. 

Adsorbed hydrogen atoms which are the intermediates of reaction 8 can be used for the hydrogenation of ethylene and acetylene. The light driven reaction occurs according to the following scheme ... 

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