Hydrogen rates

Some generalizations that pertain are (1) Terminal olefins are more rapidly reduced than internal olefins (2) conjugated olefins are not reduced at 1 atmosphere (3) ethylene is not hydrogenated. Rates of reduction compare favorably with those obtained by heterogeneous catalysts such as Raney nickel or platinim oxide. In fact, the hydrogenation of some olefins may be so rapid that the temperature of the solution (benzene) is raised to the boiling point. 

Table 10.1. Dependence of the ratio of hydrogenation rates obtained by method B (presence of H and external potential control) and by method C (electrocatalytic reduction).5 ...

Table 4. Ag/Pt molar ratio and its influence on ethylene hydrogenation rates and apparent activation energy for nanoparticle encapsulated shape-controlled Pt nanoparticles [17].

Table 6. Initial hydrogenation rates in Et0H/H20 (1/1, v/v) of simple and functionalized alkenes (0.05 M) over platinum or rhodium catalysts (30 °C, 105 kPa, M/alkene = 2 x 10, mol/mol).

Figure 12. The relationship between the logarithm of the relative hydrogenation rate over CFP-supported rhodium nanoclusters, with respect to the polymer-stabilized nanostructured catalyst, for a number of a number of alkenes, as a function of their affinity to the support (expressed as the square difference of the solubility parameter of the support and of the substrate). (Reprinted from Ref [33], 1991, with permission from the American Chemical Society.)...

The effect of catalyst particle size was investigated by two different catalyst particle size fractions 63-93 pm and 150-250 pm, respectively. The effect of the particle size is very clear as demonstrated by Figure 47.2. The overall hydrogenation rate was for smaller particles 0.17 mol/min/gNi while it was 0.06 mol/min/gNi, for the larger particles, showing the presence of diffusion limitation. This kind of studies can be used to determine the effectiveness factors. The conversion levels after 70 min time-on-stream were 21% and 3%, respectively, for these two cases. 

Citral hydrogenation was carried out in parallel reactor tubes at six different temperatures to screen the temperature effect. The initial hydrogenation rates increased with increasing temperature until 45°C, thereafter the rates were about the same due to extensive catalyst deactivation, which was more prominent at higher temperatures, especially above 60°C. The results were well reproducible. 

Table 2 Effect of pore size on initial hydrogenation rate.

In the experiments carried out, the rate of hydrogenation was first order with respect to [C=C] from 30 to 90% conversion. Pseudo first order rate constants (k ) were determined for experiments over a range of conditions in order to measure the effect of different reaction parameters. The maximum hydrogenation rate constant recorded in this study was an order of magnitude less than the rate of H2 mass transfer10 and so gas uptake measurement reflected the inherent chemically controlled kinetics of the system. 

The catalyzed hydrogenation of an aldehyde- vs. a ketone-carbonyl is invariably faster because of steric effects (23), and the data for 6 vs. 10 are in line with this (eqs. 4 and 5). Thus, conversions of 6a-c after 0.5 h at standard conditions are 86, 47, and 97%, respectively, while corresponding values for lOa-c after 4 h are 78, 36 and 49%, respectively. Indeed, the aldehydes can be reduced at 25 °C under otherwise identical conditions (6b gives 38% conversion after 4 h, and 6c gives 99% after 15 h). The above reactivity trend for the ketones lOa-c shows that the hydrogenation rates depend on the substituent para to the carbonyl functionality and increase in the order H > OMe > OH. For the aldehyde susbtrates, the more limited data (substrate 6 with R = H and R = OMe was not available) suggest a similar para-substitucnt effect (at least OMe > OH). Note that this is the reverse trend to that observed for reduction of the activated C=C systems described above. 

Hydrogenation rate as a function of catalyst concentration. [Adapted from M. Zajcew, J. Am. Oil Chem. Soc., 37 (11), 1960. Used by permission of American Oil Chemists Society.]... 

Scheme 52 explains the [(Cp )Rh(MeCN)3]2+-assisted regioselective hydrogenation of pyridines, benzoquinolines, acridines as well as indoles and benzothiophene.258 The relative hydrogenation rates were attributed to both electronic and steric effects, the rate generally decreasing with increasing basicity and steric hindrance at the nitrogen atom. 

Doi and co-workers379 carried out kinetic and mechanistic studies for the hydrogenation of ethylene with [H4Ru(CO)i2] as the precatalyst. The hydrogenation rate is first-order with respect to cluster concentration, and increased to constant values with increasing ethylene and hydrogen pressure. An inverse dependence of the reaction rate on CO pressure was also observed. The mechanism proposed is in accordance with a cluster-catalyzed reaction (Scheme 74). 

Fig. 12. Variation of C2H4 hydrogenation rate with composition (118) for Cu-Ni films (O) compared with earlier results (110) using powder catalysts ( ).

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