The rate of hydrogenation

The uncatalyzed addition of hydrogen to an alkene although exothermic is very slow The rate of hydrogenation increases dramatically however m the presence of cer tain finely divided metal catalysts Platinum is the hydrogenation catalyst most often used although palladium nickel and rhodium are also effective Metal catalyzed addi tion of hydrogen is normally rapid at room temperature and the alkane is produced m high yield usually as the only product... 

A mathematical model of the operating characteristics of a modem HLW storage tank has been developed (60). This model correlates experimental data for the rate of radiolytic destmction of nitric acid, the rate of hydrogen generation owing to radiolysis of water, and cooling coil heat transfer. These are all functions of nitric acid concentration and air-lift circulator operation. 

Alternatively, there are also iuhibitors that decrease the rate of hydrogen generation and thus decrease corrosion. Mercury, effective at inhibiting 2iac corrosion, has long been used as an additive to 2iac anodes. More recentiy, however, because of iacreased iaterest ia environmental issues, the amount of mercury ia alkaline cells has been reduced. 

The quaHty of the feedstock is important since it affects not only the product quaHty but the rate of hydrogenation. Some of the impurities that affect the rate are sulfur, phosphoms, haHdes, polyethylene, and moisture. Impurities are usually removed by clay treatment or by distillation (30). 

The resulting melt is cooled lapidly to prevent reversion to calcium cyanamide. The product is marketed in the form of flakes, dark gray because of the presence of carbon. Typical composition is shown in Table 7. Because the rate of hydrogen cyanide evolution is relatively high, it is readily adaptable to fumigation. Specific gravity of the product is 1.8 to 1.9. The price of black cyanide is generally lower than sodium cyanide it is manufactured in Canada and South Africa. 

A container of hydrogen at 2 bar at 27 F is damaged causing a 1 cm" sharp-edged opening What is the rate of hydrogen discharge into the atmosphere ... 

In general the rates of hydrogenation of steroidal double bonds can be roughly classified as follows a) readily hydrogenated A, A, A", A , A14 A diene, A , A ° and 19-vinyl (Z>) moderately difficult ... 

The rate of hydrogen (or deuterium) uptake with homogeneous catalysts is usually faster in benzene-alcohol (methanol or ethanol) solvent systems or in acetone than in tetrahydrofuran or in benzene alone. Whereas... 

Quantitative studies of the effect of pyridine on the rate of hydrogenation of imns-crotonic acid in the presence of a platinum catalyst have been carried out by Maxted and Walker who concluded that... 

The rate of reaction is variable requiring from 1-4 days. Fresh catalyst is added whenever the rate of hydrogen uptake markedly decreases. Added catalyst must first be wet with solvent. The hydrogen must be well evacuated, for opening the mixture to the atmosphere without such evacuation will produce a mixture that may explode on contact with fresh catalyst, t A eutectic mixture of diphenyl and diphenyl ether, available from Dow Chemical Co. 

Temperature can have an important influence on rate, selectivity, and catalyst life. In general, the rate of hydrogenation rises with increasing temperature the rate increase will be much larger when the reaction is... 

Hydrogenation of aromatic nitro compounds is very fast, and the rate is limited often by the rate of hydrogen transfer to the catalyst. It is accordingly easy to use inadvertently more catalyst than is actually necessary. Aliphatic nitro compounds are reduced much more slowly than are aromatic, and higher catalyst loadings (6,11) or relatively lengthy reduction times may be... 

Phenylhydroxylamine rearranges in sulfuric acid to give mainly p-aminophenol. Industrial routes to this compound have been developed in which phenylhydroxylamine, formed by hydrogenation of nitrobenzene in sulfuric acid over platinum-on-carbon, is rearranged as it is formed. Conditions are adjusted so that the rate of rearran ment is high relative to the rate of hydrogenation of hydroxylamine to aniline (15,17,86). An easy way to obtain a favorable rate ratio is to carry out the reduction with about 1% DMSO present in the sulfuric acid (79,81). 

Although the reactants have only limited solubility in the catalyst phase, the rates of hydrogenation in [BMIM][SbFg] are almost five times faster than for the comparable reaction in acetone. All ionic catalyst solutions tested could be reused repeatedly. The loss of rhodium through leaching into the organic phase lay below the detection limit of 0.02 %. These results are of general importance for the field of... 

Free radicals may also react with a hydrocarbon molecule from the feed by abstracting a hydrogen atom. In this case the attacking radical is terminated, and a new free radical is formed. Abstraction of a hydrogen atom can occur at any position along the chain. However, the rate of hydrogen abstraction is faster from a tertiary position than from a secondary, which is faster than from a primary position. 

It follows from equation 1.45 that the corrosion rate of a metal can be evaluated from the rate of the cathodic process, since the two are faradai-cally equivalent thus either the rate of hydrogen evolution or of oxygen reduction may be used to determine the corrosion rate, providing no other cathodic process occurs. If the anodic and cathodic sites are physically separable the rate of transfer of charge (the current) from one to the other can also be used, as, for example, in evaluating the effects produced by coupling two dissimilar metals. There are a number of examples quoted in the literature where this has been achieved, and reference should be made to the early work of Evans who determined the current and the rate of anodic dissolution in a number of systems in which the anodes and cathodes were physically separable. 

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