Iron-ammonia catalysts surface nitrides

The reasoning which led the author to make this first shot in the dark regarding the usefulness of combinations of solid compounds as ammonia catalysts was as follows If we assume that a labile iron nitride is an interminate in the catalytic ammonia synthesis, every addition to the iron which favors the formation of the iron nitride ought to be of advantage. In other words, the hypothesis was used that surface catalysis acts via the formation of intermediate compounds between the catalyst and one or more of the reactants. An experimental support for this theory was the fact that a stepwise synthesis via the formation and successive hydrogen reduction of nitrides had been carried out with calcium nitrides (Haber), and cerium nitrides (Lipski). Later, the author found molybdenum nitride as being the best intermediate for such a stepwise synthesis. 

It should be noted that the results for the formic acid decomposition donor reaction have no bearing for ammonia synthesis. On the contrary, if that synthesis is indeed governed by nitrogen chemisorption forming a nitride anion, it should behave like an acceptor reaction. Consistent with this view, the apparent activation energy is increased from 10 kcal/mole for the simply promoted catalyst (iron on alumina) to 13-15 kcal/mole by addition of K20. Despite the fact that it retards the reaction, potassium is added to stabilize industrial synthesis catalysts. It has been shown that potassium addition stabilizes the disorder equilibrium of alumina and thus retards its self-diffusion. This, in turn, increases the resistance of the iron/alumina catalyst system to sintering and loss of active surface during use. 

Ba-Ru/BN and Ba-Ru/AC catalysts have the same reaction kinetics. When compared with the melting iron catalysts, the influence of ammonia concentration on Ba-Ru/BN catalysts is relatively small. In given reaction conditions (temperature, pressure, H2/N2 rate and concentration of ammonia etc.), the optimum activity of Ru/BN can be obtained by selecting the appropriate surface area of boron nitride, the content of Ru and promoter, size and density of grain. Moreover, the useful... 

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