Parahydrogen conversion palladium

When studying the kinetics of diffusion of hydrogen through palladium, Farkas (28) noticed the difference in catalytic activity of both sides of the palladium disks or tubes for the parahydrogen conversion the energy of activation was greater on the inlet side than on the outlet side, where due to extensive desorption of the hydrogen its concentration could be lower. 

The poisoning effect of hydrogen when dissolved in palladium was for the first time properly described and interpreted by Couper and Eley (29) in 1950 in their study of the fundamental importance of the development of theories of catalysis on metals. The paper and the main results relate to the catalytic effect of an alloying of gold to palladium, on the parahydrogen conversion. This system was chosen as suitable for attempting to relate catalyst activity to the nature and occupation of the electronic energy... 

Gold forms a continuous series of solid solutions with palladium, and there is no evidence for the existence of a miscibility gap. Also, the catalytic properties of the component metals are very different, and for these reasons the Pd-Au alloys have been popular in studies of the electronic factor in catalysis. The well-known paper by Couper and Eley (127) remains the most clearly defined example of a correlation between catalytic activity and the filling of d-band vacancies. The apparent activation energy for the ortho-parahydrogen conversion over Pd-Au wires wras constant on Pd and the Pd-rich alloys, but increased abruptly at 60% Au, at which composition d-band vacancies were considered to be just filled. Subsequently, Eley, with various collaborators, has studied a number of other reactions over the same alloy wires, e.g., formic acid decomposition 128), CO oxidation 129), and N20 decomposition ISO). These results, and the extent to which they support the d-band theory, have been reviewed by Eley (1). We shall confine our attention here to the chemisorption of oxygen and the decomposition of formic acid, winch have been studied on Pd-Au alloy films. 

We have, then, another example of an alloy and reaction in which the simple d-band theory has to be modified in a rather speculative way in order to explain experimental results. Actually, this is unnecessary for the formic acid reaction if we take the more recent value of about 0.4 for the number of d-band holes per palladium atom. This is not a satisfactory solution, because it is then difficult to explain the low activation energy for the parahydrogen conversion on Pd-Au alloys containing between 40 and 60% Pd. 

Fig. 17. Activation energy for parahydrogen conversion on palladium-gold alloys. The broken line denotes the paramagnetic susceptibility in arbitrary units. [Couper, A., and Eley, D. D., Discusaions Faraday Soc. 8, 172 (1950).]...

Couper, A. and Eley, D.D. "The parahydrogen conversion on palladium-gold alloys." Disc. Faraday Soc. 8 172-184 1950. 

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