D.D. Eley, Herman Pines, Paul B. Weisz (Eds.)'s Advances in Catalysis, Vol. 14 PDF

By D.D. Eley, Herman Pines, Paul B. Weisz (Eds.)

ISBN-10: 0120078147

ISBN-13: 9780120078141

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Extra resources for Advances in Catalysis, Vol. 14

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Authors tried t o correlate this with the adsorption of reaction products on the surface. It appeared, however, that preadsorption of H,O, CO,, and HCHO had no influence on the kinetics, whereas CO preadsorption gave only a weak retardation, certainly much too weak to account for the effect observed. Hydrogen preadsorption produced an effect of the same order of magnitude as CO preadsorption, but in the form of an acceleration. Thus, an explanation of the inhibited zero-order kinetics could not be found.

Presumably there will be a charge gradient developed, and the fact that there are a certain number of positive holes reaching clear back into the matrix improves the conductivity between the electrodes. There is also an equilibrium in the region where the anion gives the double negative ion as well as where the cation is produced to give the double positive ion. These are in equilibrium in the two respective phases, 2 A- < A= + AI " 2 Df 1 _ D'++ Do This kind of a process is quite different from the change that results when a charge transfer complex absorbs in the charge transfer band.

The rate of reaction r is: r = ke, so that 1 1 -==rc+- r 1 klP At high pressure the whole surface is covered by intermediates (8,= l ) , so that r=k (8) In this case the reaction rate is pressure-independent and the activation energy measured is the activation energy of the decomposition of the intermediate. At Iow pressure (1 - Oi) i5 about equal to unity so that i t follows from Eqs. (4)and (6) that r = k,p (9) Under these conditions the reaction is first-order in formic acid pressure and the activation energy measured equals that of the adsorption step.

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Advances in Catalysis, Vol. 14 by D.D. Eley, Herman Pines, Paul B. Weisz (Eds.)


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