By W.G. Frankenburg, V.I. Komarewsky, E.K. Rideal (Eds.)
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Extra resources for Advances in Catalysis, Vol. 6
13). Mitchell (41) treated theoretically the absorption of light by a monolayer, showing that the apparent quantum efficiency could be directly proportional t o the absolute temperature for certain condensed films. The molecular extinction coefficient cannot be deduced from th a t in solution; it is, however, proportional t o s i l l ? 13. Apparent quantum efficiency amofthe photochcrnical (l(cwiiipobitionof fdms of stearanilide on 5 N H,SOd. The points show the experimental rcsidts; tlw full lirir is calculated from the surface dipole moment, W D , of the molecules in the film.
While for bulk reactions we have: k = pZe--B/RT (xv) the complete kinetic equation for surface reactions may be written (22) as: k = +pZe-E/Rl' (xvi) In these expressions k is the rate constant, p and E are the entropy term and the energy of activation respectively for breaking the chemical bonds; Z is the collision rate. e. the surface pressure II and the film cohesion have been included in the accessibility function 4. This is defined as the relative accessibility of the potentially reactive groups in the film; it is unity at high areas when II 4 0 and when the cohesion also becomes negligible.
V. CATALYTIC EFFECT OF ELECTKIC CHARGE At surfaces the effect of an electrical charge is much more pronounced than in bulk. There are two reasons for this. The first is that all the electrostatic lines of force, instead of radiating out spherically and symmetrically as is the case for an isolated point charge, are concentrated into the region AN CATALYSIS AND REACTION KINETICS AT LIQUID INTERFACES 37 immediately below the film (Figs. 18a and 18b), where the high density results in a very steep electrical gradient, often locally of the order of a million volts per centimeter.