Physisorption kinetics

H.J. Kreuzer

Physica A: Statistical Mechanics and its Applications, 1981, vol. 106, issue 1, 144-158

Abstract: A quantum statistical theory of phonon-mediated physisorption has been developed by setting up the initial value problem within nonequilibrium statistical mechanics and calculating the desorption times appropriate for the various experimental procedures, i.e. virgin adsorption, isothermal desorption and flash desorption. We calculate desorption times for various gas-solid systems like helium-constantan, He-LiF, He—graphite, He-Ar, Xe-W, etc. which compare favorably with experiments. We are able to delimit the temperature range over which the Arrhenius-Frenkel parameterization of the desorption time td = t0dexp(Q/kBT) is acceptable. We can correlate isothermal and flash desorption times and suggest the temperature range where differences in these times can be detected. A complete fourth-order calculation enables us to delineate the range of validity of the one-phonon (second-order) theory and of the relaxation time approach to desorption. Desorption via phonon cascades is calculated. Our theory, which is essentially parameter-free, produces prefactors t0d in the whole experimental range of physisorption from 10-7 s to 10-14 s.

Date: 1981
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Persistent link: https://EconPapers.repec.org/RePEc:eee:phsmap:v:106:y:1981:i:1:p:144-158

DOI: 10.1016/0378-4371(81)90215-6

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