Applied Surface Science, Vol.196, No.1-4, 202-208, 2002
Material properties controlling adsorption kinetics and temperature programmed desorption spectra
When statistical rate theory (SRT) is applied to obtain the expression for the gas adsorption rate on a solid surface, it is predicted that the unidirectional adsorption and desorption rates depend on the chemical potentials in the gas and the adsorbed phase. This prediction is in contrast to that obtained from transition state theory which claims the unidirectional desorption rate only depends on the chemical potential in the adsorbed phase, and in order for the theory to be consistent, imposes a condition on the chemical potential in the low pressure limit. If the coverage dependence of the chemical potential function is explicitly "own this consistency condition can be evaluated. A previously proposed chemical potential expression that is expressed in terms of the coverage dependent material properties is reviewed. These material properties can be evaluated from the measured equilibrium adsorption isotherms and the electron-energy-loss spectrum of-a well-defined gas-solid system. When this chemical potential is used with SRT, the coverage during beam-dosing adsorption kinetics can be calculated and pressure spectra during temperature programmed desorption (TPD) can be predicted and compared with experiments reported by others. Close agreement is found in both cases, giving substantial support to the expression for the chemical potential. When this same chemical potential function is used to examine transition state theory of adsorption kinetics and the expressions for the "coverage dependent reaction rate constants" inconsistencies are found. (C) 2002 Elsevier Science B.V. All rights reserved.