A technique based upon transmission FTIR to obtain rate constants for adsorption and desorption over supported metal catalysts has been developed and tested. The technique requires the use of a sinusoidal perturbation function imposed on steady state linearized adsorption-desorption kinetics. The measurement of a phase lag between the sinusoidal inlet gas phase forcing concentration and the response of surface coverage, together with a measurement of the maximum amplitudes of the forcing function and surface response enable the calculation of the relevant adsorption and desorption rate constants.
The technique has been successfully applied to the measurement of both adsorption and desorption rate constants for CO adsorbed on a 1% Pt/SiO2 catalyst. The values obtained for these rate constants at 343 K were: Ka = 0.147 s−1 and Kd = 7.28 × 10−3 s−1. A sticking coefficient corresponding to the adsorption of weakly bonded CO on Pt under conditions of high CO surface coverage was obtained.