An improved single crystal adsorption calorimeter

Abstract

Significant improvements to the single crystal adsorption calorimeter (SCAC) of Borroni-Bird and King are described. The calorimeter comprises a pulsed molecular beam source, an ultrathin single crystal and an infrared detector. It is calibrated using a chopped laser beam, and the amount of gas adsorbed or reacted per pulse is measured using the King and Wells reflection detector technique. Refinements in the molecular beam system, the optical calibration system, flux calibration system and sticking probability measurement technique have been made. The calorimeter response is accurately linear over a useful energy range; the detection limit is estimated as 10 kJ mol −1; and the accuracy in heats of adsorption for heats above ∼ 80 kJ mol −1 is estimated as ∼ 6%. Comparisons of calorimetric heats with isosteric heats and with desorption energies obtained for reversible systems, such as CO on Ni and Pt single crystal surfaces, generally yield good agreement and give support to the estimate for the absolute accuracy of the instrument.