The Adsorption, Desorption, and Exchange Reactions of Oxygen, Hydrogen, and Water on Platinum Surfaces. II. Hydrogen Adsorption, Exchange, and Equilibration

Abstract

The adsorption, desorption, exchange, and equilibration reactions of hydrogen and deuterium on a platinum filament have been investigated by thermal desorption mass spectrometry. A surface saturated with hydrogen at 120 °K has a coverage 4.2 × 1014 molecules cm−2 and gives desorption spectra with four distinct peaks: β1,(165 °K), β2(220 °K), β3(280 °K), and β4(350 °K). Apparent activation energies and pre-exponential factors were determined for the β2-, β3-, and β4-peaks. For both co-adsorption and sequential adsorption of H2 and D2 the mass 2, 3, and 4 desorption spectra have identical shapes and the gas desorbs at equilibrium throughout. It is concluded that hydrogen adsorbs dissociatively. Exchange and equilibration were studied at 120, 210, and 285 °K by determining the surface composition and isotope distribution after varying fractions of preadsorbed H had been replaced. Following exchange at 120 °K the desorption spectra show a higher D content and a lack of equilibrium in the desorbing gas at low temperature. In most other experiments the mass 2,3, and 4 desorption spectra had identical shapes and the gas desorbed at equilibrium. The results are interpreted by a model which requires that the polycrystalline platinum surface is intrinsically heterogeneous. It appears that different mechanisms are unnecessary to interpret the differences in kinetics observed for exchange and equilibration at low temperatures.