Model of Uptake of OH Radicals on Nonreactive Solids

• Published in: The journal of physical chemistry. B 2005-10, Vol.109 (42), p.20036-20043
• Main Authors: Remorov, R. G, Bardwell, M. W
• Format: Article
• Language: English
• ISSN: 1520-6106; 1520-5207
• DOI: 10.1021/jp051717h

A model of adsorption and recombination of OH radicals was developed for nonreactive solid surfaces of atmospheric interest. A parametrization of this heterogeneous mechanism was carried out to determine the role of the catalytic properties of these solid surfaces, taking into account the adsorption energy, defects, surface diffusion, and chemical reactions in the gas−solid interface. The uptake process was simulated for diffusion-controlled chemical reactions on the surface on the basis of Langmuir−Hinshelwood and Eley−Rideal mechanisms. Using an analytical approach and the Monte Carlo technique, we show the dependencies of the uptake probability of the heterogeneous reactions on the OH concentration and adsorption energy. The model is employed in the analysis of the empirically derived uptake coefficient for water ice, Al2O3, NaCl, NH4NO3, NH4HSO4, and (NH4)2SO4. We found the following values for the free energy of adsorption of OH radicals:  E ice = 7.3−7.6 kcal/mol, E Al 2 O 3 = 11−11.7 kcal/mol, E NH 4 NO 3 = 10.2 kcal/mol, E NaCl = 10.2 kcal/mol, E NH 4 HSO 4 = 9.8 kcal/mol, and E (NH 4 ) 2 SO 4 = 9.8 kcal/mol. The atmospheric implications of the catalytic reactions of OH with adsorbed reactive molecules are discussed. The results of the modeling of the uptake process showed that the heterogeneous decay rate can exceed the corresponding gas-phase reaction rate under atmospheric conditions.