Role of water on the H-abstraction from methanol by ClO

The influence of a single water molecule on the reaction mechanism and kinetics of hydrogen abstraction from methanol (CH₃OH) by the ClO radical has been investigated using ab initio calculations. The reaction proceeds through two channels: abstraction of the hydroxyl H-atom and methyl H-atom of CH₃OH by ClO, leading to the formation of CH₃O+HOCl (+H₂O) and CH₂OH+HOCl (+H₂O), respectively. In both cases, pre- and post-reactive complexes were located at the entrance and exit channel on the potential energy surfaces. Results indicate that the formation of CH₂OH+HOCl (+H₂O) is predominant over the formation of CH₃O+HOCl (+H₂O), with ambient rate constants of 3.07×10^-19 and 3.01×10^-23cm³/(molecule·sec), respectively, for the reaction without water. Over the temperature range 216.7-298.2K, the presence of water is seen to effectively lower the rate constants for the most favorable pathways by 4-6 orders of magnitude in both cases. It is therefore concluded that water plays an inhibitive role on the CH₃OH+ClO reaction under tropospheric conditions.