Use of SURFACE CHEMKIN to model multiphase atmospheric chemistry: Application to nitrogen tetroxide spills

Abstract

SURFACE CHEMKIN is a widely available computer program developed for kinetic modeling of chemical vapor deposition. We show that it may be adapted for kinetic modeling of multiphase chemistry in the atmosphere, with broad capability to deal with complex chemistry and physics. It can deal with multiple phases having different reaction manifolds in each phase, it deals with gas, surface, and bulk reactions and mass transfer rates, it keeps track of the phase equilibria with realistic activities, and it can operate in an adiabatic mode to include the effect of heat release on the system. The adapted model is applied here to the problem of a nitrogen tetroxide spill in the troposphere. The model is able to predict the formation of a nitric acid/water aerosol and to follow the chemistry taking place in both the gas and liquid phases as the spill dilutes in the surrounding atmosphere. The model predicts that in such a spill, most (70–90%) of the nitrogen oxides released are converted to nitric acid over a wide range of relative humidity.