Mechanisms of Ozone Reactions in the Troposphere

In Chapter I, we identified the origin of stratospheric ozone and its role in limiting the short wavelengths of sunlight reaching the Earth. We also saw the importance of trace impurities of NOx and hydrocarbons in the development of tropospheric ozone. In this chapter, we review and evaluate the chemical reactions of ozone that create the important hydroxyl (HO) radical. It is the photodecomposition of tropospheric ozone that is the major source of the important HO radical, and it is the HO radical that initiates the destruction of most of the reactive trace gases that are emitted into the atmosphere. Ozone also serves as a major reactant for removal of the alkenes and other reactive unsaturated compounds, and, in this chapter, we review and evaluate the rate coefficients and mechanisms of these reactions and the expected products that result from them. The reactions that generate oxygen atoms in their first excited electronic state, O(1D) atoms, and ultimately HO radicals within the atmosphere are initiated through ozone photodecomposition: . . . O3 (X1A1) + hν → O(1D) + O2(a1Δg) (I) . . . . . . → O(1D) + O2(X3Σ–g) (II) . . . A fraction of the O(1D) atoms formed in the reactions (I) and (II) react with water molecules to generate HO radicals in reaction (1) and a larger fraction are deactivated by collisions with N2 and O2 molecules to form ground state O(3P) atoms in reaction (2): . . . O(1D) + H2O → HO + HO (1) . . . . . . O(1D) + M (N2, O2) → O(3P) + M (N2, O2) (2) . . . The competition between H2O and other air molecules (N2, O2) for reaction with O(1D) atoms results in HO generation being dependent on relative humidity. Rate coefficients for reaction of O(1D) with H2O, N2, and O2 at 298 K (in units of 10−10 cm3 molecule−1 s−1) recommended by the International Union of Pure and Applied Chemistry (IUPAC) panel are 2.14, 0.31, and 0.40, respectively (Atkinson et al., 2004). To better understand the factors that control HO formation, we will review ozone photochemistry, its cross sections, quantum yields of its major photodecomposition modes, and its photolysis frequencies under varied atmospheric conditions.