| Abstract: | The quantum yields of SO3 formation have been determined in pure SO2 and in SO2 mixtures with NO, CO2, and O2 using both flow and static systems. In separate series of experiments excitation of SO2 was effected within the forbidden band, SO2(3B1) ← \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm SO}_2 (\tilde X,^1 A_1 ) $$\end{document} , and within the first allowed singlet band at 3130 Å. The values of Φ were found to be sensitive to the flow rate of the reactants. These results and the apparently divergent quantum yield results of Cox 10], Allen and coworkers 24, 26, 29], and Okuda and coworkers 11] were rationalized quantitatively in terms of the significant occurrence of the reactions SO + SO3 → 2SO2 (2), and 2SO → SO2 + S or (SO)2] (3), in experiments of long residence time. From the present rate data, values of the rate constants were estimated, k2=(1.2±0.7) × 106; k3=(5±4) × 105 l˙/mole · sec. Φ values from triplet excitation experiments at high flow rates of NO? SO2 and CO2? SO2 mixtures showed the sole reactant with SO2 leading to SO3 formation in this system to be SO2(3B1); SO2(3B1) + SO2 → SO3 + SO(3Σ?) (la); k =(4.2±0.4) × 107 l./mole · sec. With excitation of SO2 at 3130 Å both singlet and triplet excited states play a role in SO3 formation. If the reactive singlet state is 1B1, the long-lived fluorescent state, SO2(1B1) + SO2 → SO3 + SO (1 Δ or 3Σ?) (lb), then k =(2.2±0.5) × 109 l./mole · sec. From the observed inhibition of SO formation by added nitric oxide, it was found that the SO3-forming triplet state, generated in this singlet excited SO2 system, had a relative reactivity toward SO2 and NO which was equal within the experimental error to that observed here for the SO2(3B1) species. Either SO2(3B1) molecules were created with an unexpectedly high efficiency in 3130 Å excited SO2(1B1) quenching collisions, or another reactive triplet (presumably 3A2 or 3B2) of almost identical reactivity to SO2(3B1) was important here. |
