A kinetic study of the chemistry of the SO2 (3B1) reactions with cis- and trans-2-butene

摘要: The chemical reactions of SO2(3B1) molecules with cis- and trans-2-butene have been studied in gaseous mixtures at 25°C by excitation SO2 within the SO2(+, 1A1) ‘forbidden’ band using 3500–4100-A light. initial quatum yields olefin isomerization were determined as a function [SO2]/[2-butene] ratio added gases, He O2. kinetic treatment these data suggests that there is formed quenching step either or trans-2-butene, some common intermediate, probably triplet addition complex between SO- olefin. It decomposes very rapidly to form 2-butene isomers [trans-2-butene]/[cis-2-butene] = 1.8. In another series experiments was excited 3630 ± 1-A laser pulse short duration, rate constants 2-butenes from lifetime measurements. 21°C are (1.29 0.18) × 1011 (1.22 0.15) l/mole·sec cis-2-butene respectively, quencher molecule. Within experimental error equal those derived quantum yield data. Thus rate-determining reaction suggested be reaction, presumably formation SO2-2-butene complex. third light scattering measurements, it found aerosol originates largely SO3 H2SO4 mist following + SO(3Σ−). Aerosol photochemically SO2-olefin interaction unimportant systems must atmosphere.