Rate parameters for reactions of O(23P) with CS2, NO2 and olefins

Abstract

The reaction O(2³P)+ CS₂→SO + CS was initiated by flashing NO₂+ CS₂ mixtures with radiation restricted to wavelengths ≳3000 Å. Its rate was determined at 305 and 410°K, by monitoring the formation of CS by kinetic absorption spectroscopy. The rate constant k₂ in 1. mole^–1, sec^–1, may be expressed by log₁₀k₂= 9.8 (±0.2)– 600(±300) cal (mole 2.303 RT).^–1

Rate constants for the reactions of O(2³P) with but-1-ene, isobutene and NO₂ were determined relative to k₂ by observing how the total amount of CS produced varied with the composition of the flashed mixture. CS was thereby employed as a spectroscopic “marker” whose yield depended on the relative importance of reactions competing for the atomic oxygen.