Kinetics of SH with NO2, O3, O2, and H2O2

Article abstract of DOI:10.1021/j100271a038

A low pressure (1-8 torr of He) discharge flow reactor with (a) LIF detection of SH using a high repetition rate (20 kHz) metal atom laser to circumvent severe predissociation of the A²Σ⁺ state and (b) resonance fluorescence detection of OH has been used to examine the kinetics of the title reactions at 298 K: SH + NO2 -> HSO + NO, k₁=(3.0+/-0.8)x10^-11 cm³s^-1; SH + O3 -> HSO + O2,k₂ = (3.2+/- 1.0)x10^-12cm³s^-1;SH + O2 -> SO + OH,k₃ < 1x10^-17 cm³s_-1;SH + H2O2 -> H2S + HO2,k_4a;SH + H2O2 -> HSOH + OH,k_4b;SH + H2O2 -> HSO + H2O,k_4c. k₄=k_4a+k_4b+k_4c<5x10_-15 cm³s_-1.Regeneration of SH in reaction 2 by HSO + O3 is observed and is used to infer a rate constant for HSO + O3 -> products of (1.0+/-0.4)x10^-13cm³s^-1.Absence of OH production in that reaction implies that the primary products are SH + 2O2.Isotope experiments with H2S replaced by D2S substantiate that conclusion and yield a reaction rate constant for DSO + O3 -> SD + 2O2 of 9x10^-14 cm³s^-1.Brief discussions of SH reactivity compared with OH and Br are offered, as well as a summary of the atmospheric chemistry of SH.