Measurements of Rate Constants for Termolecular Reactions of O(3P) with NO, O2, CO, N2, and CO2 Using a Pulsed Vacuum-uv Photolysis—Chemiluminescent Method

Abstract

Absolute rate constants for a number of termolecular reactions of O atoms were determined at 300°K. Oxygen atoms were generated by pulsed vacuum‐uv photolyses of NO, O₂, CO₂, and N₂O and were monitored by ${\mathrm{NO}}_2^{*}$ or ${\mathrm{CO}}_2^{*}$ chemiluminescent emission. The rate constants k, in units of cm⁶ molecule⁻²·second⁻¹, for the following reactions are: $$\mathrm{O}+\mathrm{NO}+\mathrm{NO}\to {\mathrm{NO}}_2+\mathrm{NO}{\text{,\hspace{0.17em}\hspace{0.17em}\hspace{0.17em}k=1.5×10}}^{\text{−31}}\text{\hspace{0.17em}(± 10 \%)}$$ $$\mathrm{O}+\mathrm{NO}+\mathrm{He}\to {\mathrm{NO}}_2+\mathrm{He}{\text{,\hspace{0.17em}\hspace{0.17em}\hspace{0.17em}k=6.65×10}}^{\text{−32}}\text{\hspace{0.17em}(± 10\%)}$$ $$\mathrm{O}+{\mathrm{O}}_2+{\mathrm{O}}_2\to {\mathrm{O}}_3+{\mathrm{O}}_2{\text{,\hspace{0.17em}\hspace{0.17em}\hspace{0.17em}k=6.4×10}}^{\text{−34}}\text{\hspace{0.17em}(± 25 \%)}$$ $$\mathrm{O}+{\mathrm{O}}_2+{\mathrm{N}}_2\to {\mathrm{O}}_3+{\mathrm{N}}_2{\text{,\hspace{0.17em}\hspace{0.17em}\hspace{0.17em}k=5.4×10}}^{\text{−34}}\text{\hspace{0.17em}(± 25 \%)}$$ $$\mathrm{O}+{\mathrm{O}}_2+\mathrm{CO}\to {\mathrm{O}}_3+\mathrm{CO}{\text{,\hspace{0.17em}\hspace{0.17em}\hspace{0.17em}k=6.7×10}}^{\text{−34}}\text{\hspace{0.17em}(± 25 \%)}$$ $$\mathrm{O}+\mathrm{CO}+\mathrm{CO}\to {\mathrm{CO}}_2+\mathrm{CO}{\text{,\hspace{0.17em}\hspace{0.17em}\hspace{0.17em}k=3.2×10}}^{\text{−36}}\text{\hspace{0.17em}(± 25 \%)}$$ $$\mathrm{O}+\mathrm{CO}+{\mathrm{N}}_2\to {\mathrm{CO}}_2+{\mathrm{N}}_2{\text{,\hspace{0.17em}\hspace{0.17em}\hspace{0.17em}k=2.2×10}}^{\text{−36}}\text{\hspace{0.17em}(± 25 \%)}$$ $$\mathrm{O}+\mathrm{CO}+\mathrm{He}\to {\mathrm{CO}}_2+\mathrm{He}{\text{,\hspace{0.17em}\hspace{0.17em}\hspace{0.17em}k=1.7×10}}^{\text{−36}}\text{\hspace{0.17em}(± 25 \%)}$$ $$\mathrm{O}+{\mathrm{CO}}_2+\mathrm{CO}\to {\mathrm{CO}}_3+\mathrm{CO}{\text{,\hspace{0.17em}\hspace{0.17em}\hspace{0.17em}k〈9×10}}^{\text{−36}}$$ $$\mathrm{O}+{\mathrm{N}}_2+{\mathrm{N}}_2\to {\mathrm{N}}_2\mathrm{O}+{\mathrm{N}}_2{\text{,\hspace{0.17em}\hspace{0.17em}\hspace{0.17em}k〈5×10}}^{\text{−38}}.$$