ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The room-temperature photolysis of N2O (10-100 torr) at 2139 Å to produce O(1D) has been studied in the presence of CH4 (10-891 torr). The reactions of O(1D) with CH4 were found to be \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {(4)} & {{\rm O(}^{\rm 1} D{\rm)} + {\rm CH}_{\rm 4} } & \to & {{\rm HO + CH}_{\rm 3} } & {0.95 \pm 0.05} \\ {(8)} & {} & \to & {{\rm O(}^{\rm 3} P{\rm)} + {\rm CH}_{\rm 4} } & {{\rm 0}{\rm .05} \pm {\rm 0}{\rm .05}} \\ {} & {} & \to & {{\rm CH}_{\rm 2} + {\rm H}_{\rm 2} {\rm O}} & {{\rm 〈 0}{\rm .03}} \\ {} & {} & \to & {{\rm CH}_{\rm 3} {\rm OH}} & {{\rm 〈 0}{\rm .01}} \\ {} & {} & \to & {{\rm CH}_{\rm 2} {\rm O + H}_{\rm 2}} & {{\rm 〈 0}{\rm .002}} \\\end{array}$$\end{document} The method of chemical difference was used to measure the rate constant ratio k4/(k2 + k3), where reactions (2) and (3) are \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {(2)} & {{\rm O(}^{\rm 1} D{\rm)} + {\rm N}_{\rm 2} {\rm O}} & { \to {\rm N}_{\rm 2} + {\rm O}_{\rm 2} } \\ {(3)} & {} & { \to 2{\rm NO}} \\\end{array}$$\end{document} The CH3 radicals produced in reaction (4) react with the O2 and NO produced in reactions (2) and (3). Thus, near the endpoint of the internal titration, φ{C2H6} gives an accurate measure of k4/(k2 + k3). For the translationally energetic O(1D) atoms produced in the photolysis, k4/(k2 + k3) = 2.28 ± 0.20. However, if He is added to remove the excess translational energy, then k4/(k2 + k3) drops to 1.35 ± 0.3.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550040406
