Reaction of OH with CINO: kinetics and mechanisms
The kinetics and products of the gas-phase reaction of OH with CINO have been studied in a fast flow discharge system using the reaction of hydrogen atoms with NO/sub 2/ as the source of OH. The decay of OH in excess CINO at a total pressure of 1.05 +/- 0.05 Torr in He was followed by resonance fluorescence at 309.5 nm at temperatures from 262 to 373K. The stable products observed by mass spectrometry from 276 to 353 K and from 0.2 to 0.8 Torr total pressure were HOCl, HONO, and Cl/sub 2/. Molecular Cl/sub 2/ results from the reaction of Cl atoms with the excess CINO present. The ratio of the products HOCl/Cl/sub 2/ did not change significantly with temperature or total pressure. The Arrhenius expression for the rate constant k/sub 1/ (= k/sub 1a/ + k/sub 1b/) for the reaction of Oh with CINO is k/sub 1/ = (1.5/sub -0.1//sup +0.1/ x 10/sup -12/) exp(-(458 +/- 27)/T) cm/sup 3/ molecule/sup -1/ s/sup -1/, with k/sub 1/ = (3.2 +/- 0.5) x 10/sup -13/ cm/sup 3/ molecule/sup -1/ cm/sup 3/ molecule/sup -1/ s/sup -1/ at 298 K, where all errors are two standard deviations. From these kinetic data, a typical tropospheric lifetime of CINO with respect to reaction with Oh is calculated to be approx.36 days, too slow to compete with CINO photolysis.
- Research Organization:
- California State Univ., Fullerton
- OSTI ID:
- 6559310
- Journal Information:
- J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 91:9; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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54 ENVIRONMENTAL SCIENCES
ANIONS
ARRHENIUS EQUATION
CHARGED PARTICLES
CHEMICAL REACTIONS
CHLORINE COMPOUNDS
EQUATIONS
HALOGEN COMPOUNDS
HYDROXY COMPOUNDS
IONS
MASS SPECTROSCOPY
NITROGEN COMPOUNDS
ORGANIC COMPOUNDS
OXYCHLORIDES
OXYGEN COMPOUNDS
SPECTROSCOPY
TEMPERATURE DEPENDENCE