Formation and decay of ( sup 3 P sub J )O atoms in the laser flash photolysis of chlorine dioxide (OClO) at 308 nm

Journal Article · Thu Dec 27 04:00:00 EST 1990 · Journal of Physical Chemistry; (USA)

DOI:https://doi.org/10.1021/j100389a014· OSTI ID:6103757

Colussi, A J ^[1]

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1. California Institute of Technology, Pasadena (USA)

The primary quantum yields of O({sup 3}P{sub J}) and Cl({sup 2}P{sub 3/2}) atoms in the laser flash photolysis of OClO(g) at 308 nm and 298 K and the kinetics of the subsequent oxygen atom decay have been investigated by time-resolved atomic resonance fluorescence measurements. The determined quantum yields are {phi}{sub o} = 1.02 {plus minus} 0.05 and {phi}{sub Cl} < 0.01. Second-order rate constants for the reaction between O atoms and OClO are pressure dependent with a finite intercept. The rate constant for the bimolecular channel O + OClO {yields} O{sub 2} + ClO (1) has a value of k{sub 1} = (1.6 {plus minus} 0.4) {times} 10{sup {minus}13} cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. Termolecular reaction rates for O + OClO + Ar {yields} ClO{sub 3} + Ar (2) can be fit with k{sub 20} = (1.4 {plus minus} 0.3) {times} 10{sup {minus}31} cm{sup 6} molecule{sup {minus}2}s{sup {minus}1} and k{sub 2{infinity}} = (3.1 {plus minus} 0.8) {times} 10{sup {minus}11} cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}.

• OSTI ID: 6103757
• Journal Information: Journal of Physical Chemistry; (USA), Journal Name: Journal of Physical Chemistry; (USA) Vol. 94:26; ISSN 0022-3654; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500 -- Photochemistry
54 ENVIRONMENTAL SCIENCES
540120* -- Environment
Atmospheric-- Chemicals Monitoring &amp; Transport-- (1990-)
ATMOSPHERIC CHEMISTRY
CHALCOGENIDES
CHEMICAL REACTIONS
CHEMISTRY
CHLORINE COMPOUNDS
CHLORINE OXIDES
DATA
DECOMPOSITION
EMISSION SPECTROSCOPY
EXPERIMENTAL DATA
FLUORESCENCE SPECTROSCOPY
HALOGEN COMPOUNDS
INFORMATION
KINETICS
MEASURING METHODS
MEDIUM TEMPERATURE
NUMERICAL DATA
OXIDES
OXYGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
REACTION KINETICS
SPECTROSCOPY