Rate constants for the reactions OH + HOCl. -->. H/sub 2/O + ClO and H + HOCl. -->. products

Journal Article · Thu Mar 10 04:00:00 EST 1988 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100316a024· OSTI ID:7148538

Ennis, C A; Birks, J W

A new laboratory source of gaseous hypochlorous acid (HOCl) has been used in two kinetics investigations in a mass spectrometry-resonance fluorescence discharge flow system. Two potential removal reactions of stratospheric HOCl were studied. The rate constant for the reaction OH + HOCl ..-->.. H/sub 2/O + ClO (1) at 298 K was found to be lower than the NASA estimate by a factor of about 2-12; a value in the range (1.7-9.5) x 10/sup -13/ cm/sup 3/ molecule/sup -1/ s/sup -1/ for k/sub 1/ is reported here. The reaction of Cl/sub 2/O + OH interfered in the study of k/sub 1/ and was the subject of a preliminary investigation. Its rate constant was determined to be (9.4 +/- 1.0) x 10/sup -12/ cm/sup 3/ molecule/sup -1/ s/sup -1/ at 298 K. The rate constant for the reaction H + HOCl ..-->.. products (2) was determined to be (5.0 +/- 1.4) x 298 K. Although branching ratios for three possible products channels could not be determined, OH was identified as a product. The results of this work imply that reactions 1 and 2 are not competitive with direct photolysis in the removal of HOCl from the stratosphere.

• Research Organization: Univ. of Colorado, Boulder (USA)
• OSTI ID: 7148538
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 92:5; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
500100 -- Environment
Atmospheric-- Basic Studies-- (-1989)
54 ENVIRONMENTAL SCIENCES
ABSORPTION
ANIONS
BRANCHING RATIO
CATIONS
CHARGED PARTICLES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DATA
EMISSION SPECTROSCOPY
EXPERIMENTAL DATA
FLUORESCENCE SPECTROSCOPY
HYDROGEN COMPOUNDS
HYDROXY COMPOUNDS
HYPOCHLOROUS ACID
INFORMATION
INORGANIC ACIDS
IONS
KINETICS
MASS SPECTROSCOPY
MEDIUM TEMPERATURE
NUMERICAL DATA
ORGANIC COMPOUNDS
REACTION KINETICS
RESONANCE ABSORPTION
SPECTROSCOPY