Reaction and deactivation of HCl (v=1, 2) by O atoms

Journal Article · Sun Jan 15 04:00:00 EST 1978 · J. Chem. Phys.; (United States)

DOI:https://doi.org/10.1063/1.435760· OSTI ID:5253695

Macdonald, R G; Moore, C B

Laser-induced fluorescence, following direct excitation of HCl (v=2), was used to measure the total deactivation rate constant for HCl (v=2) by O(/sup 3/P/sub g/) atoms as (5.2 +- 0.4) x 10/sup -12/ cm/sup 3/ molecule/sup -1/ sec/sup -1/. This is partitioned into a reaction rate constant of (1.5 +- 1.2) x 10/sup -12/ cm/sup 3/ molecule/sup -1/ sec/sup -1/ for HCl (v=2)+O(/sup 3/P/sub g/) ..-->..OH (v=1, 0)+Cl and a relaxation rate constant for HCl (v=2)+O(/sup 3/P/sub g/) ..-->..HCl (v=1)+O(/sup 3/P/sub g/) of (3.7 +- 1.2) x 10/sup -12/ cm/sup 3/ molecule/sup -1/ sec/sup -1/. The total deactivation rate constant for HCl (v=1)+O(/sup 3/P/sub g/) atoms, including reaction and relaxation, was measured to be (8.9 +- 1.3) x 10/sup -13/ cm/sup 3/ molecule/sup -1/ sec/sup -1/. All measurements were carried out at 296 +- 2 /sup 0/K. The vibrationally enhanced chemical reaction rate constant for HCl (v=2) is roughly a factor of 10/sup 4/ greater than the reaction rate constant for HCl (v=0) with O atoms. The reaction appears to occur adiabatically on the lowest triplet potential hypersurface. For HCl (v=2, 1)+O vibrational relaxation is faster than chemical reaction even though the total energy is well above the barrier to reaction.

• Research Organization: Department of Chemistry, University of California, and Materials and Molecular Research Division of the Lawrence Berkeley Laboratory, Berkeley, California 94720
• OSTI ID: 5253695
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 68:2; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CHEMICAL REACTION KINETICS
CRYOGENIC FLUIDS
ELEMENTS
ENERGY LEVELS
EXCITED STATES
FLUIDS
FLUORESCENCE
HYDROCHLORIC ACID
HYDROGEN COMPOUNDS
INORGANIC ACIDS
KINETICS
LUMINESCENCE
NONMETALS
OXYGEN
REACTION KINETICS
RELAXATION
VIBRATIONAL STATES