Reaction of ozone with hydrogen sulfide and its organic derivatives

Conference · Wed Jan 01 04:00:00 EST 1975 · Int. J. Chem. Kinet.; (United States)

OSTI ID:7291295

Becker, K H; Inocencio, M A; Schurath, U

Chemiluminescent and dark reactions of the aeronomically important trace gases hydrogen sulfide, methyl mercaptan, and dimethyl sulfide with ozone were studied in a flow tube and a low pressure reactor. The maximum of the oxidation rate and of the chemiluminescence intensity in the H/sub 2/S/O/sub 3/ system under static conditions was preceded by an induction period of up to several minutes. The oxidation rate depended strongly on the ozone concentration but followed no clearly defined rate law. The stoichiometry of ozone versus H/sub 2/S consumption was close to unity only at high reaction rates. Trace amounts of nitrogen dioxide quenched the chemiluminescence and also reduced the rate of ozone consumption. More detailed studies in a flow tube revealed that singlet sulfur dioxide chemiluminescence accompanied the reactions of ozone with H/sub 2/S as well as its methyl derivatives. Triplet SO/sub 2/ was completely quenched at moderate fuel concentrations. A new emission spectrum that was characteristic only of the H/sub 2/S/O/sub 3/ system was discovered above 5200 A. Meinel bands from vibrationally excited hydroxyl radicals were observed in its place when the methyl derivatives were used as fuels. A reaction mechanism based on sulfhydryl and hydroxyl radicals and a long-lived intermediate was proposed.

• Research Organization: Univ., Bonn
• OSTI ID: 7291295
• Conference Information: Journal Name: Int. J. Chem. Kinet.; (United States) Journal Volume: 7:Suppl. 1
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500 -- Photochemistry
500100* -- Environment
Atmospheric-- Basic Studies-- (-1989)
54 ENVIRONMENTAL SCIENCES
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHEMILUMINESCENCE
EARTH ATMOSPHERE
ENVIRONMENTAL TRANSPORT
HYDROCARBONS
HYDROGEN COMPOUNDS
HYDROGEN SULFIDES
HYDROXYL RADICALS
KINETICS
LUMINESCENCE
MASS TRANSFER
MICROORGANISMS
NITROGEN COMPOUNDS
NITROGEN DIOXIDE
NITROGEN OXIDES
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
OZONE
PHOTOCHEMICAL OXIDANTS
RADICALS
REACTION KINETICS
SULFIDES
SULFUR COMPOUNDS
SULFUR DIOXIDE
SULFUR OXIDES