Kinetics of some reactions of atmospheric interest: hydrolysis of carbonyl sulfide, and reaction rates of thermal chlorine atoms with carbonyl sulfide, methanol, hydrogen sulfide, and methyl chloride
The hydrolysis appeared pseudo first order in OCS and showed a rate constant of (1.04 /times/ 10/sup 11/) exp(/minus/10800/T) sec /sup /minus/1/. The hydrolysis of OCS can be increased in rate by the presence of OH/sup /minus// concentration and showed a bimolecular rate constant of (8.12 /times/ 10/sup 9/) exp(/minus/6040/T) 1 mole/sup /minus/1/ sec /sup /minus/1/. The rate corresponds to a lifetime for dissolved OCS of 1.7 days. A two-layer diffusion model with accurate Henry's Law constant and hydrolysis rate constant can obtain air-sea exchange flux. The lifetime for transport of OCS from the troposphere to the ocean with respect to this flux is about 12 years. The ocean is most likely a net source of OCS rather than a sink, but hydrolysis of OCS still occurs in the ocean. The relative rate constants for the gas phase reactions of thermal chlorine atoms have been measured with H/sub 2/S, CH/sub 3/OH, C/sub 2/H/sub 6/, and CH/sub 2/ = CHBr over the temperature range from 232 to 359 K. These data for Cl atoms reaction with H/sub 2/S at a pressure of 4000 Torr of CClF/sub 3/ are consistent with a temperature-dependent rate constant of (10.5 /+-/ 0.4) /times/ 10/sup /minus/11/ cm/sup 3/ molecule/sup /minus/1/ sec/sup /minus/1/. The absolute rate constant for Cl atoms reaction with CH/sub 3/OH is determined to be (9.14 /+-/ 1.02) /times/ 10/sup /minus/11/ cm/sup 3/ molecule/sup /minus/1/ sec/sup /minus/1/ at temperature 295 K. We have carried out a series of competitive runs of OCS with CH/sub 2/ = CHBr and trans-2,3-DCHF-2B. The results of these runs do not indicate any rapid removal of /sup 38/Cl through reaction with OCS with or without the presence of O/sub 2/. An upper limit of 1 /times/ 10/sup /minus/15/ cm/sup 3/ molecule/sup /minus/1/ sec/sup /minus/1/ for the reaction of /sup 38/Cl with OCS.
- Research Organization:
- California Univ., Irvine (USA)
- OSTI ID:
- 6259594
- Resource Relation:
- Other Information: Thesis (Ph. D.)
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
58 GEOSCIENCES
CARBON OXYSULFIDE
CHEMICAL REACTIONS
HYDROLYSIS
CHLORINE
HYDROGEN SULFIDES
METHANOL
METHYL CHLORIDE
AIR
CHEMICAL REACTION KINETICS
CHLORINE 37
CHLORINE 38
DIFFUSION
ENVIRONMENTAL TRANSPORT
KINETIC EQUATIONS
SEAS
TROPOSPHERE
ALCOHOLS
BETA DECAY RADIOISOTOPES
BETA-MINUS DECAY RADIOISOTOPES
CARBON COMPOUNDS
CHALCOGENIDES
CHLORINATED ALIPHATIC HYDROCARBONS
CHLORINE ISOTOPES
DECOMPOSITION
EARTH ATMOSPHERE
ELEMENTS
EQUATIONS
FLUIDS
GASES
HALOGENATED ALIPHATIC HYDROCARBONS
HALOGENS
HYDROGEN COMPOUNDS
HYDROXY COMPOUNDS
ISOMERIC TRANSITION ISOTOPES
ISOTOPES
KINETICS
LIGHT NUCLEI
LYSIS
MASS TRANSFER
MINUTES LIVING RADIOISOTOPES
NONMETALS
NUCLEI
ODD-EVEN NUCLEI
ODD-ODD NUCLEI
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
RADIOISOTOPES
REACTION KINETICS
SECONDS LIVING RADIOISOTOPES
SOLVOLYSIS
STABLE ISOTOPES
SULFIDES
SULFUR COMPOUNDS
SURFACE WATERS
500200* - Environment
Atmospheric- Chemicals Monitoring & Transport- (-1989)
520200 - Environment
Aquatic- Chemicals Monitoring & Transport- (-1989)
580500 - Oceanography- (1980-1989)