High-pressure discharge flow kinetics study of OH + CH{sub 3}SCH{sub 3}, CH{sub 3}SSCH{sub 3} {yields} products from 297 to 368 K

Journal Article · Thu Feb 20 04:00:00 EST 1992 · Journal of Physical Chemistry

DOI:https://doi.org/10.1021/j100183a053· OSTI ID:554992

Abbatt, J P.D.; Fenter, F F; Anderson, J G ^[1]

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1. Harvard Univ., Cambridge, MA (United States)

Due to a host of experimental and chemical complications, there has been extremely high variability in the literature results for the kinetics of the H atom abstraction reaction between OH and CH{sub 3}SCH{sub 3} (DMS). In particular, as a result of a wall reaction between OH and DMS, this reaction stands as the prime example of one which severely restricts the capability of the low-pressure discharge flow technique to measure gas-phase, homogeneous rate constants. In this study, the {open_quotes}wall-less{close_quotes} high-pressure discharge flow technique is used to measure the kinetics for this reaction, and for the related reaction between OH and CH{sub 3}SSCH{sub 3} (DMDS), over the temperature range from 297 to 368 K. To the 95% confidence level, the results are as follows: for OH/CH{sub 3}SCH{sub 3}, (1.35 {+-} 0.62) x 10{sup {minus}11}e{sup (285{+-}135)/T} and (4.98 {+-} 0.46) x 10{sup {minus}12} at 297 K, and for OH/CH{sub 3}SSCH{sub 3}, (6.2 {+-} 4.9) x 10{sup {minus}11}e{sup (410{+-}210)/T} and (2.39 {+-} 0.30) x 10{sup {minus}10} at 297 K, where the units are cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. The results for the OH/DMS reaction are similar to those of specific studies performed with the complementary flash photolysis technique. The agreement between two dissimilar approaches increases the authors confidence in the literature database for this reaction. The mechanisms of these reactions are discussed in terms of orbital interactions. 36 refs., 11 figs., 5 tabs.

• Sponsoring Organization: USDOE
• OSTI ID: 554992
• Journal Information: Journal of Physical Chemistry, Journal Name: Journal of Physical Chemistry Journal Issue: 4 Vol. 96; ISSN JPCHAX; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

54 ENVIRONMENTAL SCIENCES
ADDUCTS
ATMOSPHERIC CHEMISTRY
CHEMICAL REACTION KINETICS
DIMETHYL SULFIDE
EARTH ATMOSPHERE
HYDROGEN TRANSFER
HYDROXYL RADICALS
TEMPERATURE RANGE 0273-0400 K