Temperature dependence of CH (CD) + D sub 2 reaction kinetics
- Naval Research Lab., WA (USA)
The temperature dependence of the rate coefficients for the reactions of ground-state CH and CD + D{sub 2} has been measured over the temperature range 298-1,260 and 560-1,120 K, respectively. The methylidyne radical is generated by laser photolysis at 248 nm of CHBr{sub 2}Cl for CH and CDBr{sub 3} for CD and detected via laser-induced fluorescence. No pressure dependence over the range 10-100 Torr at room temperature is observed for the CH + D{sub 2} reaction. The CH + D{sub 2} rate coefficients are fit to the Arrhenius expression k(T) = A exp({minus}E{sub a}/RT) and yield k(T) = (4.29 {plus minus} 0.27) {times} 10{sup {minus}11} cm{sup 3} s{sup {minus}1} exp ((450 {plus minus} 50 cal mol{sup {minus}1})/RT). The data are fit equally well by k(T) = (1.13 {plus minus} 0.36) {times} 10{sup {minus}9} T{sup {minus}(0.45 {plus minus} 0.06)}. For the reaction CD + D{sub 2}, a rate expression for the endothermic addition-elimination channel is derived from the measured temperature dependence. The fit expression yields k{sub abs}(T) = (5.56 {plus minus} 2.82) {times} 10{sup {minus}11} cm{sup 3}s{sup {minus}1} exp(({minus}275 {plus minus} 900 cal mol{sup {minus}1})/RT). Error limits of the fitted parameters represent 1 {sigma} values.
- OSTI ID:
- 5169674
- Journal Information:
- Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 95:3; ISSN JPCHA; ISSN 0022-3654
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
ALKYL RADICALS
ARRHENIUS EQUATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DATA
DECOMPOSITION
EMISSION SPECTROSCOPY
EQUATIONS
EXPERIMENTAL DATA
FLUORESCENCE SPECTROSCOPY
HIGH TEMPERATURE
INFORMATION
KINETICS
MEDIUM TEMPERATURE
NUMERICAL DATA
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
RADICALS
REACTION KINETICS
SPECTROSCOPY
TEMPERATURE DEPENDENCE