A kinetics study of the O({sup 3}P) + CH{sub 3}Cl reaction over the 556-1485 K range by the HTP and LP-ST techniques

Conference · Sat Nov 30 23:00:00 EST 1991

OSTI ID:10152028

Ko, Taeho; Fontijn, A ^[1]; Lim, K P; Michael, J V ^[2]

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1. Rensselaer Polytechnic Inst., Troy, NY (United States). High-Temperature Reaction Kinetics Lab.
2. Argonne National Lab., IL (United States)

The high-temperature photochemistry (HTP) and laser photolysis-shock tube (LP-ST) techniques have been combined to study the kinetics of the reaction between ground-state oxygen atoms with CH{sub 3}Cl over the temperature range, 556--1485 K. In the HTP reactor, used for the 556--1291 K range, O atoms were generated by flash photolysis of O{sub 2}, CO{sub 2} or SO{sub 2}, and the atom concentrations were monitored by resonance fluorescence, while with the LP-ST technique, used for the 916--1485 K range, O atoms were generated by the photolysis of either SO{sub 2} or NO with the 193 nm light from a pulsed ArF excimer laser, and atomic resonance absorption spectroscopy (ARAS) was used to monitor [O]{sub t}. In both studies, rate coefficients were derived from the [O] profiles under the pseudo-first-order condition, [O]{much_lt}[CH{sub 3}Cl]. The data obtained by the two techniques are in excellent agreement and are best represented by the expression, k(T) = 2.57 {times} 10{sup {minus}11} (T/K){sup 0.31} exp({minus}5633 K/T) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1} with a 2{sigma} precision varying from {plus_minus}6 {plus_minus}22% and an estimated 2{sigma} accuracy of {plus_minus}21% to {plus_minus}30%, depending on temperature. The rate coefficients for the title reaction are essentially identical to those for the O + CH{sub 4} reaction over the observed temperature range, the reasons for which are discussed.

• Research Organization: Argonne National Lab., IL (United States)
• Sponsoring Organization: USDOE, Washington, DC (United States)
• DOE Contract Number: W-31109-ENG-38
• OSTI ID: 10152028
• Report Number(s): ANL/CP--75075; CONF-920707--30; ON: DE92015267
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500
664300
74 ATOMIC AND MOLECULAR PHYSICS
ARRHENIUS EQUATION
ATOMS
CHEMICAL REACTIONS
COLLISION PHENOMENA
EXCIMER LASERS
GROUND STATES
METHYL CHLORIDE
OXYGEN
OXYGEN COMPOUNDS
PHOTOCHEMISTRY
PHOTOLYSIS
SHOCK TUBES
TEMPERATURE RANGE 1000-4000 K