Study of the recombination reaction CH/sub 3/ + CH/sub 3/ yields C/sub 2/H/sub 6/: Theory

Conference · Thu Jan 01 04:00:00 EST 1987

OSTI ID:6358591

Wagner, A F; Wardlaw, D M

A microcanonical variational RRKM rate constant calculation, based on the flexible transition state theory of Wardlaw and Marcus and an adjustable empirical potential energy surface, is compared to measurements of the methyl radical self-recombination rate constant in Ar buffer gas. The calculations contain two adjustable parameters: a potential parameter ..cap alpha.., which influences the tightness of the transition state and <..delta..E>/sub tot/, the total average energy change in metastable C/sub 2/H/sub 6/ per collision with the buffer gas. When the parameters are optimized, the resulting calculated rate constants have a 10.7% rms error with the measurements in Ar buffer gas. The rate calculations have been extended to 2000K and then fit over the full temperature and pressure range to a relatively simple functional form suitable for modeling studies.

• Research Organization: Argonne National Lab., IL (USA); Queen's Univ., Kingston, Ontario (Canada). Dept. of Chemistry
• DOE Contract Number: W-31109-ENG-38
• OSTI ID: 6358591
• Report Number(s): CONF-870541-2; ON: DE87011424
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical &amp; Physicochemical Properties
ALKANES
ALKYL RADICALS
ARGON
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
ELEMENTS
ETHANE
FLUIDS
GASES
HYDROCARBONS
KINETICS
MATHEMATICAL MODELS
METHYL RADICALS
NONMETALS
ORGANIC COMPOUNDS
RADICALS
RARE GASES
REACTION KINETICS
RECOMBINATION
YIELDS