Kinetics studies of the O([sup 3]P) + CH[sub 2]Cl[sub 2] and CHCl[sub 3] reactions over the 468-1355 and 499-1090 K ranges using two techniques

Journal Article · Thu Aug 25 04:00:00 EDT 1994 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100085a023· OSTI ID:6970678

Su, M C; Lim, K P; Michael, J V ^[1]; Hranisavljevic, J; Xun, Y M; Fontijn, A ^[2]

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1. Argonne National Lab., IL (United States)
2. Rensselaer Polytechnic Inst., Troy, NY (United States)

The thermal bimolecular rate coefficients, O + CH[sub 2]Cl[sub 2] and O + CHCl[sub 3], have been investigated in this work over the respective temperature ranges 468-1355 and 499-1090 K using two entirely different techniques. The first technique, HTP (high-temperature photochemistry) at Rensselaer, provided results for the lower temperatures of these ranges, while the higher temperature measurements were carried out at Argonne using the LP-ST (laser photolysis-shock tube) method. Substantial variations in source and reactant molecular concentrations, as well as in other experimental parameters specific to each experiment, were employed in each of the studies. Temperature overlap in the databases was possible with CH[sub 2]Cl[sub 2] but not with CHCl[sub 3]. The combined results for (1) O + CH[sub 2]Cl[sub 2] [yields] OH + CHCl[sub 2] and (2) O + CHCl[sub 3] [yields] OH + CCl[sub 3] are k[sub 1] = 1.1 x 10[sup [minus]17] (T/K)[sup 1.99] exp(-2855 K/T) and [kappa][sub 2] = 1.9 x 10[sup [minus]11] (T/K)[sup 0.22] exp(-4755 K/T) cm[sub 3] molecule[sup [minus]1] S[sup [minus]1], with estimated 1 [sigma] accuracy limits of [+-]25%. The present results are compared to the related O + CH[sub 4] and O + CH[sub 3]Cl reactions. The four reactions have nearly equal rate coefficients. This is discussed on the basis of BEBO calculations. 38 refs., 8 figs., 6 tabs.

• DOE Contract Number: W-31109-ENG-38
• OSTI ID: 6970678
• Journal Information: Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 98:34; ISSN JPCHAX; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400500 -- Photochemistry
99 GENERAL AND MISCELLANEOUS
990200 -- Mathematics & Computers
CHEMICAL REACTIONS
CHEMISTRY
CHLORINATED ALIPHATIC HYDROCARBONS
CHLOROFORM
COMPILED DATA
DATA
DECOMPOSITION
ELEMENTS
FLUIDS
GASES
HALOGENATED ALIPHATIC HYDROCARBONS
HELIUM
INFORMATION
KINETICS
LASERS
MATHEMATICAL MODELS
METHYLENE CHLORIDE
NONMETALS
NUMERICAL DATA
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
OXYGEN
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
PHOTOLYSIS
RARE GASES
REACTION KINETICS
SHOCK TUBES