Diode laser study of the Cl + C[sub 2]H[sub 5] reaction
- Ford Motor Company, Dearborn, MI (United States)
Real time IR absorption measurements of the formation of C[sub 2]H[sub 4] and HCl following the Cl initiated chain reaction between chlorine and ethane are presented. The ethylene molecules, formed by the reaction between chlorine atoms and ethyl radicals, arc born highly vibrationally excited and are only slowly relaxed in a N[sub 2] bath gas. The addition of C[sub 2]F[sub 6] provides efficient vibrational relaxation and reveals a very fast rise in the ethylene concentration. The measured Cl + C[sub 2]H[sub 5] rare constant is k[sub 3](295 K) = (2.9 [+-] 0.6) X 10[sup [minus]10] cm[sup 3] s[sup [minus]1] and resolves a discrepancy of a factor of 20 in previous reports of this rate constant. Measurements of the HCl concentration reveal a relatively short chain length under conditions for which the steady-state Cl and C[sub 2]H[sub 5] concentrations are comparable. Fits of the [HCl] time dependence yield a value of k[sub 3] = (3.4 [+-] 0.6) X 10[sup [minus]10] cm[sup 3] s[sup [minus]1] for the Cl + C[sub 2]H[sub 5] rate constant, in agreement with the value derived from the formation of C[sub 2]H[sub 4]. We have also measured the rate constant for the addition of chlorine atoms to ethylene and find that k[sub 6] = (1.4 [+-] 0.2) X 10[sup [minus]11] and (3.5 [+-] 0.7) X 10[sup [minus]11] cm[sup 3] s[sup [minus]1] respectively at 30 and 120 Torr total pressure and 295 K, in good agreement with literature values. 31 refs., 7 figs., 6 tabs.
- OSTI ID:
- 6019430
- Journal Information:
- Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 97:30; ISSN JPCHAX; ISSN 0022-3654
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400500 -- Photochemistry
54 ENVIRONMENTAL SCIENCES
540110*
ALKANES
ALKENES
CHEMICAL REACTIONS
CHLORINE
CHLORINE COMPOUNDS
DATA
DECOMPOSITION
ELEMENTS
ETHANE
ETHYLENE
EXPERIMENTAL DATA
HALOGEN COMPOUNDS
HALOGENS
HYDROCARBONS
HYDROCHLORIC ACID
HYDROGEN COMPOUNDS
INFORMATION
INFRARED SPECTRA
INORGANIC ACIDS
KINETICS
LASERS
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC FLUORINE COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
OZONE
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
RADICALS
REACTION KINETICS
SPECTRA
THERMODYNAMICS