Journal of Physical Chemistry A, Vol.101, No.32, 5776-5782, 1997
Infrared-Absorption Probing of the Cl+c3H6 Reaction - Rate Coefficient for HCl Production Between 290-K and 800-K
The reaction of Cl with propylene, C3H6, has been investigated as a function of temperature (293-800 K) and pressure (3-10 Torr) using the laser photolysis/infrared long-path absorption (LP/IRLPA) technique. The measured rate coefficient for HCl production is well-described by a simple Arrhenius expression (4.9 +/- 0.5) x 10(-11) exp[-(90 +/- 50)/T] cm(3) molecule(-1) s(-1) (all error estimates +/- 2 sigma). At T less than or equal to 400 K biexponential time behavior of the HCl production is observed, arising from excited C3H6Cl adduct dissociation, but at higher temperature single-exponential behavior is seen. Comparison of measurements in CO2. buffer, where HCl vibrational relaxation is rapid, and in Ar buffer allows extraction of the HCl(upsilon = 1) + C3H6 vibrational relaxation rate and the fraction of vibrationally excited HCl produced in the reaction. The measured rate coefficient for HCl(upsilon=1) vibrational relaxation by C3H6 is (3.7 +/- 0.7) x 10(-12) cm(3) molecule(-1) s(-1), and the fraction of vibrationally excited HCl produced in the reaction is 0.48 +/- 0.06 at 293 K. The observations are consistent with a dominant direct abstraction mechanism and a smaller contribution from addition-elimination.
Keywords:UNIMOLECULAR ELIMINATION-REACTIONS;CHLORINE ATOMS;LASER;RADICALS;PHOTOFRAGMENTATION;ABSTRACTION;DYNAMICS;EMISSION;SPECTRA;SYSTEM