ATMOSPHERIC CHEMISTRY OF 1,1,1-TRICHLOROETHANE - UV ABSORPTION-SPECTRA AND SELF-REACTION KINETICS OF CCL3CH2 AND CCL3CH2O2 RADICALS, KINETICS OF THE REACTIONS OF THE CCL3CH2O2 RADICAL WITH NO AND NO2, AND THE FATE OF THE ALKOXY RADICAL CCL3CH2O
J. Platz et al., ATMOSPHERIC CHEMISTRY OF 1,1,1-TRICHLOROETHANE - UV ABSORPTION-SPECTRA AND SELF-REACTION KINETICS OF CCL3CH2 AND CCL3CH2O2 RADICALS, KINETICS OF THE REACTIONS OF THE CCL3CH2O2 RADICAL WITH NO AND NO2, AND THE FATE OF THE ALKOXY RADICAL CCL3CH2O, Journal of physical chemistry, 99(17), 1995, pp. 6570-6579
A pulse radiolysis technique was used to measure the UV absorption spe
ctra of CCl3CH2 and CCl3CH2O2 radicals over the range 220-300 nm. At 2
20 nm, sigma(CCl3CH2) = (9.4 +/- 1.1) x 10(-18) cm(2) molecule(-1); at
250 nm, sigma(CCl3CH2O2) = (2.9 +/- 0.3) x 10(-18) cm(2) molecule(-1)
. The observed self-reaction rate constants, defined as -d[CCl3CH2]/dt
= 2k(4)[CCl3CH2] and -d[CCl3CH2O2]/dt = 2k(5obs)[CCl3CH2O2](2), were
k(4) = (9.1 +/- 1.1) x 10(-12) and k(5obs) = (4.7 +/- 1.6) x 10(-12) c
m(3) molecule(-1) s(-1). The reaction of CCl3CH2O2 radicals with NO gi
ves CCl2CH2O radicals. In the atmosphere, >96% of the CCl3CH2O radical
s react with O-2 to give CCl3CHO. The rate constants for the reactions
of CCl3CH2O2 radicals with NO and NO2 were determined to be k(6) grea
ter than or equal to 6.1 x 10(-12) cm(3) molecule(-1) s(-1) and k(7) =
(6.5 +/- 0.4) x 10(-12) cm(3) molecule(-1) s(-1), respectively. As a
part of this work, the rate constant for the reaction between F atoms
and CCl3CH3 was determined to be k(3) = (6.8 +/- 1.5) x 10(-12) cm(3)
molecule(-1) s(-1). A relative rate technique was used to measure rate
constants for the reactions of Cl atoms with: CCl3CH3, (9.9 +/- 2.0)
x 10(-15); CCl3CHO, (6.0 +/- 1.3) x 10(-12); and CCl3CH2OH (3.0 +/- 0.
6) x 10(-12) (units of cm(3) molecule(-1) s(-1)) at 296 K. Results are
discussed in the context of the atmospheric chemistry of 1,1,1-trichl
oroethane.