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Substituent effects on the disproportionation-combination rate constant ratios for gas-phase halocarbon radicals. II. Reactions of •CF3 +CF3CH2CH2• and CF3CH2CH2• + CF3CH2CH2•

✍ Scribed by Derek R. McDowell; Jennie Weston; Bert E. Holmes

Publisher
John Wiley and Sons
Year
1996
Tongue
English
Weight
634 KB
Volume
28
Category
Article
ISSN
0538-8066

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✦ Synopsis

Disproportionation/combination rate constant ratios, k , / k , , have been measured for the collision between CF3CH2CH2 and CF3 radicals to be 0.022 ? 0 002 and for CF3CH2CH2 and CF3CH2CH2 radicals to be 0.100 IT 0.002. Comparison to previous work from this laboratory for the reaction of CF3CH2CHCI with CF3 radicals shows that substitution of C1 for H increases the k d / k , by about 50%; however, for the auto disproportionation-combination of CF3CH2CH2 radicals the chlorine substituent decreases the observed rate constant ratio by a factor of two. The chlorine substituent effect on the observed k d / k , ratios is compared to predictions from molecular orbital calculations. Q 1996 john Wiley & Sons, inc

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## Abstract Rate constants for the gas‐phase reactions of CH~3~OCH~2~CF~3~ (__k__~1~), CH~3~OCH~3~ (__k__~2~), CH~3~OCH~2~CH~3~ (__k__~3~), and CH~3~CH~2~OCH~2~CH~3~ (__k__~4~) with NO~3~ radicals were determined by means of a relative rate method at 298 K. NO~3~ radicals were prepared by thermal d