Determination of the rate constants for the reactions of CFCl2O2 radical with NO and NO2 by laser photolysis and time resolved mass spectrometry

✍ Scribed by R. Lesclaux; F. Caralp

• Publisher: John Wiley and Sons
• Year: 1984
• Tongue: English
• Weight: 560 KB
• Volume: 16
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550160907

✦ Synopsis

The rate constants for reactions (4) and (5) ( 4 ) CFCI,O, 7 NO -+CFCI,O + NO, ( 5 ) CFCI,O, + NO, + M -CFCI,O,NO, -M were determined at room temperature by pulsed laser photolysis and time resolved mass spectrometry. A description of the experimental setup is given. CFCI,O, radicals were generated by photolysis of CFCI, a t 193 nm in the presence of an excess of oxygen, using an excimer laser. The rate constant for reaction (4). determined under different experimental conditions is: k, = 1.6 ( 2 0 . 2 ) x 10. I ' cm3 molecule ' . s I

The rate constant of reaction ( 5 ) was determined in the pressure range of 1-12 torr, using oxygen as the buffer gas. The reaction is in its fall-off region and the parameters determined by using the semiempirical method of Troe, taking F, = 0.6 are: k(0) = 3.5 ( 2 0.5) x 10 -'' cm' . molecule ' . s k ( r ) 6.0 ( f 1 .O) x 10 I' cm.' . molecule . s

I

The value of k ( x ) is obtained from the low-pressure measurements and therefore the uncertainty on the actual high-pressure limit is higher than the error limits quoted above. The results a r e compared with those reported for similar reactions.