Kinetics of CN radical reactions with formaldehyde and 1,3,5-trioxane

✍ Scribed by Tao Yu; David L. Yang; M. C. Lin

• Publisher: John Wiley and Sons
• Year: 1993
• Tongue: English
• Weight: 570 KB
• Volume: 25
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550251210

✦ Synopsis

Absolute rate constants were measured for the reaction CN + CH20 over the temperature range 297-673 K and CN + 1,3,5-trioxane over the range of 297-600 K by the laser photolysis/laser induced fluorescence technique. The rate constants for these reactions can be effectively represented, in units of cm3/s, by: W(CH20) = 2.82 X p.72 exp(718/T), and k(l,3,5-trioxane) = 1.39 X T'.26 exp(1333/T), respectively. Transition state theory calculations were able to fit the temperature dependence of the CN + CH20 rates relatively well. We attempted to correlate the CN reaction rate with CH20 and other molecules which occur through simple abstraction with the corresponding OH reaction rates, yielding only a qualitative linear correlation for a majority of the processes. The reactions which deviated significantly from linearity include those which contain strong dipoles, highlighting the significant role long-range attractive forces play in CN and OH reactions. Using a simple electrostatic potential, cross-sections were determined for reactions with CN. No linear correlation was found between the calculated and experimental cross sections for the majority of the reactions studied.