Kinetics of the reaction CH + N2 rarr; [M]⇒[M] products in the range 10–620 torr and 298–1059 K

✍ Scribed by K. H. Becker; H. Geiger; P. Wiesen

• Publisher: John Wiley and Sons
• Year: 1996
• Tongue: English
• Weight: 616 KB
• Volume: 28
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/(sici)1097-4601(1996)28:2<115::aid-kin7>3.0.co;2-y

✦ Synopsis

The gas-phase reaction of CH(X'II) radicals with molecular nitrogen was studied in the temperature range 298-1059 K at total pressures between 10 and 620 torr. CH radicals were generated by excimer laser photolysis of CHCIBrz at 248 nrn and were detected by laserinduced fluorescence The investigated reaction shows a strong temperature and pressure dependence. At pressures of 20, 100, and 620 torr the Arrhenius plots exhibit a strong decrease of the rate constant with increasing temperature. The rate constant is well described by kpolorr) = (24 C 6) X T-'525'0.051 X exp[-(7.57 C 0.83)/RT] cm3 s-', k l l W ,on) = (107 T 25) X T-(s2"0.0s) X exp[-(7.38 C 0.83)/RT] cm3 S C ' , k(620 ion) = (1467 C 350) X T-'54*'0051 x exp[-(7.82 c ~.oo)/RT] cm3 s -' , with Eo in klhol. The pressure dependence was studied at temperatures of 298, 410, 561, and 750 K The rate constants for each temperature were fitted by the Troe formalism. From the calculated values of ko and k,, the Arrhenius expressions, ko = (1.1 2 0.2) x k , = (1.9::;) X x P 5 ' -0 . 3 x e xp[-(6.4 2 0.5)/RT] crn6 s -' and X exp[(3.6 2 0.4)/RT] cm3 s -' ,

were obtained with Eo(k0) and EA(k,) in units of kJ/mol. Within the range of 298-750 K the temperature dependence of the broadening factor is well described by F, = 0.