Kinetics and mechanism of the reaction H + CH3ONO

✍ Scribed by G. K. Moortgat; F. ŠSlemr; P. Warneck

• Publisher: John Wiley and Sons
• Year: 1977
• Tongue: English
• Weight: 845 KB
• Volume: 9
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550090209

✦ Synopsis

The reaction of hydrogen atoms with methyl nitrite was studied in a fast-flow system

The associated biusing photoionization mass spectrometry and excess atomic hydrogen. molecular rate coefficient can be expressed by k, = (4.3 f 0.9) x 10-13 exp [ -(1900 f 110) cal/mol . R T ] cm3/molecule . sec in the temperature range of 223-398°K. main products; OH and CH3 radicals were detectable intermediates. deduced from the observed product yields using normal and deuterated reactants. primary reaction steps were identified aa NO, CHZOH, CH,, CZH,, CHZO, and HZO are the The mechanism was The (la) H + CHIONO + CHaOH + NO 47 f 5% 53 f 5% I + CHzONO + Hz -+ CH30 + HNO followed by a rapid unimolecular decomposition of CHzONO into CH20 and NO. Since the extent of reaction channel (lb) could not be determined independently, only extreme limits could be obtained for the individual contributions of the two channels of reaction (3) which follows the generation of CHIO radicals: ( 3 4 H + CH30 -tCHzO + Hz 0-61%

-+ CH3 + OH 100-39%

The most probable values, ka,/kz = 0.31 f 0.30 and k3t,/k3 = 0.69 f 0.30, support the previous results on this reaction, although the range of uncertainties is much greater here.