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A kinetic and product study of the gas‐phase reaction of ozone with vinylcyclohexane and methylene cyclohexane
Author(s) -
Grosjean Eric,
Grosjean Daniel
Publication year - 1997
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/(sici)1097-4601(1997)29:11<855::aid-kin7>3.0.co;2-l
Subject(s) - chemistry , cyclohexane , methylene , formaldehyde , cyclohexanone , reaction rate constant , ozonolysis , medicinal chemistry , photochemistry , ozone , reaction rate , organic chemistry , kinetics , catalysis , physics , quantum mechanics
The gas‐phase reaction of ozone with vinylcyclohexane and methylene cyclohexane has been investigated at ambient T and p =1 atm of air in the presence of sufficient cyclo‐hexane or 2‐propanol added to scavenge OH. The reaction rate constants, in units of 10 −18 cm 3 molecule −1 s −1 , are 7.52±0.97 for vinylcyclohexane ( T =292±2 K) and 10.6±1.9 for methylene cyclohexane ( T =293±2 K). Carbonyl reaction products were cyclohexyl meth‐anal (0.62±0.03) and formaldehyde (0.47±0.04) from vinylcyclohexane and cyclohexanone (0.55±0.10) and formaldehyde (0.60±0.05) from methylene cyclohexane, where the yields given in parentheses are expressed as carbonyl formed, ppb/reacted ozone, ppb. The sum of the yields of the primary carbonyls is close to the value of 1.0 that is consistent with the simple mechanisms: O 3 +cyclo(C 6 H 11 )−CH(DOUBLEBOND)CH 2 →α(HCHO+cyclo(C 6 H 11 )CHOO)+(1−α)(HCHOO+cyclo(C 6 H 11 )CHO) for vinylcyclohexane andO 3 +(CH 2 ) 5 C(DOUBLEBOND)CH 2 →α(HCHO +(CH 2 ) 5 COO)+(1−α)(HCHOO+(CH 2 ) 5 C(DOUBLEBOND)O) for methylene cyclohexane. The coefficients α are 0.43±0.10 for vinylcyclohexane and 0.52±0.05 for methylene cyclohexane, i.e., (formaldehyde+the substituted biradical) and (HCHOO+cyclohexyl methanal or cyclo‐hexanone) are formed in ca. equal yields. Reaction rate constants, carbonyl yields, and reaction mechanisms are compared to those for alkene structural homologues. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 855–860, 1997