TY - JOUR
T1 - Reactions of NO3 with the man-made emissions 2-methylpent-2-ene, (Z)-3-methylpent-2-ene, ethyl vinyl ether, and the stress-induced plant emission ethyl vinyl ketone
AU - Pfrang, C.
AU - Tooze, C.
AU - Nalty, A.
AU - Canosa-Mas, C.E.
AU - Wayne, R.P.
PY - 2006
Y1 - 2006
N2 - Rate coefficients for reactions of nitrate radicals (NO3) with the anthropogenic emissions 2-methylpent-2-ene, (Z)-3-methylpent-2-ene, ethyl vinyl ether, and the stress-induced plant emission ethyl vinyl ketone (pent-1-en-3-one) were determined to be (9.3±1.1)×10−12, (9.3±3.2)×10−12, (1.7±1.3)×10−12 and (9.4±2.7)×10−17 cm3 molecule−1 s−1. We performed kinetic experiments at room temperature and atmospheric pressure using a relative-rate technique with GC–FID analysis. Experiments with ethyl vinyl ether required a modification of our established procedure that might introduce additional uncertainties, and the errors suggested reflect these difficulties. Rate coefficients are discussed in terms of electronic and steric influences. Atmospheric lifetimes with respect to important oxidants in the troposphere were calculated. NO3-initiated oxidation is found to be the strongly dominating degradation route for 2-methylpent-2-ene, (Z)-3-methylpent-2-ene and ethyl vinyl ether. Atmospheric concentrations of the alkenes and their relative contribution to the total NMHC emissions from trucks can be expected to increase if plans for the introduction of particle filters for diesel engines are implemented on a global scale. Thus more kinetic data are required to better evaluate the impact of these emissions.
AB - Rate coefficients for reactions of nitrate radicals (NO3) with the anthropogenic emissions 2-methylpent-2-ene, (Z)-3-methylpent-2-ene, ethyl vinyl ether, and the stress-induced plant emission ethyl vinyl ketone (pent-1-en-3-one) were determined to be (9.3±1.1)×10−12, (9.3±3.2)×10−12, (1.7±1.3)×10−12 and (9.4±2.7)×10−17 cm3 molecule−1 s−1. We performed kinetic experiments at room temperature and atmospheric pressure using a relative-rate technique with GC–FID analysis. Experiments with ethyl vinyl ether required a modification of our established procedure that might introduce additional uncertainties, and the errors suggested reflect these difficulties. Rate coefficients are discussed in terms of electronic and steric influences. Atmospheric lifetimes with respect to important oxidants in the troposphere were calculated. NO3-initiated oxidation is found to be the strongly dominating degradation route for 2-methylpent-2-ene, (Z)-3-methylpent-2-ene and ethyl vinyl ether. Atmospheric concentrations of the alkenes and their relative contribution to the total NMHC emissions from trucks can be expected to increase if plans for the introduction of particle filters for diesel engines are implemented on a global scale. Thus more kinetic data are required to better evaluate the impact of these emissions.
UR - http://www.scopus.com/inward/record.url?eid=2-s2.0-29344455125&partnerID=MN8TOARS
U2 - 10.1016/j.atmosenv.2005.10.009
DO - 10.1016/j.atmosenv.2005.10.009
M3 - Article
SN - 1352-2310
VL - 40
SP - 786
EP - 792
JO - Atmospheric Environment
JF - Atmospheric Environment
IS - 4
ER -