TY - JOUR
T1 - Gas-phase rate coefficients for the reactions of NO3, OH and O3 with α,β-unsaturated esters and ketones: Structure-activity relations (SARs)
AU - Pfrang, C.
AU - King, M.D.
AU - Canosa-Mas, C.E.
AU - Flugge, M.
AU - Wayne, R.P.
PY - 2007/3
Y1 - 2007/3
N2 - Gas-phase rate coefficients for the atmospherically important reactions of NO3, OH and O3 are predicted for 55 α,β-unsaturated esters and ketones. The rate coefficients were calculated using a correlation described previously [Pfrang, C., King, M.D., C. E. Canosa-Mas, C.E., Wayne, R.P., 2006. Atmospheric Environment 40, 1170–1179]. These rate coefficients were used to extend structure–activity relations for predicting the rate coefficients for the reactions of NO3, OH or O3 with alkenes to include α,β-unsaturated esters and ketones. Conjugation of an alkene with an α,β-keto or α,β-ester group will reduce the value of a rate coefficient by a factor of ∼110, ∼2.5 and ∼12 for reaction with NO3, OH or O3, respectively. The actual identity of the alkyl group, R, in −C(O)R or −C(O)OR has only a small influence. An assessment of the reliability of the SAR is given that demonstrates that it is useful for reactions involving NO3 and OH, but less valuable for those of O3 or peroxy nitrate esters.
AB - Gas-phase rate coefficients for the atmospherically important reactions of NO3, OH and O3 are predicted for 55 α,β-unsaturated esters and ketones. The rate coefficients were calculated using a correlation described previously [Pfrang, C., King, M.D., C. E. Canosa-Mas, C.E., Wayne, R.P., 2006. Atmospheric Environment 40, 1170–1179]. These rate coefficients were used to extend structure–activity relations for predicting the rate coefficients for the reactions of NO3, OH or O3 with alkenes to include α,β-unsaturated esters and ketones. Conjugation of an alkene with an α,β-keto or α,β-ester group will reduce the value of a rate coefficient by a factor of ∼110, ∼2.5 and ∼12 for reaction with NO3, OH or O3, respectively. The actual identity of the alkyl group, R, in −C(O)R or −C(O)OR has only a small influence. An assessment of the reliability of the SAR is given that demonstrates that it is useful for reactions involving NO3 and OH, but less valuable for those of O3 or peroxy nitrate esters.
UR - http://www.scopus.com/inward/record.url?eid=2-s2.0-33846450641&partnerID=MN8TOARS
U2 - 10.1016/j.atmosenv.2006.11.026
DO - 10.1016/j.atmosenv.2006.11.026
M3 - Article
SN - 1352-2310
VL - 41
SP - 1792
EP - 1802
JO - Atmospheric Environment
JF - Atmospheric Environment
IS - 8
ER -