TY - JOUR
T1 - Kinetic studies of reactions of the nitrate radical (NO3) with peroxy radicals (RO2)
T2 - an indirect source of OH at night?
AU - Vaughan, S.
AU - Canosa-Mas, C.E.
AU - Pfrang, C.
AU - Shallcross, D.E.
AU - Watson, L.
AU - Wayne, R.P.
PY - 2006/7/12
Y1 - 2006/7/12
N2 - A discharge–flow system, coupled to cavity-enhanced absorption spectroscopy (CEAS) detection systems for NO3 at λ = 662 nm and NO2 at λ = 404 nm, was used to investigate the kinetics of the reactions of NO3 with eight peroxy radicals at P ∼ 5 Torr and T ∼ 295 K. Values of the rate constants obtained were (k/10−12 cm3 molecule−1 s−1): CH3O2 (1.1 ± 0.5), C2H5O2 (2.3 ± 0.7), CH2FO2 (1.4 ± 0.9), CH2ClO2 (3.8+1.4−2.6), c-C5H9O2 (1.2+1.1−0.5), c-C6H11O2 (1.9 ± 0.7), CF3O2 (0.62 ± 0.17) and CF3CFO2CF3 (0.24 ± 0.13). We explore possible relationships between k and the orbital energies of the reactants. We also provide a brief discussion of the potential impact of the reactions of NO3 with RO2 on the chemistry of the night-time atmosphere.
AB - A discharge–flow system, coupled to cavity-enhanced absorption spectroscopy (CEAS) detection systems for NO3 at λ = 662 nm and NO2 at λ = 404 nm, was used to investigate the kinetics of the reactions of NO3 with eight peroxy radicals at P ∼ 5 Torr and T ∼ 295 K. Values of the rate constants obtained were (k/10−12 cm3 molecule−1 s−1): CH3O2 (1.1 ± 0.5), C2H5O2 (2.3 ± 0.7), CH2FO2 (1.4 ± 0.9), CH2ClO2 (3.8+1.4−2.6), c-C5H9O2 (1.2+1.1−0.5), c-C6H11O2 (1.9 ± 0.7), CF3O2 (0.62 ± 0.17) and CF3CFO2CF3 (0.24 ± 0.13). We explore possible relationships between k and the orbital energies of the reactants. We also provide a brief discussion of the potential impact of the reactions of NO3 with RO2 on the chemistry of the night-time atmosphere.
UR - http://www.scopus.com/inward/record.url?eid=2-s2.0-33747334970&partnerID=MN8TOARS
U2 - 10.1039/b605569a
DO - 10.1039/b605569a
M3 - Article
SN - 1463-9076
VL - 8
SP - 3749
EP - 3760
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
IS - 32
ER -