Atmospheric chemistry of 1,3,5-trioxane: UV spectra of c-C₃H₅O₃(•) and (c-C₃H₅O₃)O₂(•) radicals, kinetics of the reactions of (c-C₃H₅O₃)O₂(•) radicals with NO and NO₂, and atmospheric fate of the alkoxy radical

TY - JOUR

T1 - Atmospheric chemistry of 1,3,5-trioxane

T2 - UV spectra of c-C3H5O3(•) and (c-C3H5O3)O2(•) radicals, kinetics of the reactions of (c-C3H5O3)O2(•) radicals with NO and NO2, and atmospheric fate of the alkoxy radical

AU - Platz, J.

AU - Christensen, L. K.

AU - Sehested, J.

AU - Nielsen, O. J.

AU - Wallington, T. J.

AU - Sauer, C.

AU - Barnes, Ian

AU - Becker, K. H.

AU - Vogt, R.

PY - 1998/6/18

Y1 - 1998/6/18

N2 - A pulse radiolysis technique was used to measure the UV absorption spectra of c-C3H5O3(•) and (c-C3H5O3)-O2(•) radicals over the range 220-300 nm, with σ(c-C3H5O3(«))250 nm = (5.2 ± 0.7) × 10-18 and σ((c-C3H5O3)-O2(•)) 250 nm = (3.7 ± 0.4) × 10-18 cm2 molecule-1. The self-reaction rate constant for the c-C3H5O3(•) radicals, defined as d[c-C3H5O3(•)]/dt = 2k4[c-C3H5O3(•)]2, was k4 = (3.1 ± 0.6) × 10-11 cm3 molecule-1 s-1. The rate constants for reactions of (c-C3H5O3)O2(•) radicals with NO and NO2 were k6 = (5.8 ± 1.4) × 10-12 and k7 = (1.1 ± 0.2) × 10-11 cm3 molecule-1 s-1, respectively. The rate constants for the reaction of F atoms with 1,3,5-trioxane and the reaction of c-C3H5O3(•) radicals with O2 were k3 = (1.1 ± 0.4) × 10-10 and k2 = (7.4 ± 1.1) × 10-12 cm3 molecule-1 s-1, respectively. Relative rate techniques were used to measure the rate constants for the reactions of OH radicals and Cl atoms with 1,3,5-trioxane and Cl atoms with H(O)-COCH2OC(O)H, k20 = (6.0 ± 1.0) × 10-12, k24 = (1.0 ± 0.2) × 10-10, and k25 = (5.1 ± 1.0) × 10-13 cm3 molecule-1 s-1, respectively. FTIR-smog chamber systems were used to show that the atmospheric fate of the alkoxy radical (c-C3H5O3)O(•) is decomposition via C-O bond scission leading to the formation of H(O)-COCH2OC(O)H (methylene glycol diformate). The IR spectrum of the peroxynitrate (c-C3H5O3)O2NO2 is presented. The results are discussed with respect to the atmospheric chemistry of 1,3,5-trioxane.

AB - A pulse radiolysis technique was used to measure the UV absorption spectra of c-C3H5O3(•) and (c-C3H5O3)-O2(•) radicals over the range 220-300 nm, with σ(c-C3H5O3(«))250 nm = (5.2 ± 0.7) × 10-18 and σ((c-C3H5O3)-O2(•)) 250 nm = (3.7 ± 0.4) × 10-18 cm2 molecule-1. The self-reaction rate constant for the c-C3H5O3(•) radicals, defined as d[c-C3H5O3(•)]/dt = 2k4[c-C3H5O3(•)]2, was k4 = (3.1 ± 0.6) × 10-11 cm3 molecule-1 s-1. The rate constants for reactions of (c-C3H5O3)O2(•) radicals with NO and NO2 were k6 = (5.8 ± 1.4) × 10-12 and k7 = (1.1 ± 0.2) × 10-11 cm3 molecule-1 s-1, respectively. The rate constants for the reaction of F atoms with 1,3,5-trioxane and the reaction of c-C3H5O3(•) radicals with O2 were k3 = (1.1 ± 0.4) × 10-10 and k2 = (7.4 ± 1.1) × 10-12 cm3 molecule-1 s-1, respectively. Relative rate techniques were used to measure the rate constants for the reactions of OH radicals and Cl atoms with 1,3,5-trioxane and Cl atoms with H(O)-COCH2OC(O)H, k20 = (6.0 ± 1.0) × 10-12, k24 = (1.0 ± 0.2) × 10-10, and k25 = (5.1 ± 1.0) × 10-13 cm3 molecule-1 s-1, respectively. FTIR-smog chamber systems were used to show that the atmospheric fate of the alkoxy radical (c-C3H5O3)O(•) is decomposition via C-O bond scission leading to the formation of H(O)-COCH2OC(O)H (methylene glycol diformate). The IR spectrum of the peroxynitrate (c-C3H5O3)O2NO2 is presented. The results are discussed with respect to the atmospheric chemistry of 1,3,5-trioxane.

UR - http://www.scopus.com/inward/record.url?scp=0000688712&partnerID=8YFLogxK

M3 - Journal article

AN - SCOPUS:0000688712

SN - 1089-5639

VL - 102

SP - 4829

EP - 4838

JO - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

JF - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

IS - 25

ER -