Experimental and theoretical studies of gas phase NO3 and OH radical reactions with formaldehyde, acetaldehyde and their isotopomersElectronic supplementary information (ESI) available: program package FACSIMILE for simulation of the complex set of reactions and the kinetics of the reactor system. Kinetic data from the acetaldehyde studies, the spectral ranges and the compounds included in the subtraction procedures, and a full report of the statistical analyses. Calculated energies of the reactants, intermediate stationary points of the potential energy surface, and the products. Calculated vibrational wavenumbers of the reactants and transition states. See http://www.rsc.org/suppdata/cp/b2/b211234p/

Abstract

The vapour phase reactions of formaldehyde, formaldehyde-d2, 13C-formaldehyde, acetaldehyde, acetaldehyde-1-d1, acetaldehyde-2,2,2-d3, and acetaldehyde-d4 with NO3 and OH radicals were studied at 298 ± 2 K and 1013 ± 10 mbar using long-path FTIR detection. The values of the kinetic isotope effects at 298 K, as determined by the relative rate method, were: kNO3+HCHO/kNO3+DCDO = 2.97 ± 0.14, kNO3+HCHO/kNO3+H13CHO = 0.97 ± 0.02, kOH+HCHO/kOH+DCDO = 1.62 ± 0.08, and kOH+H13CHO/kOH+DCDO = 1.64 ± 0.12, kOH+HCHO/kOH+H13CHO = 0.97 ± 0.11, kNO3+CH3CHO/kNO3+CD3CHO = 1.19 ± 0.11, kNO3+CH3CHO/kNO3+CD3CDO = 2.51 ± 0.09, kOH+CH3CHO/kOH+CH3CDO = 1.42 ± 0.10, kOH+CH3CHO/kOH+CD3CHO = 1.13 ± 0.04, and kOH+CH3CHO/kOH+CD3CDO = 1.65 ± 0.08. Quoted errors represent 3σ from the statistical analyses. These errors do not include possible systematic errors.