Using a fast-flow-discharge technique, absolute rate coefficients for the gas-phase reactions of the NO3 radical with a series of branched aldehydes (2-methylpropanal, 2,2-dimethylpropanal, 2-methylbutanal and 3-methylbutanal) have been determined. The experiments were carried out monitoring the NO3 radical by laser induced fluorescence (LIF). The temperature dependence of the reaction was studied in the range between 298 and 433 K. The proposed Arrhenius expressions, are respectively:
k 1 = (1.0 ± 0.5) × 10−10exp[−(2598 ± 384)/T]/cm3 molecule−1 s−1,
k 2 = (2.7 ± 1.2) × 10−11exp[−(2063 ± 356)/T]/cm3 molecule−1 s−1,
k 3 = (5.5 ± 3.1) × 10−11exp[−(2296 ± 555)/T]/cm3 molecule−1 s−1,
k 4 = (3.7 ± 1.4) × 10−11exp[−(2184 ± 230)/T]/cm3 molecule−1 s−1.
Tropospheric lifetimes for these aldehydes have been calculated at night and during the daytime for typical NO3 and OH average concentrations.