Kinetics for the reaction of Criegee intermediate CH2OO with n-butyraldehyde and its atmospheric implications

Experimental and theoretical study of Criegee intermediate (CH2OO) reactions with n-butyraldehyde and isobutyraldehyde: kinetics, implications and atmospheric fate

“…35,79 The Arrhenius equations for (R4) and (R5) determined from the fit of the experimental results in Fig. 5 55 are also depicted in Fig. 5, which shows excellent agreement with the current study.…”

“…At high pressures, all these states are accessible, which makes the high-pressure limit rate coefficients larger. The high-pressure limit rate coefficients (k CVT/SCTÀHR ) at 298 K were calculated to be 5.62 Â 10 À12 cm 3 molecule À1 s À1 , whereas the same obtained by Liu et al 55 using the Lindemann fitting of the experimental rate coefficients was (3.05 AE 0.55) Â 10 À12 cm 3 molecule À1 s À1 . This deviation can be attributed to the dominance of the loose TS at low temperatures for which no special treatment (VRC) was performed in the current study.…”

“…At room temperature, the rate coefficients obtained for (R4) and (R5) are (2.63 AE 0.14) Â 10 À12 and (2.20 AE 0.21) cm 3 molecule À1 s À1 , respectively, at 298 K and 50 torr. The rate coefficient for CH 2 OO + nBD was reported to be (2.92 AE 0.53) Â 10 À12 cm 3 molecule À1 s À1 at 298 K and 50 torr by an indirect measurement, by probing the OH radicals generated in the reaction, using the Laser-Induced Fluorescence (LIF) technique by Liu et al 35,55 The room temperature rate coefficient for (R4) was B13% higher in their study, which comes in the reported error limit of 18%.…”

“…5. From MESMER calculations, the addition rate coefficients for CH 2 OO + n BD/iBD were found to be independent of pressure in the range 2–1000 torr and at 298 K. Liu et al 55 reported that for CH 2 OO + n BD reaction, the rate coefficient reaches 95% of the high-pressure limit at 15 torr. This means that above 15 torr, the pressure dependence should be negligible, which was observed in the case of the MESMER results in the current study.…”

“…A very recent study has reported the rate coefficient for CH 2 OO + n BD to be (2.97 ± 0.53) × 10 −12 cm 3 molecule −1 s −1 at 298 K and 50 torr. 55 The temperature- and pressure-dependent rate coefficients were obtained by an indirect kinetic approach by monitoring the OH radicals generated from the CH 2 OO intermediates at a particular reaction time. However, no such kinetic data was available for the reaction of CH 2 OO with iBD in the literature.…”