Thermal and photochemical reactions of nitrogen dioxide with butyraldehyde in gas phase

Abstract

The rates of thermal and photochemical reactions of butyraldehyde with NO2 were measured. The thermal rate constant was determined to be 107•4 exp (-12,400/ RT) lm-1 sec-1. The rate constant for the reaction of oxygen atoms with butyraldehyde was determined to be 1.5 X 10s lm"1 sec-1 at 25°C. These results are close to those for the lower-molecular-weight aldehydes and indicate that they may all be treated by means of one general mechanism. 530 (1973).

Theoretical study of the reaction mechanism and kinetics of low-molecular-weight atmospheric aldehydes (C1–C4) with NO2

“…From the (Alvarez-Idaboy et al, 2001). This discrepancy between our calculated data and experimental results (Jaffe and Wan, 1974) may be explained that the activities of LMW aldehydes are not only relative to the aldehydic CeH bond energy, but also affected by the steric effect and electronic effect of the alkyl group within long-chain LMW aldehydes. (Zheng and Truhlar, 2010).…”

“…As for the reaction of butanal with NO 2 , as shown in Fig. 5d, the calculated CVT/SCT rate constants are also close to the available experimental values (Jaffe and Wan, 1974) with the largest deviation within a factor of 1.9 within the temperature range of 250e360 K. As indicated in the above results, the good match was observed between the theoretical results and the experimental values for above three aldehydes. Therefore, for the reaction of propanal with NO 2 , despite the absence of the available experimental values, the calculated rate constants should be reliable.…”

“…And, the total CVT/SCT rate constants obtained as the sum of the individual rate constants associated with the syn-R O-abs 1 and R N-sbs 1 channels are shown in Fig. 5aed along with the available previous experimental values (Christie and Voisey, 1967;Davis and Corcoran, 1972;Jaffe and Wan, 1974).…”

“…As for acetaldehyde, the rate constants measured by four experimental groups (Christie and Voisey, 1967;Davis and Corcoran, 1972;Mcdowell and Thomas, 1950;Pedler and Pollard, 1957) are not consistent well with each other. But there is no reported on propanal and much limited information is reported relative to butanal based on the experiments (Jaffe and Wan, 1974). The author summarized that the kinetics and mechanisms of butanal with NO 2 are all similar to three LMW aldehydes (up to propanal) based on previously experimental results (Jaffe and Wan, 1974).…”

“…But there is no reported on propanal and much limited information is reported relative to butanal based on the experiments (Jaffe and Wan, 1974). The author summarized that the kinetics and mechanisms of butanal with NO 2 are all similar to three LMW aldehydes (up to propanal) based on previously experimental results (Jaffe and Wan, 1974). Therefore, the questions will arise: are the mechanisms of the reaction of propanal with NO 2 similar to the other LMW aldehydes?…”