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

Ji, Yuemeng; Gao, Yanpeng; Li, Guiying; An, Taicheng

doi:10.1016/j.atmosenv.2012.02.040

Cited by 30 publications

(23 citation statements)

References 39 publications

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“…Photolysis and reactions with OH· could change the distributions of carbonyls (Atkinson, 2000;Pang and Lee, 2010), and the reaction with OH· was often the dominant loss (Atkinson, 2000), depending on reaction rate constants, e.g., the reaction rate constants are 0.98 and 1.58 (×10 11 cm 3 /molecule/s) for formaldehyde and acetaldehyde, respectively. The relative long-chain low-weight carbonyls were more reactive than those short-chain carbonyls in the atmosphere (Ji et al, 2012). So, the expected C 1 /C 2 ratio would increase under active photochemical conditions.…”

Section: Concentration Ratiosmentioning

confidence: 99%

“…Long-chain low-weight carbonyls were more reactive than those short-chain carbonyls (Atkinson, 2000;Ji et al, 2012), which could result in the faster photochemical loss of the former under high temperature condition. As presented in Table 2, the recorded temperature and sunlight intensity were higher in summer than that in spring.…”

Section: Seasonal and Diurnal Variationsmentioning

confidence: 99%

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Seasonal and Diurnal Characteristics of Carbonyls in Urban Air in Qinzhou, China

Guo

Chen

et al. 2014

Aerosol Air Qual. Res.

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Ambient carbonyls in urban air in Qinzhou were studied form October 2011 to July 2012 to investigate their distribution characteristics and sources. Acetaldehyde (8.04 ± 9.00 µg/m 3 ), formaldehyde (6.70 ± 6.36 µg/m 3 ) and acetone (2.43 ± 2.81 µg/m 3 ) were three most abundant carbonyls, accounting for ~90% of the seven carbonyls identified. Concentrations of most carbonyls showed significantly higher levels in spring and summer than those in autumn and winter. Seasonal and diurnal variations indicated that formaldehyde and acetaldehyde were related to barbecue emissions and photochemical loss, while solvent usage was responsible for acetone. The average C 1 /C 2 ratio was higher (1.92) in summer than that during other seasons (0.52-1.78), implying the positive impact of photochemical loss or formation; and a significantly lower C 2 /C 3 ratio (2.57) was observed in winter than during other seasons (12.47-52.82), suggesting significant emissions from straw burning and barbecues. Formaldehyde and acetaldehyde were the two major contributors (63-97%) to O 3 formation, particularly in spring and summer.

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Section: Concentration Ratiosmentioning

confidence: 99%

Section: Seasonal and Diurnal Variationsmentioning

confidence: 99%

Seasonal and Diurnal Characteristics of Carbonyls in Urban Air in Qinzhou, China

Guo

Chen

et al. 2014

Aerosol Air Qual. Res.

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“…As a part of our ongoing study, the MPWB1K function (Zhao and Truhlar, 2004) was also used in this work, which has been already employed to successfully calculate the homogenous reactions of VOCs with RSs (Ji et al, 2012). The geometrical parameters of all stationary points were calculated with a standard 6-311G(d,p) basis set, and hereinafter the employed function level was denoted as MPWB1K/6-311G(d,p) level.…”

Section: Methodsmentioning

confidence: 99%

“…NO 2 is not only an important constituent of the natural unpolluted atmosphere, but also one of the major pollutants from anthropogenic sources such as motor vehicles (Power et al, 2011), power plants (Jurkat et al, 2011) and combustion process (Zhang et al, 2006). Thus, it has taken a great deal of research to the reaction of HCHO and NO 2 in the absence of SiO 2 (Ji et al, 2012;Xu and Lin, 2003) or to the adsorption performance of HCHO onto SiO 2 (Carlos-Cuellar et al, 2003;Iuga et al, 2008), but to our knowledge, no prior theoretical and experimental studies have been explored the heterogeneous reaction of HCHO with NO 2 in the presence of SiO 2 . The goals of this study are as follows: (i) find a reasonable theoretical method to model the heterogeneous reaction of VOCs; (ii) specify which species is more easily absorbed onto the mineral dust aerosol surface: organic or inorganic compounds; (iii) probe the role of mineral dust aerosol on the atmospheric reaction.…”

Section: Introductionmentioning

confidence: 99%

“…Due to the potential adverse effects on human health and the active involvement in the atmospheric reactions (Ji et al, 2012), the atmospheric reactions of VOCs have attracted significant scientific and regulatory attention. Therefore, the homogeneous atmospheric reactions of VOCs with various reactive species (RSs) have been investigated in detail currently, and significant advances were made to understand both the kinetics and mechanisms of these reactions, as well as their global impact on the atmosphere (Alvarez-Idaboy et al, 2001;Atkinson, 2000;Atkinson and Arey, 2003;Stemmler et al, 1997).…”

Section: Introductionmentioning

confidence: 99%

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Theoretical investigation on the role of mineral dust aerosol in atmospheric reaction: A case of the heterogeneous reaction of formaldehyde with NO 2 onto SiO 2 dust surface

Wang

et al. 2015

Atmospheric Environment

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Theoretical study on the atmospheric degradation mechanism and subsequent products of E,E‐2,4‐hexadienal with hydroxyl radical

Sun

Yao

Tang

et al. 2020

Int J of Quantum Chemistry

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E,E‐2,4‐hexadienal is probably a precursor of secondary organic aerosol (SOA) and plays an important role in the atmospheric chemistry. Its main degradation routs are the reactions with OH, Cl, NO3 as well as photolysis. Atmospheric hydroxyl radical, as the most important oxidant, generally controls the removal of volatile organic compounds in the atmosphere. Thus, the quantum chemical calculations are used to investigate the reaction mechanism of E,E‐2,4‐hexadienal with hydroxyl radical, which would give us a better understanding for the main degradation products. The reaction paths of E,E‐2,4‐hexadienal with OH radical have been calculated accurately by using the BMC‐CCSD//M06‐2X/6‐311G (d, p) level at atmospheric pressure and room temperature. There are six hydrogen abstraction and four carbon addition paths at the first stages of this reaction. Due to the low energy barrier and exothermic reaction, the ten paths would contribute to the total reaction. Furthermore, the peroxy (RO2) and alkoxy (RO) radicals from the most important adduct IM1(CH3CHOHCHCHCHCHO) would be formed in the atmospheric environment. Hence, the reaction mechanism of the peroxy radical (CH3CHOHCHO2CHCHCHO) with NO, NO2, HO2, and self‐reaction have been also studied by using the same quantum chemical methods. And the reaction paths of alkoxy radical (CH3CHOHCHOCHCHCHO) have been also originally studied. It is found that the subsequent reactions play a key role in the cycling of atmospheric radicals, production of ozone, and SOA formation. What is more, the reaction mechanism of this study accords with the reported experimental observations. Meanwhile, the theoretical rate constant of 1.05 × 10−10 cm3 molecule−1 s−1 of E,E‐2,4‐hexadienal with OH reaction at 298 K is close to experimental data. The atmospheric lifetime of E,E‐2,4‐hexadienal with OH radical is about 2.6 h at 298 K. This study provides insight into the transformation of E,E‐2,4‐hexadienal in the atmospheric environment.

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

Cited by 30 publications

References 39 publications

Seasonal and Diurnal Characteristics of Carbonyls in Urban Air in Qinzhou, China

Seasonal and Diurnal Characteristics of Carbonyls in Urban Air in Qinzhou, China

Theoretical investigation on the role of mineral dust aerosol in atmospheric reaction: A case of the heterogeneous reaction of formaldehyde with NO 2 onto SiO 2 dust surface

Theoretical study on the atmospheric degradation mechanism and subsequent products of E,E‐2,4‐hexadienal with hydroxyl radical

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