Theoretical Investigation of the NO3 Radical Addition to Double Bonds of Limonene

Jiang, Lei; Wang, Wei; Xu, Yisheng

doi:10.3390/ijms10093743

Cited by 19 publications

(9 citation statements)

References 36 publications

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“…Recently, Xu et al . performed theoretical calculation on the addition of NO 3 to CC double bond in limonene . They explained the branching ratio of the final product by calculating the energy and activation energy of the radical intermediate produced by the addition of NO 3 to two CC double bonds in limonene.…”

Section: Total Energies For the Species Involved In The Reactions Of supporting

confidence: 69%

Theoretical Study on the Reaction of Sabinene with NO₃

Park

Kim

2020

Bulletin Korean Chem Soc

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Section: Total Energies For the Species Involved In The Reactions Of supporting

confidence: 69%

Theoretical Study on the Reaction of Sabinene with NO₃

Park

Kim

2020

Bulletin Korean Chem Soc

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“…Theoretical investigations have revealed that NO3 addition on the endocyclic C=C double bond is more favorable than the exocyclic one due to a lower energy barrier (Jiang et al, 2009). Typically, in the limonene + NO3 reaction, the endocyclic double bond of limonene tends to be attacked by NO3 and leads to products including hydroxysubstituted ON or diketone products.…”

Section: Introductionmentioning

confidence: 99%

Identification of highly oxygenated organic molecules and their role in aerosol formation in the reaction of limonene with nitrate radical

Guo

Shen

Pullinen³

et al. 2022

Preprint

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Abstract. Nighttime nitrate radical(NO3)-initiated oxidation of biogenic volatile organic compounds (BVOC) such as monoterpenes is important for the formation and growth of secondary organic aerosol (SOA), which has significant impact on climate, air quality and human health. In SOA formation and growth from the oxidation of monoterpenes by NO3, highly oxygenated organic molecules (HOM) may be crucial, but their formation pathways and role in aerosol formation have yet to be clarified. Among monoterpenes, limonene is of research interest for its high emission globally and high SOA yield. In this work, HOM formation in the reaction of limonene with nitrate radical was investigated in the SAPHIR chamber (Simulation of Atmospheric PHotochemistry In a large Reaction chamber). About 280 HOM products were identified, grouped into 6 monomer series (each including 3 families) and one family, 11 dimer families and 3 trimer families. Both closed-shell products and open-shell peroxy radicals (RO2•) were observed, and many of them have not been reported previously. Monomers and dimers accounted for over 90 % of HOM concentrations. In the most abundant monomer series – C10H15–17NO6–14, carbonyl products outnumbered hydroxyl products, indicating the importance of the unimolecular RO2• termination pathway. Both RO2• autoxidation and alkoxy-peroxy pathways were found to be important processes leading to HOM. Time-dependent concentration profiles of monomer products containing nitrogen showed mainly second-generation formation patterns. Dimers were likely formed via the accretion reaction of two monomer RO2•, and HOM-trimers via the accretion reaction between monomer RO2• and dimer RO2•. Trimers are suggested to play an important role in new particle formation (NPF) observed in our experiment. A HOM yield of 1.5 % (+1.7 %/−0.7 %) was estimated considering only first-generation products. SOA mass growth could be reasonably explained by HOM condensation on particles assuming irreversible uptake of extremely low volatility organic compounds (ELVOC) and low volatility organic compounds (LVOC). This work provides evidence for the important role of HOM formed via the limonene + NO3 reaction in NPF and SOA growth.

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“…The reaction mechanism involves the initial addition of NO3 across a double bond to form a nitrooxyalkyl radical, which, in air, forms a nitrooxyalkyl peroxy radical. Product studies suggest that attack of NO3 at the exocyclic double bond of limonene is insignificant (Spittler et al 2006), which is supported by theoretical calculations (Jiang et al, 2009).…”

Section: Comments On Preferred Valuesmentioning

confidence: 57%

Supplementary material to "Evaluated kinetic and photochemical data for atmospheric chemistry: Volume VIII – gas phase reactions of organic species with four, or more, carbon atoms (≥ C<sub>4</sub>)"

Mellouki¹,

Ammann²,

Cox³

et al. 2020

Preprint

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Relative Rate Coefficients 9.9 × 10-12 753 Baker et al., 1970; Baldwin and Walker, 1979 RR (b) (9.3 ± 0.8) × 10-12 653 Hucknall et al, 1975 RR (c) (2.64 ± 0.25) × 10-12 299 ± 2 Atkinson et al., 1981 RR (d) (2.92 ± 0.32) × 10-12 295 ± 1 Atkinson and Aschmann, 1984 RR (d) (2.45 ± 0.34) × 10-12 300 ± 2 Barnes et al., 1986 RR (e) (2.36 ± 0.04) × 10-12 300 Behnke et al., 1988 RR (f) 1.39 × 10-11 exp(-526/T) 235-361 DeMore and Bayes, RR (g) 2.33 × 10-12 298 Comments (a) Indicated errors are one standard deviation. Overall uncertainties were assessed to be 7.5% for temperatures >250 K and 10% for temperatures <250 K. (b) Derived from the effects of the addition of small amounts of n-butane to slowly reacting mixtures of H2 + O2. The loss of H2 was followed by monitoring the pressure change due to the reaction 2H2 + O2  2H2O, and the loss of n-butane was measured by GC. The rate coefficient ratio k(HO + n-butane)/k(HO + H2) = 13.2 is placed on an absolute basis using k(HO + H2) = 7.87 10-13 cm 3 molecule-1 s-1 at 753 K (Atkinson, 2003). (c) HO radicals were generated by the decomposition of H2O2 in a boric acid-coated reaction vessel, and the concentrations of n-butane and propane (the reference compound) were measured by GC. The measured rate coefficient ratios of k(HO + n-butane)/k(HO + propane) = 1.54 ± 0.13 is placed on an absolute value using k(HO + propane) = 6.16 10-12 cm 3 molecule-1 s-1 at 653 K (IUPAC, 2019). (d) HO radicals were generated by the photolysis of CH3ONO in one atmosphere of air. The concentrations of n-butane and propene (the reference compound) were measured by GC. The measured rate coefficient ratios of k(HO + n-butane)/k(HO + propene) = 0.0962 ± 0.0093 at 299 2 K (Atkinson et al., 1981) and 0.101 0.012 at 295 1 K (Atkinson and Aschmann, 1984) are placed on an absolute value using k(HO + propene) = 2.85 10-11 at 299 K and 2.89 10-11 at 295 K cm 3 molecule-1 s-1 at atmospheric pressure of air (IUPAC, 2019). (e) HO radicals were generated by the photolysis of H2O2 in air at atmospheric pressure, and the concentrations of n-butane and ethene (the reference compound) were measured by GC. The measured rate coefficient ratio of k(HO + n-butane)/k(HO + ethene) = 0.32 ± 0.04 is placed on an absolute basis using k(HO + ethene) = 7.78 10-12 cm 3 molecule-1 s-1 at 300 K and atmospheric pressure of air (IUPAC, 2019). (f) HO radicals were generated by the photolysis of NOx-organic-air mixtures at atmospheric pressure. The concentrations of n-butane and n-octane (the reference compound) were measured by GC, and the measured rate coefficient ratio of k(HO + n-butane)/k(HO + noctane) is placed on an absolute basis using k(HO + n-octane) = 8.15 10-12 cm 3 molecule-1 s-1 at 300 K (Atkinson, 2003). (g) HO radicals were generated by the photolysis of H2O at 185 nm or, at low temperatures, by the photolysis of N2O at 185 nm in the presence of H2. The concentrations of n-butane and propane (the reference compound) were measured by GC. The measured rate coefficient ratios k(HO + n-butane)/k(HO + propane) are placed o...

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Theoretical Investigation of the NO3 Radical Addition to Double Bonds of Limonene

Cited by 19 publications

References 36 publications

Theoretical Study on the Reaction of Sabinene with NO₃

Theoretical Study on the Reaction of Sabinene with NO₃

Identification of highly oxygenated organic molecules and their role in aerosol formation in the reaction of limonene with nitrate radical

Supplementary material to "Evaluated kinetic and photochemical data for atmospheric chemistry: Volume VIII – gas phase reactions of organic species with four, or more, carbon atoms (≥ C<sub>4</sub>)"

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Theoretical Investigation of the NO3 Radical Addition to Double Bonds of Limonene

Cited by 19 publications

References 36 publications

Theoretical Study on the Reaction of Sabinene with NO3

Theoretical Study on the Reaction of Sabinene with NO3

Identification of highly oxygenated organic molecules and their role in aerosol formation in the reaction of limonene with nitrate radical

Supplementary material to &quot;Evaluated kinetic and photochemical data for atmospheric chemistry: Volume VIII – gas phase reactions of organic species with four, or more, carbon atoms (≥ C&lt;sub&gt;4&lt;/sub&gt;)&quot;

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Theoretical Study on the Reaction of Sabinene with NO₃

Theoretical Study on the Reaction of Sabinene with NO₃

Supplementary material to "Evaluated kinetic and photochemical data for atmospheric chemistry: Volume VIII – gas phase reactions of organic species with four, or more, carbon atoms (≥ C<sub>4</sub>)"