Formation of alkyl nitrates from the reaction of branched and cyclic alkyl peroxy radicals with NO

1984 ◽  
Vol 16 (9) ◽  
pp. 1085-1101 ◽  
Author(s):  
Roger Atkinson ◽  
Sara M. Aschmann ◽  
William P. L. Carter ◽  
Arthur M. Winer ◽  
James N. Pitts
Keyword(s):  
Peroxy Radicals ◽  
Alkyl Nitrates ◽  
Alkyl Peroxy Radicals

ChemInform Abstract: FORMATION OF ALKYL NITRATES FROM THE REACTION OF BRANCHED AND CYCLIC ALKYL PEROXY RADICALS WITH NITRIC OXIDE

1984 ◽  
Vol 15 (51) ◽  
Author(s):  
R. ATKINSON ◽  
S. M. ASCHMANN ◽  
W. P. L. CARTER ◽  
A. M. WINER ◽  
J. N. JUN. PITTS
Keyword(s):  
Nitric Oxide ◽  
Peroxy Radicals ◽  
Alkyl Nitrates ◽  
Alkyl Peroxy Radicals

Rate Coefficients and Mechanisms for the Atmospheric Oxidation of the N-Atom-Containing Oxygenates

2011 ◽  
Author(s):  
Jack Calvert ◽  
Abdelwahid Mellouki ◽  
John Orlando ◽  
Michael Pilling ◽  
Timothy Wallington
Keyword(s):  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Photochemical Reactions ◽  
Rate Coefficients ◽  
Peroxy Radicals ◽  
Alkyl Nitrates ◽  
Volatile Organic ◽  
Peroxyacyl Nitrates ◽  
Alkyl Peroxy Radicals ◽  
The Many

The many different nitrogen-containing oxygenated volatile organic compounds that are present in the troposphere play important roles in the chemistry of our atmosphere. They can be emitted directly into the atmosphere, such as in the case of amides that are widely used as organic solvents, starting materials, or intermediates in different industries (e.g., synthetic polymers, manufacture of dyes, and synthesis of pesticides). Amides are formed in situ as intermediate products in the degradation of amines (e.g., see Tuazon et al., 1994; Finlayson-Pitts and Pitts, 2000). Nitrogen-containing oxygenated organic compounds are formed in the atmosphere also via reactions of alkoxy (RO) and alkyl peroxy radicals (RO2) with NO or NO2 leading to alkyl nitrates, alkyl nitrites, and peroxy acetyl nitrates. However, primary sources of these organic species have also been suggested such as diesel and other engines and biomass burning (e.g., see Simpson et al., 2002). Alkyl nitrates (RONO2) have been detected in both the urban and the remote troposphere (e.g., see Roberts, 1990; Walega et al., 1992; Atlas et al., 1992; Ridley et al., 1997; and Stroud et al., 2001; see also section I-D). Nitrates are formed as minor products in the reaction of peroxy radicals with NO. The nitrate yield increases with the size of peroxy radicals and can be as high as 20–30% for large (>C6) radicals (Calvert et al., 2008). Peroxyacyl nitrates (RC(O)O2NO2) are important constituents of urban air pollution. They have been identified in ambient air (e.g., see Bertman and Roberts, 1991; Williams et al., 1997, 2000; Nouaime et al., 1998; Hansel and Wisthaler, 2000; also see section I-D). They are formed from photochemical reactions via RC(O)O2 + NO2. A major role of these compounds is their capacity to act as a reservoir for NOx that can be transported from polluted urban to remote regions that are poor NOx regions and where their presence can increase NOx levels (Roberts, 1990). As with other volatile organic compounds (VOCs), once released to the atmosphere, nitrogen-containing organic compounds are expected to undergo degradation primarily via reaction with hydroxyl and nitrate radicals, reaction with ozone, and photolysis. Thermal decomposition is an important loss process for the peroxyacyl nitrates.

Calculated Hydrogen Shift Rate Constants in Substituted Alkyl Peroxy Radicals

2018 ◽  
Vol 122 (43) ◽  
pp. 8665-8673 ◽  
Author(s):  
Rasmus V. Otkjær ◽  
Helene H. Jakobsen ◽  
Camilla Mia Tram ◽  
Henrik G. Kjaergaard
Keyword(s):  
Rate Constants ◽  
Peroxy Radicals ◽  
Hydrogen Shift ◽  
Alkyl Peroxy Radicals

Modeling the Organic Nitrate Yields in the Reaction of Alkyl Peroxy Radicals with Nitric Oxide. 2. Reaction Simulations

2003 ◽  
Vol 107 (38) ◽  
pp. 7434-7444 ◽  
Author(s):  
John R. Barker ◽  
Lawrence L. Lohr ◽  
Robert M. Shroll ◽  
Susan Reading
Keyword(s):  
Nitric Oxide ◽  
Organic Nitrate ◽  
Peroxy Radicals ◽  
Alkyl Peroxy Radicals

scholarly journals New insight into the spatiotemporal variability and source apportionments of C<sub>1</sub>–C<sub>4</sub> alkyl nitrates in Hong Kong

2016 ◽  
Vol 16 (13) ◽  
pp. 8141-8156 ◽  
Author(s):  
Zhenhao Ling ◽  
Hai Guo ◽  
Isobel Jane Simpson ◽  
Sandra Maria Saunders ◽  
Sean Ho Man Lam ◽  
...  
Keyword(s):  
Hong Kong ◽  
Biomass Burning ◽  
Spatiotemporal Variability ◽  
Urban Site ◽  
Mesoscale Circulation ◽  
Peroxy Radicals ◽  
Alkyl Nitrates ◽  
Regional Transport ◽  
Secondary Formation ◽  
Alkyl Nitrate

Abstract. C1–C4 alkyl nitrates (RONO2) were measured concurrently at a mountain site, Tai Mo Shan (TMS), and an urban site, Tsuen Wan (TW), at the base of the same mountain in Hong Kong from September to November 2010. Although the levels of parent hydrocarbons were much lower at TMS (p  <  0.05), similar alkyl nitrate levels were found at both sites regardless of the elevation difference, suggesting various source contributions of alkyl nitrates at the two sites. Prior to using a positive matrix factorization (PMF) model, the data at TW were divided into "meso" and "non-meso" scenarios for the investigation of source apportionments with the influence of mesoscale circulation and regional transport, respectively. Secondary formation was the prominent contributor of alkyl nitrates in the meso scenario (60 ± 2 %, 60.2 ± 1.2 pptv), followed by biomass burning and oceanic emissions, while biomass burning and secondary formation made comparable contributions to alkyl nitrates in the non-meso scenario, highlighting the strong emissions of biomass burning in the inland Pearl River delta (PRD) region. In contrast to TW, the alkyl nitrate levels measured at TMS mainly resulted from the photooxidation of the parent hydrocarbons at TW during mesoscale circulation, i.e., valley breezes, corresponding to 52–86 % of the alkyl nitrate levels at TMS. Furthermore, regional transport from the inland PRD region made significant contributions to the levels of alkyl nitrates (∼  58–82 %) at TMS in the non-meso scenario, resulting in similar levels of alkyl nitrates observed at the two sites. The simulation of secondary formation pathways using a photochemical box model found that the reaction of alkyl peroxy radicals (RO2) with nitric oxide (NO) dominated the formation of RONO2 at both sites, and the formation of alkyl nitrates contributed negatively to O3 production, with average reduction rates of 4.1 and 4.7 pptv pptv−1 at TMS and TW, respectively.

scholarly journals Secondary organic aerosol yields of 12-carbon alkanes

2013 ◽  
Vol 13 (8) ◽  
pp. 20677-20727 ◽  
Author(s):  
C. L. Loza ◽  
J. S. Craven ◽  
L. D. Yee ◽  
M. M. Coggon ◽  
R. H. Schwantes ◽  
...  
Keyword(s):  
Vapor Phase ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Peroxy Radicals ◽  
Branch Points ◽  
Wall Losses ◽  
Alkyl Peroxy Radicals ◽  
Wall Loss ◽  
Yield Uncertainty ◽  
Modeling Study

Abstract. Secondary organic aerosol (SOA) yields were measured for cyclododecane, hexylcyclohexane, n-dodecane, and 2-methylundecane under high- and low-NOx conditions, in which alkyl peroxy radicals (RO2) react primarily with NO and HO2, respectively, for multiple initial alkane concentrations. Experiments were run until 95–100% of the initial alkane had reacted. Particle wall loss was evaluated as two limiting cases. SOA yield differed by 2 orders of magnitude between the two limiting cases, but the same trends among alkane precursors were observed for both limiting cases. Vapor-phase wall losses were addressed through a modeling study and increased SOA yield uncertainty by approximately 30%. SOA yields were highest from cyclododecane under both NOx conditions. Under high-NOx conditions, SOA yields increased from 2-methylundecane < dodecane ~ hexylcyclohexane < cyclododecane, consistent with previous studies. Under low-NOx conditions, SOA yields increased from 2-methylundecane ~ dodecane < hexylcyclohexane < cyclododecane. The presence of cyclization in the parent alkane structure increased SOA yields, whereas the presence of branch points decreased SOA yields due to increased vapor-phase fragmentation. Vapor-phase fragmentation was found to be more prevalent under high-NOx conditions than under low-NOx conditions. For different initial concentrations of the same alkane and same NOx conditions, SOA yield did not correlate with SOA mass throughout SOA growth, suggesting kinetically limited SOA growth for these systems.

scholarly journals A two-channel, Thermal Dissociation Cavity-Ringdown Spectrometer for the detection of ambient NO<sub>2</sub>, RO<sub>2</sub>NO<sub>2</sub> and RONO<sub>2</sub>

2015 ◽  
Vol 8 (11) ◽  
pp. 11533-11596
Author(s):  
J. Thieser ◽  
G. Schuster ◽  
G. J. Phillips ◽  
A. Reiffs ◽  
U. Parchatka ◽  
...  
Keyword(s):  
Laboratory Experiments ◽  
Thermal Dissociation ◽  
Organic Radicals ◽  
Peroxy Radicals ◽  
Correction Factors ◽  
Alkyl Nitrates ◽  
Cavity Ringdown ◽  
Mixing Ratios ◽  
Peroxy Nitrates ◽  
Reference Samples

Abstract. We describe a Thermal Dissociation Cavity-Ring-Down Spectrometer (TD-CRDS) for measurement of ambient NO2, total peroxy nitrates (ΣPNs) and total alkyl nitrates (ΣANs). The spectrometer has two separate cavities operating at ~ 405.2 and 408.5 nm, one cavity (reference) samples NO2 continuously from an inlet at ambient temperature, the other samples sequentially from an inlet at 473 K in which PNs are converted to NO2 or from an inlet at 723 K in which both PNs and ANs are converted to NO2, difference signals being used to derive mixing ratios of ΣPNs and ΣANs. We describe an extensive set of laboratory experiments and numerical simulations to characterise the fate of organic radicals in the hot inlets and cavity and derive correction factors to account for the bias resulting from interaction of peroxy radicals with ambient NO and NO2. Finally, we present the first measurements and comparison with other instruments during a field campaign, outline the limitations of the present instrument and provide an outlook for future improvements.

scholarly journals Thermal dissociation cavity enhanced absorption spectrometer for detecting NO<sub>2</sub>, RO<sub>2</sub>NO<sub>2</sub> and RONO<sub>2</sub> in the atmosphere

2021 ◽  
Author(s):  
Chunmeng Li ◽  
Haichao Wang ◽  
Xiaorui Chen ◽  
Tianyu Zhai ◽  
Shiyi Chen ◽  
...  
Keyword(s):  
Limit Of Detection ◽  
Thermal Dissociation ◽  
Lookup Table ◽  
Organic Nitrates ◽  
Peroxy Radicals ◽  
Alkyl Nitrates ◽  
Mixing Ratios ◽  
Enhanced Absorption ◽  
Field Deployment ◽  
Set Up

Abstract. We developed a thermal dissociation cavity enhanced absorption spectroscopy (TD-CEAS) for the in-situ measurement of NO2, total peroxy nitrates (PNs, RO2NO2), and total alkyl nitrates (ANs, RONO2) in the atmosphere. PNs and ANs are thermally converted to NO2 at the corresponding pyrolysis temperatures and detected by CEAS at 435–455 nm. The instrument samples sequentially from three channels at ambient temperature, 453 K and 653 K, with a cycle of 3 minutes, for measuring NO2, NO2+PNs, and NO2+PNs+ANs, respectively. The absorptions between the three channels are used to derive the mixing ratios of PNs and ANs by the spectral fitting. The limit of detection (LOD) is estimated to be 97 pptv (1σ) at 6 s intervals for NO2. The measurement uncertainty of NO2 is estimated to be 8 %, while the uncertainties of PNs and ANs detection is larger than NO2 due to some chemical interferences in the heating channels, such as the reaction of NO (or NO2) with the peroxy radicals produced by the thermal dissociation of organic nitrates. Based on the laboratory experiments and numerical simulations, we set up a lookup table method to correct these interferences in PNs and ANs channel under various concentrations of ambient organic nitrates, NO, and NO2. Finally, we present the first field deployment and compared it with other instruments during a field campaign in China, the advantage and limitations of this instrument are outlined.

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