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The use of oxidation flow reactors (OFRs) has been rapidly increasing. We investigate organic peroxy radical (RO2) chemistry in OFRs by kinetic modeling. It is found that, at low NO, UV intensity should be limited to avoid high radical levels leading to significant reaction of RO2 with OH and negligible RO2 isomerization, both of which are atmospherically irrelevant. We also develop two RO2 fate estimators (for general use and for OFRs) to aid experiment design and interpretation.
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ACP | Articles | Volume 19, issue 2
Atmos. Chem. Phys., 19, 813–834, 2019
https://doi.org/10.5194/acp-19-813-2019
Atmos. Chem. Phys., 19, 813–834, 2019
https://doi.org/10.5194/acp-19-813-2019

Research article 22 Jan 2019

Research article | 22 Jan 2019

Organic peroxy radical chemistry in oxidation flow reactors and environmental chambers and their atmospheric relevance

Zhe Peng et al.

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Assaf, E., Song, B., Tomas, A., Schoemaecker, C., and Fittschen, C.: Rate Constant of the Reaction between CH3O2 Radicals and OH Radicals Revisited, J. Phys. Chem. A, 120, 8923–8932, https://doi.org/10.1021/acs.jpca.6b07704, 2016. 
Assaf, E., Tanaka, S., Kajii, Y., Schoemaecker, C., and Fittschen, C.: Rate constants of the reaction of C2–C4 peroxy radicals with OH radicals, Chem. Phys. Lett., 684, 245–249, https://doi.org/10.1016/j.cplett.2017.06.062, 2017a. 
Assaf, E., Sheps, L., Whalley, L., Heard, D., Tomas, A., Schoemaecker, C., and Fittschen, C.: The Reaction between CH3O2 and OH Radicals: Product Yields and Atmospheric Implications, Environ. Sci. Technol., 51, 2170–2177, https://doi.org/10.1021/acs.est.6b06265, 2017b. 
Assaf, E., Schoemaecker, C., Vereecken, L., and Fittschen, C.: Experimental and theoretical investigation of the reaction of RO2 radicals with OH radicals: Dependence of the HO2 yield on the size of the alkyl group, Int. J. Chem. Kinet., 50, 670–680, https://doi.org/10.1002/kin.21191, 2018. 
Atkinson, R. and Arey, J.: Atmospheric degradation of volatile organic compounds, Chem. Rev., 103, 4605–4638, https://doi.org/10.1021/cr0206420, 2003. 
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Short summary
The use of oxidation flow reactors (OFRs) has been rapidly increasing. We investigate organic peroxy radical (RO2) chemistry in OFRs by kinetic modeling. It is found that, at low NO, UV intensity should be limited to avoid high radical levels leading to significant reaction of RO2 with OH and negligible RO2 isomerization, both of which are atmospherically irrelevant. We also develop two RO2 fate estimators (for general use and for OFRs) to aid experiment design and interpretation.
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Final-revised paper
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