An Intramolecular Hydrogen‐Shift in a Peroxy Radical at Cryogenic Temperatures: The Reaction of 2‐Hydroxyphenyl Radical with O 2

2020 ◽  
Vol 26 (53) ◽  
pp. 12119-12124 ◽  
Author(s):  
J. Philipp Wagner
Keyword(s):  
Peroxy Radical ◽  
Cryogenic Temperatures ◽  
Hydrogen Shift ◽  
Intramolecular Hydrogen

The atmospheric oxidation of dimethyl, diethyl, and diisopropyl ethers. The role of the intramolecular hydrogen shift in peroxy radicals

2016 ◽  
Vol 18 (11) ◽  
pp. 7707-7714 ◽  
Author(s):  
Sainan Wang ◽  
Liming Wang
Keyword(s):  
Atmospheric Oxidation ◽  
Peroxy Radicals ◽  
Hydrogen Shift ◽  
Intramolecular Hydrogen ◽  
Clean Atmosphere

Ethers can be auto-oxidized with no O3 formation in a ‘clean’ atmosphere.

The Importance of Peroxy Radical Hydrogen-Shift Reactions in Atmospheric Isoprene Oxidation

2019 ◽  
Vol 123 (4) ◽  
pp. 920-932 ◽  
Author(s):  
Kristian H. Møller ◽  
Kelvin H. Bates ◽  
Henrik G. Kjaergaard
Keyword(s):  
Peroxy Radical ◽  
Hydrogen Shift ◽  
Isoprene Oxidation

scholarly journals Cost-Effective Implementation of Multiconformer Transition State Theory for Peroxy Radical Hydrogen Shift Reactions

2016 ◽  
Vol 120 (51) ◽  
pp. 10072-10087 ◽  
Author(s):  
Kristian H. Møller ◽  
Rasmus V. Otkjær ◽  
Noora Hyttinen ◽  
Theo Kurtén ◽  
Henrik G. Kjaergaard
Keyword(s):  
Transition State ◽  
Transition State Theory ◽  
Peroxy Radical ◽  
Cost Effective ◽  
State Theory ◽  
Hydrogen Shift ◽  
Effective Implementation

scholarly journals Multigenerational Theoretical Study of Isoprene Peroxy Radical 1–5-Hydrogen Shift Reactions that Regenerate HOx Radicals and Produce Highly Oxidized Molecules

2018 ◽  
Vol 123 (4) ◽  
pp. 906-919 ◽  
Author(s):  
Ivan R. Piletic ◽  
Richard Howell ◽  
Libero J. Bartolotti ◽  
Tadeusz E. Kleindienst ◽  
Surender M. Kaushik ◽  
...  
Keyword(s):  
Theoretical Study ◽  
Peroxy Radical ◽  
Hydrogen Shift

scholarly journals Atmospheric autoxidation is increasingly important in urban and suburban North America

2017 ◽  
Vol 115 (1) ◽  
pp. 64-69 ◽  
Author(s):  
Eric Praske ◽  
Rasmus V. Otkjær ◽  
John D. Crounse ◽  
J. Caleb Hethcox ◽  
Brian M. Stoltz ◽  
...  
Keyword(s):  
Hydrogen Transfer ◽  
Peroxy Radical ◽  
Rate Coefficients ◽  
Peroxy Radicals ◽  
Molecular Configuration ◽  
Atmospheric Pollutant ◽  
Kinetic Isotope ◽  
Experimental Approaches ◽  
Intramolecular Hydrogen ◽  
American Cities

Gas-phase autoxidation—regenerative peroxy radical formation following intramolecular hydrogen shifts—is known to be important in the combustion of organic materials. The relevance of this chemistry in the oxidation of organics in the atmosphere has received less attention due, in part, to the lack of kinetic data at relevant temperatures. Here, we combine computational and experimental approaches to investigate the rate of autoxidation for organic peroxy radicals (RO2) produced in the oxidation of a prototypical atmospheric pollutant, n-hexane. We find that the reaction rate depends critically on the molecular configuration of the RO2 radical undergoing hydrogen transfer (H-shift). RO2 H-shift rate coefficients via transition states involving six- and seven-membered rings (1,5 and 1,6 H-shifts, respectively) of α-OH hydrogens (HOC-H) formed in this system are of order 0.1 s−1 at 296 K, while the 1,4 H-shift is calculated to be orders of magnitude slower. Consistent with H-shift reactions over a substantial energetic barrier, we find that the rate coefficients of these reactions increase rapidly with temperature and exhibit a large, primary, kinetic isotope effect. The observed H-shift rate coefficients are sufficiently fast that, as a result of ongoing NOx emission reductions, autoxidation is now competing with bimolecular chemistry even in the most polluted North American cities, particularly during summer afternoons when NO levels are low and temperatures are elevated.

A Computational Kinetics Study on the Intramolecular Hydrogen Shift Reactions of Alkylperoxy Radicals in 2-Methyltetrahydrofuran Oxidation

2017 ◽  
Vol 49 (6) ◽  
pp. 419-437 ◽  
Author(s):  
Prajakta R. Parab ◽  
Naoki Sakade ◽  
Yasuyuki Sakai ◽  
Ravi Fernandes ◽  
K. Alexander Heufer
Keyword(s):  
Kinetics Study ◽  
Hydrogen Shift ◽  
Intramolecular Hydrogen ◽  
Alkylperoxy Radicals

Theoretical Investigation of Intramolecular Hydrogen Shift Reactions in 3-Methyltetrahydrofuran (3-MTHF) Oxidation

2015 ◽  
Vol 119 (44) ◽  
pp. 10917-10928 ◽  
Author(s):  
Prajakta R. Parab ◽  
Naoki Sakade ◽  
Yasuyuki Sakai ◽  
Ravi Fernandes ◽  
K. Alexander Heufer
Keyword(s):  
Theoretical Investigation ◽  
Hydrogen Shift ◽  
Intramolecular Hydrogen
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