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

Reactions of alkoxy and alkyl peroxy radicals

1987 ◽  
Vol 6 (1) ◽  
pp. 53-90 ◽  
Author(s):  
L. Batt
Keyword(s):  
Peroxy Radicals ◽  
Alkyl Peroxy Radicals

Absolute rate constants for hydrocarbon autoxidation. VI. Alkyl aromatic and olefinic hydrocarbons

1967 ◽  
Vol 45 (8) ◽  
pp. 793-802 ◽  
Author(s):  
J. A. Howard ◽  
K. U. Ingold
Keyword(s):  
Hydrogen Atom ◽  
Steric Hindrance ◽  
Rate Constants ◽  
Peroxy Radical ◽  
Electron System ◽  
Chain Termination ◽  
The Self ◽  
Hydrogen Atom Abstraction ◽  
Peroxy Radicals ◽  
Absolute Rate

Absolute rate constants have been measured for the autoxidation of a large number of hydrocarbons at 30 °C. The chain-propagating and chain-terminating rate constants depend on the structure of the hydrocarbon and also on the structure of the chain-carrying peroxy radical. With certain notable exceptions which are mainly due to steric hindrance, the rate constants for hydrogen-atom abstraction increase in the order primary < secondary < tertiary; and, for compounds losing a secondary hydrogen atom, the rate constants increase in the order unactivated < acyclic activated by a single π-electron system < cyclic activated by a single Π-system < acyclic activated by two π-systems < cyclic activated by two π-systems. The rate constants for chain termination by the self-reaction of two peroxy radicals generally increase in the order tertiary peroxy radicals < acyclic allylic secondary  [Formula: see text] cyclic secondary  [Formula: see text] acyclic benzylic secondary < primary peroxy radicals < hydroperoxy radicals.

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.

Generation and detection of alkyl peroxy radicals in a supersonic jet expansion

2006 ◽  
Vol 125 (1) ◽  
pp. 014310 ◽  
Author(s):  
H. B. Fu ◽  
Y. J. Hu ◽  
E. R. Bernstein
Keyword(s):  
Supersonic Jet ◽  
Peroxy Radicals ◽  
Alkyl Peroxy Radicals ◽  
Supersonic Jet Expansion

Studies of radiation-induced reactions of ethylene in aqueous solution II. Reactions in the presence of oxygen as studied by pulse radiolysis and γ -irradiation techniques

1967 ◽  
Vol 300 (1463) ◽  
pp. 443-454 ◽  
Keyword(s):  
Aqueous Solution ◽  
Hydrogen Peroxide ◽  
Rate Constants ◽  
Pulse Radiolysis ◽  
Major Product ◽  
Peroxy Radicals ◽  
Ferrous Ions ◽  
Constant Composition ◽  
Γ Irradiation ◽  
Radiation Induced

The radiolysis of dilute aqueous solutions containing ethylene and oxygen has been investigated. Pulse radiolysis was used to measure the rate constants for the addition of hydroxyl radicals to ethylene, the binary decomposition of the resulting hydroxyethyl radicals and their addition to ethylene and reaction with oxygen to yield peroxy radicals. The rate constants have also been determined for the mutual interaction of the peroxy radicals and their reaction with ferrous ions. The principal products of γ -irradiation were aldehydes and organic hydroperoxides. Hydrogen peroxide was found in yields close to the molecular yield from water. The polymer produced in the absence of oxygen was not formed, and glycollaldehyde, reported as a major product by previous workers, could not be detected. At constant composition of the gas mixtures, product yields were unaffected by total pressure in the range up to 40 atm, but were strongly dependent on the proportion of oxygen. Aldehyde yields were markedly greater at pH 1.2 than in neutral solution. The influence of ferrous ions an d of added hydrogen peroxide has been determined. The pulse radiolysis and γ -irradiation experiments complement one another and show that the radiation-induced oxidation of ethylene in aqueous solution involves the same primary reactions as occur in the absence of oxygen, followed by the formation and further reactions of peroxy radicals.

Hydrogen shift reactions in four methyl-buten-ol (MBO) peroxy radicals and their impact on the atmosphere

2016 ◽  
Vol 147 ◽  
pp. 79-87 ◽  
Author(s):  
Hasse C. Knap ◽  
Johan A. Schmidt ◽  
Solvejg Jørgensen
Keyword(s):  
Peroxy Radicals ◽  
Hydrogen Shift

scholarly journals Atmospheric photooxidation and ozonolysis of Δ<sup>3</sup>-carene and 3-caronaldehyde: Rate constants and product yields

2021 ◽  
Author(s):  
Luisa Lamberta Hantschke ◽  
Anna Novelli ◽  
Birger Bohn ◽  
Changmin Cho ◽  
David Reimer ◽  
...  
Keyword(s):  
Rate Constants ◽  
Reactive Nitrogen Species ◽  
Oxidation Products ◽  
Organic Nitrate ◽  
Effective Quantum Yield ◽  
Peroxy Radicals ◽  
Atmospheric Conditions ◽  
Mixing Ratios ◽  
Photolysis Frequency ◽  
First Time

Abstract. The oxidation of Δ3-carene and one of its main oxidation products, caronaldehyde, by the OH radical and O3 was investigated in the atmospheric simulation chamber SAPHIR under atmospheric conditions for NOx mixing ratios below 2 ppbv. Within this study, the rate constants of the reaction of Δ3-carene with OH and O3, and of the reaction of caronaldehyde with OH were determined to be (8.0 ± 0.5) × 10−11 cm3 s−1 at 304 K, (4.4 ± 0.2) × 10−17 cm3 s−1 at 300 K and (4.6 ± 1.6) × 10−11 cm3 s−1 at 300 K, respectively, in agreement with previously published values. The yields of caronaldehyde from the reaction of OH and ozone with Δ3-carene were determined to be (0.30 ± 0.05) and (0.06 ± 0.02), respectively. Both values are in reasonably well agreement with reported literature values. An organic nitrate (RONO2) yield from the reaction of NO with RO2 derived from Δ3-carene of (0.25 ± 0.04) was determined from the analysis of the reactive nitrogen species (NOy) in the SAPHIR chamber. The RONO2 yield of the reaction of NO with RO2 derived from the reaction of caronaldehyde with OH was found to be (0.10 ± 0.02). The organic nitrate yields of Δ3-carene and caronaldehyde oxidation with OH are reported here for the first time in the gas phase. An OH yield of (0.65 ± 0.10) was determined from the ozonolysis of Δ3-carene. Calculations of production and destruction rates of the sum of hydroxyl and peroxy radicals (ROx = OH+HO2+RO2) demonstrated that there were no unaccounted production or loss processes of radicals in the oxidation of Δ3-carene for conditions of the the chamber experiments. In an OH free experiment with added OH scavenger, the photolysis frequency of caronaldehyde was obtained from its photolytical decay. The experimental photolysis frequency was a factor of 7 higher than the value calculated from the measured solar acintic flux density, an absorption cross section from the literature and an assumed effective quantum yield of unity for photodissociation.

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
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