Atmospheric oxidation mechanism of naphthalene initiated by OH radical. A theoretical study

2012 ◽  
Vol 14 (8) ◽  
pp. 2645 ◽  
Author(s):  
Zhijie Zhang ◽  
Ling Lin ◽  
Liming Wang
Keyword(s):  
Theoretical Study ◽  
Oxidation Mechanism ◽  
Atmospheric Oxidation ◽  
Oh Radical

Atmospheric oxidation mechanism of polyfluorinated sulfonamides — A quantum chemical and kinetic study

2013 ◽  
Vol 91 (6) ◽  
pp. 472-478 ◽  
Author(s):  
Xiaoyan Sun ◽  
Lei Ding ◽  
Qingzhu Zhang ◽  
Wenxing Wang
Keyword(s):  
Rate Constants ◽  
Density Functional ◽  
Single Point ◽  
Oxidation Mechanism ◽  
Basis Set ◽  
Atmospheric Oxidation ◽  
Oh Radicals ◽  
Oh Radical ◽  
Orbital Theory ◽  
Point Energy

Polyfluorinated sulfonamides (FSAs, F(CF2)nSO2NR1R2) are present in the atmosphere and may serve as the source of perfluorocarboxylates (PFCAs, CF3(CF2)nCOO–) in remote locations through long-range atmospheric transport and oxidation. Density functional theory (DFT) molecular orbital theory calculations were carried out to investigate OH radical-initiated atmospheric oxidation of a series of sulfonamides, F(CF2)nSO2NR1R2 (n = 4, 6, 8). Geometry optimizations of the reactants as well as the intermediates, transition states, and products were performed at the MPWB1K level with the 6-31G+(d,p) basis set. Single-point energy calculations were carried out at the MPWB1K/6-311+G(3df,2p) level of theory. The OH radical-initiated reaction mechanism is given and confirms that the OH addition to the sulfone double bond producing perfluoroalkanesulfonic acid directly cannot occur in the general atmosphere. Canonical variational transition-state (CVT) theory with small curvature tunneling (SCT) contribution was used to predict the rate constants. The overall rate constants were determined, k(T) (N-EtFBSA + OH) = (3.21 × 10−12) exp(–584.19/T), k(T) (N-EtFHxSA + OH) = (3.21 × 10−12) exp(–543.24/T), and k(T) (N-EtFOSA + OH) = (2.17 × 10−12) exp(–504.96/T) cm3 molecule−1 s−1, over the possible atmospheric temperature range of 180–370 K, indicating that the length of the F(CF2)n group has no large effect on the reactivity of FSAs. Results show that the atmospheric lifetime of FSAs determined by OH radicals will be 20–40 days, which agrees well with the experimental values (20–50 days), 20 thus they may contribute to the burden of perfluorinated pollution in remote regions.

Theoretical study for OH radical-initiated atmospheric oxidation of ethyl acrylate

Chemosphere ◽  
2015 ◽  
Vol 119 ◽  
pp. 626-633 ◽  
Author(s):  
Yanhui Sun ◽  
Qingzhu Zhang ◽  
Jingtian Hu ◽  
Jianmin Chen ◽  
Wenxing Wang
Keyword(s):  
Theoretical Study ◽  
Ethyl Acrylate ◽  
Atmospheric Oxidation ◽  
Oh Radical

A theoretical study of OH radical-initiated atmospheric oxidation of 1-chloronaphthalene

2018 ◽  
Vol 699 ◽  
pp. 40-47 ◽  
Author(s):  
Yang Cui ◽  
Zhezheng Ding ◽  
Yanhui Sun ◽  
Yayi Yi ◽  
Fei Xu ◽  
...  
Keyword(s):  
Theoretical Study ◽  
Atmospheric Oxidation ◽  
Oh Radical

scholarly journals Theoretical study of the OH-initiated atmospheric oxidation mechanism of perfluoro methyl vinyl ether, CF3OCFCF2

2015 ◽  
Vol 17 (43) ◽  
pp. 28697-28704 ◽  
Author(s):  
L. Vereecken ◽  
J. N. Crowley ◽  
D. Amedro
Keyword(s):  
Vinyl Ether ◽  
Theoretical Study ◽  
Oxidation Mechanism ◽  
Atmospheric Oxidation ◽  
Methyl Vinyl ◽  
Methyl Vinyl Ether

The fluorinated product glycolaldehyde can be catalytically converted to glyoxal + HF by H2O.

The atmospheric oxidation mechanism and kinetics of 1,3,5-trimethylbenzene initiated by OH radicals – a theoretical study

2017 ◽  
Vol 41 (18) ◽  
pp. 10259-10271 ◽  
Author(s):  
S. Ponnusamy ◽  
L. Sandhiya ◽  
K. Senthilkumar
Keyword(s):  
Theoretical Study ◽  
Oxidation Mechanism ◽  
Peroxy Radical ◽  
Ring Closure ◽  
Oh Radicals ◽  
Oh Radical ◽  
Radical Ring ◽  
Atmospheric Fate ◽  
Mechanism And Kinetics ◽  
Kinetics Of

The atmospheric fate of 1,3,5-trimethylbenzene is determined by OH-radical addition, and subsequent bicyclic peroxy radical ring closure and ring breaking pathways.

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