Kinetics and Mechanistic Investigations of Atmospheric Oxidation of HFO-1345fz by OH Radical: Insights from Theory

2017 ◽  
Vol 121 (3) ◽  
pp. 595-607 ◽  
Author(s):  
Pradeep Kumar Rao ◽  
Shridhar P. Gejji
Keyword(s):  
Atmospheric Oxidation ◽  
Oh Radical ◽  
Mechanistic Investigations

Atmospheric oxidation of fluoroalcohols initiated by ·OH radical in the presence of water and mineral dusts: Mechanism, kinetics, and risk assessment

2021 ◽  
Author(s):  
Feng-Yang Bai ◽  
Ming-Shuai Deng ◽  
Mei-Yan Chen ◽  
Lian Kong ◽  
Shuang Ni ◽  
...  
Keyword(s):  
Risk Assessment ◽  
Environmental Risks ◽  
Atmospheric Oxidation ◽  
Oh Radical ◽  
Mineral Dusts

The transport and formation of fluorinated compounds are greatly significant due to their possible environmental risks. In this work, the ·OH-mediated degradation of CF3CF2CF2CH2OH and CF3CHFCF2CH2OH in the existence of...

Theoretical investigation on atmospheric oxidation of fluorene initiated by OH radical

2019 ◽  
Vol 669 ◽  
pp. 920-929 ◽  
Author(s):  
Zhezheng Ding ◽  
Yayi Yi ◽  
Qingzhu Zhang ◽  
Tao Zhuang
Keyword(s):  
Theoretical Investigation ◽  
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.

BrHgO• + C2H4 and BrHgO• + HCHO in Atmospheric Oxidation of Mercury: Determining Rate Constants of Reactions with Pre-Reactive Complexes and a Bifurcation

2019 ◽  
Author(s):  
Khoa T. Lam ◽  
Curtis J. Wilhelmsen ◽  
Theodore Dibble
Keyword(s):  
Hydrogen Atom ◽  
Quantum Chemistry ◽  
Transition State ◽  
Rate Constant ◽  
Rate Constants ◽  
Minimum Energy ◽  
Atmospheric Oxidation ◽  
Minimum Energy Path ◽  
Oh Radical ◽  
Hydrogen Atoms

Models suggest BrHgONO to be the major Hg(II) species formed in the global oxidation of Hg(0), and BrHgONO undergoes rapid photolysis to produce the thermally stable radical BrHgO•. We previously used quantum chemistry to demonstrate that BrHgO• can, like OH radical, readily can abstract hydrogen atoms from sp<sup>3</sup>-hybridized carbon atoms as well as add to NO and NO<sub>2</sub>. In the present work, we reveal that BrHgO• can also add to C<sub>2</sub>H<sub>4</sub> to form BrHgOCH<sub>2</sub>CH<sub>2</sub>•, although this addition appears to proceed with a lower rate constant than the analogous addition of •OH to C<sub>2</sub>H<sub>4</sub>. Additionally, BrHgO• can readily react with HCHO in two different ways: either by addition to the carbon or by abstraction of a hydrogen atom. The minimum energy path for the BrHgO• + HCHO reaction bifurcates, forming two pre-reactive complexes, each of which passes over a separate transition state to form a different product.

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
Sign in / Sign up

Export Citation Format

Share Document