First-principle studies on the gas phase OH-initiated oxidation of O-toluidine

被引：15
作者：
Abdel-Rahman, Mohamed A. [1 ]
Shibl, Mohamed F. [2 ,3 ]
El-Demerdash, Safinaz H. [1 ]
El-Nahas, Ahmed M. [1 ]
机构：
[1] Menoufia Univ, Chem Dept, Fac Sci, Shibin Al Kawm, Egypt
[2] Qatar Univ, Coll Arts & Sci, Dept Chem & Earth Sci, POB 2713, Doha, Qatar
[3] Cairo Univ, Chem Dept, Fac Sci, Giza, Egypt
来源：
COMPUTATIONAL AND THEORETICAL CHEMISTRY | 2019年 / 1170卷
关键词：
O-toluidine; OH oxidant; ROCBS-QB3; Thermochemistry; Kinetics; RRKM-ME; ATMOSPHERIC OXIDATION; ORGANIC-COMPOUNDS; THEORETICAL INVESTIGATIONS; DENSITY FUNCTIONALS; PEROXY-RADICALS; AROMATIC-AMINES; RATE CONSTANTS; MECHANISM; CHEMISTRY; KINETICS;
D O I：
10.1016/j.comptc.2019.112634
中图分类号：
O64 [物理化学（理论化学）、化学物理学];
学科分类号：
070304 ; 081704 ;
摘要：
In the present work, the gas phase reaction of OH radical initiated 0-toluidine (OTOD) oxidation is investigated at ROCBS-QB3. Different pathways for OH radical additions to the benzene ring sites and H-atom abstractions are explored in details. At 200 K, the oxidation mechanism of OTOD is thoroughly dominated by the OH-addition to the aromatic ring, whereas the main favorable route is the OH addition to C2 atom with a branching ratio of 52.76%. Raising temperature to 1000 K, the total abstraction of amine's hydrogens becomes the main oxidation pathway for OTOD with contributions of 29.29%. The atmospheric lifetimes of aniline and OTOD are calculated to be 20.74 and 11.23 min., respectively. The fate of OTOD-OH2 (P2) adduct with atmospheric O-2 molecule is inspected using the unimolecular Rice-Ramsperger-Kassel-Marcus (RRKM-ME) to verify our results at transition state theory (TST) and shows pressure and temperature dependence of the secondary oxidation mechanism.
引用
收藏
页数：15
相关论文
共 39 条
[31]   Temperature dependent rate constants for the gas phase reactions of OH radical with first generation products of monoterpenes oxidation: nopinone, limononaldehyde, myrtenal and ketolimonene [J].
Fakih, M. ;
Abou-Dib, A. ;
Chakir, A. ;
Roth, E. .
ATMOSPHERIC ENVIRONMENT, 2025, 356
[32]   Atmospheric Reactivity of Vinyl Acetate: Kinetic and Mechanistic Study of Its Gas-Phase Oxidation by OH, O3, and NO3 [J].
Picquet-Varrault, B. ;
Scarfogliero, M. ;
Doussin, J. -F. .
ENVIRONMENTAL SCIENCE & TECHNOLOGY, 2010, 44 (12) :4615-4621
[33]   First-principle investigation the initial oxidation of methane on Pd doped LaCo0.2Fe0.8O3-δ anode surfaces of solid oxide fuel cells [J].
Liu, Fangjie ;
Li, Haizhao ;
Fan, Chenyang ;
Li, Fan ;
Zheng, Jingyang ;
Shang, Weiwei ;
Wang, Xin ;
Xu, Liyou ;
Guo, Guanlun .
MOLECULAR CATALYSIS, 2024, 562
[34]   Gas-Phase Oxidation of Allyl Acetate by O3, OH, CI, and NO3: Reaction Kinetics and Mechanism [J].
Wang, Shuyan ;
Du, Lin ;
Zhu, Jianqiang ;
Tsona, Narcisse T. ;
Liu, Shijie ;
Wang, Yifeng ;
Ge, Maofa ;
Wang, Wenxing .
JOURNAL OF PHYSICAL CHEMISTRY A, 2018, 122 (06) :1600-1611
[35]   Sulfur isotope fractionation during oxidation of sulfur dioxide: gas-phase oxidation by OH radicals and aqueous oxidation by H2O2, O3 and iron catalysis [J].
Harris, E. ;
Sinha, B. ;
Hoppe, P. ;
Crowley, J. N. ;
Ono, S. ;
Foley, S. .
ATMOSPHERIC CHEMISTRY AND PHYSICS, 2012, 12 (01) :407-423
[36]   Gas-phase oxidation of CH2=C(CH3)CH2Cl initiated by OH radicals and Cl atoms: kinetics and fate of the alcoxy radical formed [J].
Rivela, Cynthia ;
Gibilisco, Rodrigo G. ;
Teruel, Mariano A. .
JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, 2015, 28 (07) :480-484
[37]   Selected ion flow tube studies of the gas-phase reactions of O-center dot-, O-2(center dot-) and OH- with a variety of brominated compounds [J].
Thomas, R ;
Liu, Y ;
Mayhew, CA ;
Peverall, R .
INTERNATIONAL JOURNAL OF MASS SPECTROMETRY AND ION PROCESSES, 1996, 155 (03) :163-183
[38]   Studies of the Gas Phase Reactions of Linalool, 6-Methyl-5-hepten-2-ol and 3-Methyl-1-penten-3-ol with o3 and OH Radicals [J].
Bernard, Francois ;
Daele, Veronique ;
Mellouki, Abdelwahid ;
Sidebottom, Howard .
JOURNAL OF PHYSICAL CHEMISTRY A, 2012, 116 (24) :6113-6126
[39]   First evidence of the dramatic enhancement of the reactivity of methyl formate (HC(O)OCH3) with OH at temperatures of the interstellar medium: a gas-phase kinetic study between 22 K and 64 K [J].
Jimenez, E. ;
Antinolo, M. ;
Ballesteros, B. ;
Canosa, A. ;
Albaladejo, J. .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2016, 18 (03) :2183-2191
1234