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

被引：13
|
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.
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页数：15
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