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

页数：15

共 69 条

[21] Investigation of the Role of Bicyclic Peroxy Radicals in the Oxidation Mechanism of Toluene [J].

Birdsall, Adam W. ;

Andreoni, John F. ;

Elrod, Matthew J. .

JOURNAL OF PHYSICAL CHEMISTRY A, 2010, 114 (39) :10655-10663

[22] Bond dissociation energies of organic molecules [J].

Blanksby, SJ ;

Ellison, GB .

ACCOUNTS OF CHEMICAL RESEARCH, 2003, 36 (04) :255-263

[23] Formation of peroxy radicals from OH-toluene adducts and O2 [J].

Bohn, B .

JOURNAL OF PHYSICAL CHEMISTRY A, 2001, 105 (25) :6092-6101

[24] The aromatic amine carcinogens o-toluidine and o-anisidine induce free radicals and intrachromosomal recombination in Saccharomyces cerevisiae [J].

Brennan, RJ ;

Schiestl, RH .

MUTATION RESEARCH-FUNDAMENTAL AND MOLECULAR MECHANISMS OF MUTAGENESIS, 1999, 430 (01) :37-45

[25] KiSThelP: A Program to Predict Thermodynamic Properties and Rate Constants from Quantum Chemistry Results [J].

Canneaux, Sebastien ;

Bohr, Frederic ;

Henon, Eric .

JOURNAL OF COMPUTATIONAL CHEMISTRY, 2014, 35 (01) :82-93

[26] Bladder cancer incidence among workers exposed to o-toluidine, aniline and nitrobenzene at a rubber chemical manufacturing plant [J].

Carreon, Tania ;

Hein, Misty J. ;

Hanley, Kevin W. ;

Viet, Susan M. ;

Ruder, Avima M. .

OCCUPATIONAL AND ENVIRONMENTAL MEDICINE, 2014, 71 (03) :175-182

[27] Increased bladder cancer risk among workers exposed to o-toluidine and aniline: a reanalysis [J].

Carreon, Tania ;

Hein, Misty J. ;

Viet, Susan M. ;

Hanley, Kevin W. ;

Ruder, Avima M. ;

Ward, Elizabeth M. .

OCCUPATIONAL AND ENVIRONMENTAL MEDICINE, 2010, 67 (05) :348-350

[28] Long-range corrected hybrid density functionals with damped atom-atom dispersion corrections [J].

Chai, Jeng-Da ;

Head-Gordon, Martin .

PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2008, 10 (44) :6615-6620

[29] Atmospheric Chemistry of 2-Aminoethanol (MEA): Reaction of the NH2•CHCH2OH Radical with O2 [J].

da Silva, Gabriel .

JOURNAL OF PHYSICAL CHEMISTRY A, 2012, 116 (45) :10980-10986

[30] Theoretical investigations of the gas phase reaction of limonene (C10H16) with OH radical [J].

Dash, Manas Ranjan ;

Rajakumar, B. .

MOLECULAR PHYSICS, 2015, 113 (21) :3202-3215

← 1 2 3 4 5 6 7 →