The Gas-Phase Decomposition of CF3OH with Water: A Radical-Catalyzed Mechanism

被引：43

作者：

Buszek, Robert J. ^{[1
]}

Francisco, Joseph S. ^{[1
]}

机构：

[1] Purdue Univ, Dept Chem, W Lafayette, IN 47907 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2009年 / 113卷 / 18期

关键词：

ATMOSPHERIC CHEMISTRY; HYDROGEN-FLUORIDE; AB-INITIO; TRIFLUOROMETHANOL; DEGRADATION; ABSORPTION; PHOTOLYSIS; ENERGETICS; ALCOHOLS; OZONE;

D O I：

10.1021/jp900642q

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：

CF3OH is an atmospheric sink for hydrofluorocarbons (HFCs) and hydrofluoroethers (HFEs). Several new mechanisms, including catalyzation via H2O and OH radical, for the decomposition of CF3OH into HF and CF2O are studied using ab inito methods. The present work demonstrates that the OH radical has a strong catalytic effect on the transition state for the decomposition of CF3OH. The barrier is found to be reduced from 45.9 kcal mol(-1) for the unimolecular decomposition to 11.0 kcal mol(-1) for decomposition including H2O and OH.

引用

收藏

页码：5333 / 5337

页数：5

相关论文

共 28 条

[1]

[Anonymous], 2016, GAUSSIAN 16 REV B01

[2] POTENTIAL FOR WATER CATALYSIS IN FLAVIN-MEDIATED HYDROXYLATION - A THEORETICAL-STUDY [J].

BACH, RD ;

MCDOUALL, JJW ;

OWENSBY, AL ;

SCHLEGEL, HB .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (19) :7064-7065

[3] Theoretical study on the kinetics and mechanism of the hydrogen atom abstraction reactions of CF3O+H2O and CF3OH+OH [J].

Brudnik, K ;

Jodkowski, JT ;

Ratajczak, E ;

Venkatraman, R ;

Nowek, A ;

Sullivan, RH .

CHEMICAL PHYSICS LETTERS, 2001, 345 (5-6) :435-444

[4] Vibrational deactivation studies of OH X 2Π (ν=1-5) by N2 and O2 [J].

D'Ottone, L ;

Bauer, D ;

Campuzano-Jost, P ;

Fardy, M ;

Hynes, AJ .

PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2004, 6 (17) :4276-4282

[5] Atmospheric photochemistry via vibrational overtone absorption [J].

Donaldson, DJ ;

Tuck, AF ;

Vaida, V .

CHEMICAL REVIEWS, 2003, 103 (12) :4717-4729

[6] Degradation of fluorotelomer alcohols: A likely atmospheric source of perfluorinated carboxylic acids [J].

Ellis, DA ;

Martin, JW ;

De Silva, AO ;

Mabury, SA ;

Hurley, MD ;

Andersen, MPS ;

Wallington, TJ .

ENVIRONMENTAL SCIENCE & TECHNOLOGY, 2004, 38 (12) :3316-3321

[7] Thermolysis of fluoropolymers as a potential source of halogenated organic acids in the environment [J].

Ellis, DA ;

Mabury, SA ;

Martin, JW ;

Muir, DCG .

NATURE, 2001, 412 (6844) :321-324

[8] LARGE LOSSES OF TOTAL OZONE IN ANTARCTICA REVEAL SEASONAL CLOX/NOX INTERACTION [J].

FARMAN, JC ;

GARDINER, BG ;

SHANKLIN, JD .

NATURE, 1985, 315 (6016) :207-210

[9]

FINZI J, 1977, J CHEM PHYS, V67, P4053, DOI 10.1063/1.435379

[10] AN EXAMINATION OF PRIMARY AND SECONDARY DISSOCIATION PATHWAYS OF TRIFLUOROMETHANOL - IDENTIFICATION OF PLAUSIBLE ROUTES LEADING TO THE FORMATION OF HYDROGEN-FLUORIDE [J].

FRANCISCO, JS .

CHEMICAL PHYSICS, 1991, 150 (01) :19-27