Elucidation of structure-reactivity relationships in hindered phenols via quantum chemistry and transition state theory

被引：27

作者：

Pfaendtner, Jim ^{[1
]}

Broadbelt, Linda J. ^{[1
]}

机构：

[1] Northwestern Univ, Dept Chem & Biol Engn, Evanston, IL 60208 USA

来源：

CHEMICAL ENGINEERING SCIENCE | 2007年 / 62卷 / 18-20期

基金：

美国国家科学基金会;

关键词：

computation; computational chemistry; kinetics; reaction engineering; hindered phenols; hydrogen abstraction;

D O I：

10.1016/j.ces.2006.12.080

中图分类号：

TQ [化学工业];

学科分类号：

0817 ;

摘要：

Quantum chemistry and transition state theory were used to study 10 different radical reactions of peroxy radicals abstracting the phenolic hydrogen of several antioxidants. The B3LYP functional with a 6-31G(d) basis set was used to characterize transition states with as many as 20 heavy atoms. The impact of quantum tunneling was investigated for a representative reaction, and it was shown that the Wigner correction provides a good approximation to more advanced semi-classical transmission coefficients. A kinetic correlation was developed that is suitable for use in kinetic modeling, allowing antioxidant chemistry to be included in large mechanistic models of hydrocarbon oxidation. (c) 2007 Elsevier Ltd. All rights reserved.

引用

页码：5232 / 5239

页数：8

共 54 条

[1] DRAMATIC SOLVENT EFFECTS ON THE ABSOLUTE RATE CONSTANTS FOR ABSTRACTION OF THE HYDROXYLIC HYDROGEN-ATOM FROM TERT-BUTYL HYDROPEROXIDE AND PHENOL BY THE CUMYLOXYL RADICAL - THE ROLE OF HYDROGEN-BONDING [J].

AVILA, DV ;

INGOLD, KU ;

LUSZTYK, J ;

GREEN, WH ;

PROCOPIO, DR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (10) :2929-2930

[2] Phenolic compounds in plants and agri-industrial by-products: Antioxidant activity, occurrence, and potential uses [J].

Balasundram, Nagendran ;

Sundram, Kalyana ;

Samman, Samir .

FOOD CHEMISTRY, 2006, 99 (01) :191-203

[3] DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].

BECKE, AD .

JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652

[4] Engineering approximations for activation energies in hydrogen transfer reactions [J].

Blowers, P ;

Masel, R .

AICHE JOURNAL, 2000, 46 (10) :2041-2052

[5] Quantum chemical studies on the thermochemistry of alkyl and peroxyl radicals [J].

Brinck, T ;

Lee, HN ;

Jonsson, M .

JOURNAL OF PHYSICAL CHEMISTRY A, 1999, 103 (35) :7094-7104

[6] Lexicography of kinetic modeling of complex reaction networks [J].

Broadbelt, LJ ;

Pfaendtner, J .

AICHE JOURNAL, 2005, 51 (08) :2112-2121

[7] A new integral equation formalism for the polarizable continuum model: Theoretical background and applications to isotropic and anisotropic dielectrics [J].

Cances, E ;

Mennucci, B ;

Tomasi, J .

JOURNAL OF CHEMICAL PHYSICS, 1997, 107 (08) :3032-3041

[8] Methyl radical addition to C=S double bonds: Kinetic versus thermodynamic preferences [J].

Coote, ML ;

Wood, GPF ;

Radom, L .

JOURNAL OF PHYSICAL CHEMISTRY A, 2002, 106 (50) :12124-12138

[9]

Denisov E.T., 1974, LIQUID PHASE REACTIO

[10] MECHANISMS OF ACTION AND REACTIVITIES OF THE FREE-RADICALS OF INHIBITORS [J].

DENISOV, ET ;

KHUDYAKOV, IV .

CHEMICAL REVIEWS, 1987, 87 (06) :1313-1357

← 1 2 3 4 5 6 →