Kinetics and Thermodynamics of Limonene Ozonolysis

被引：24

作者：

Baptista, Leonardo ^{[1
]}

Pfeifer, Rene ^{[2
]}

da Silva, Edilson Clement ^{[2
]}

Arbilla, Graciela ^{[2
]}

机构：

[1] Univ Estado Rio De Janeiro, Fac Tecnol, Dept Quim & Ambiental, Resende, RJ, Brazil

[2] Univ Fed Rio de Janeiro, Inst Quim, BR-21941909 Rio De Janeiro, Brazil

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2011年 / 115卷 / 40期

关键词：

ORGANIC AEROSOL FORMATION; GAS-PHASE OZONOLYSIS; VIBRATIONAL FREQUENCIES; ALPHA-PINENE; OXIDATION MECHANISM; TERPENE OZONOLYSIS; RATE CONSTANTS; OZONE; ISOPRENE; GERANIOL;

D O I：

10.1021/jp205734h

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：

Using density functional methods, the initial reaction steps of limonene ozonolysis have been investigated with a focus on primary ozonide formation and its decomposition to Criegee intermediates and carbonyl compounds. The ozonide formation is highly exothermic, and the decomposition channels have similar free energies of activation, Delta G*, indicating that there is no primary pathway for ozonide decomposition. Assuming that ozonide formation is the rate limiting step, the theoretical rate coefficient, k = 1.6 x 10(-16) molecule(-1) cm(3) s(-1), evaluated at the CCSD(T)/6-31G(d,p)//BHandHLYP/cc-pvdz level and 298.15 K for d-limonene is in good agreement with the experimental value, k(exp) = 3.3 x 10(-16) molecule(-1) cm(3) s(-1). The theoretical Arrhenius expression is also in good agreement with experimental results.

引用

页码：10911 / 10919

页数：9

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