The Formation of Highly Oxidized Multifunctional Products in the Ozonolysis of Cyclohexene

被引：234

作者：

Rissanen, Matti P. ^{[1
]}

Kurten, Theo ^{[2
]}

Sipila, Mikko ^{[1
]}

Thornton, Joel A. ^{[3
]}

Kangasluoma, Juha ^{[1
]}

Sarnela, Nina ^{[1
]}

Junninen, Heikki ^{[1
]}

Jorgensen, Solvejg ^{[4
]}

Schallhart, Simon ^{[1
]}

Kajos, Maija K. ^{[1
]}

Taipale, Risto ^{[1
]}

Springer, Monika ^{[5
]}

Mentel, Thomas F. ^{[5
]}

Ruuskanen, Taina ^{[1
]}

Petaja, Tuukka ^{[1
]}

Worsnop, Douglas R. ^{[1
,6
]}

Kjaergaard, Henrik G. ^{[4
]}

Ehn, Mikael ^{[1
]}

机构：

[1] Univ Helsinki, Dept Phys, Helsinki 00014, Finland

[2] Univ Helsinki, Dept Chem, Helsinki 00014, Finland

[3] Univ Washington, Dept Atmospher Sci, Seattle, WA 98195 USA

[4] Univ Copenhagen, Dept Chem, DK-2100 Copenhagen O, Denmark

[5] Forschungszentrum Julich, Inst Energy & Climate Res IEK 8, D-52425 Julich, Germany

[6] Aerodyne Res Inc, Billerica, MA 01821 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2014年 / 136卷 / 44期

基金：

芬兰科学院;

关键词：

SECONDARY ORGANIC AEROSOL; GAS-PHASE OZONOLYSIS; LOW-MOLECULAR-WEIGHT; ATMOSPHERIC CHEMISTRY; PRESSURE-DEPENDENCE; CYCLIC ALKENES; ALPHA-PINENE; OZONE; O-3; OXIDATION;

D O I：

10.1021/ja507146s

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The prompt formation of highly oxidized organic compounds in the ozonolysis of cyclohexene (C6H10) was investigated by means of laboratory experiments together with quantum chemical calculations. The experiments were performed in borosilicate glass flow tube reactors coupled to a chemical ionization atmospheric pressure interface time-of-flight mass spectrometer with a nitrate ion (NO3-)-based ionization scheme. Quantum chemical calculations were performed at the CCSD(T)-F12a/VDZ-F12//pi B97XD/aug-cc-pVTZ level, with kinetic modeling using multiconformer transition state theory, including Eckart tunneling corrections. The complementary investigation methods gave a consistent picture of a formation mechanism advancing by peroxy radical (RO2) isomerization through intramolecular hydrogen shift reactions, followed by sequential O-2 addition steps, that is, RO2 autoxidation, on a time scale of seconds. Dimerization of the peroxy radicals by recombination and cross-combination reactions is in competition with the formation of highly oxidized monomer species and is observed to lead to peroxides, potentially diacyl peroxides. The molar yield of these highly oxidized products (having O/C > 1 in monomers and O/C > 0.55 in dimers) from cyclohexene ozonolysis was determined as (4.5 +/- 3.8)%. Fully deuterated cyclohexene and cis-6-nonenal ozonolysis, as well as the influence of water addition to the system (either H2O or D2O), were also investigated in order to strengthen the arguments on the proposed mechanism. Deuterated cyclohexene ozonolysis resulted in a less oxidized product distribution with a lower yield of highly oxygenated products and cis-6-nonenal ozonolysis generated the same monomer product distribution, consistent with the proposed mechanism and in agreement with quantum chemical modeling.

引用

页码：15596 / 15606

页数：11

共 93 条

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