Direct observation of OH formation from stabilised Criegee intermediates

被引：111

作者：

Novelli, A. ^{[1
]}

Vereecken, L. ^{[1
]}

Lelieveld, J. ^{[1
]}

Harder, H. ^{[1
]}

机构：

[1] Max Planck Inst Chem, Atmospher Chem Dept, D-55128 Mainz, Germany

来源：

PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 2014年 / 16卷 / 37期

关键词：

GAS-PHASE OZONOLYSIS; VOLATILE ORGANIC-COMPOUNDS; SULFURIC-ACID CONCENTRATIONS; SUBSTITUTED CARBONYL OXIDES; DIRECT KINETIC MEASUREMENTS; ATMOSPHERIC OXIDATION; MEXICO-CITY; TROPOSPHERIC DEGRADATION; AEROSOL FORMATION; CH2OO REACTIONS;

D O I：

10.1039/c4cp02719a

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：

The syn-CH3CHOO Criegee intermediate formed from the ozonolysis of propene and (E)-2-butene was detected via unimolecular decomposition and subsequent detection of OH radicals by a LIF-FAGE instrument. An observed time dependent OH concentration profile was analysed using a detailed model focusing on the speciated chemistry of Criegee intermediates based on the recent literature. The absolute OH concentration was found to depend on the steady state concentration of syn-CH3CHOO at the injection point while the time dependence of the OH concentration profile was influenced by the sum of the rates of unimolecular decomposition of syn-CH3CHOO and wall loss. By varying the most relevant parameters influencing the SCI chemistry in the model and based on the temporal OH concentration profile, the unimolecular decomposition rate k (293 K) of syn-CH3CHOO was shown to lie within the range 3-30 s(-1), where a value of 20 +/- 10 s(-1) yields the best agreement with the CI chemistry literature.

引用

页码：19941 / 19951

页数：11

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