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Journal ArticleDOI

Production of stabilized Criegee intermediates and peroxides in the gas phase ozonolysis of alkenes: 1. Ethene, trans‐2‐butene, and 2,3‐dimethyl‐2‐butene

TLDR
In this paper, the formation of hydrogen peroxide and organic hydroperoxides was investigated in the gas phase ozonolysis of ethene, trans-2-butene, and 2,3-dimethyl-2butene.
Abstract
Ozone-alkene reactions generate stabilized Criegee intermediates (of the form R1R2COO), which are believed to react with water molecules to form organic hydroperoxides, hydrogen peroxide and carboxylic acids. These reactions are thought to be significant sources of these environmentally important compounds, yet both the yields of stabilized Criegee intermediates and the branching ratios from their reaction with water are not well known. The formation of hydrogen peroxide and organic hydroperoxides was investigated in the gas phase ozonolysis of ethene, trans-2-butene, and 2,3-dimethyl-2-butene for relative humidities (RH) from 0 and 80% by gas chromatography with flame ionization detection and high-performance liquid chromatography with fluorescence detection. Additionally, yields of acetaldehyde and acetic acid from trans-2-butene and acetone from 2,3-dimethyl-2-butene were measured. The reactions of stabilized Criegee intermediates with water were found to proceed almost entirely via organic hydroperoxide or hydrogen peroxide formation with little acid formation. Stabilized Criegee intermediate yields of 0.39, 0.24, and 0.10 were obtained for ethene, trans-2-butene, and 2,3-dimethyl-2-butene, respectively.

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Journal ArticleDOI

The gas-phase ozonolysis of unsaturated volatile organic compounds in the troposphere.

TL;DR: The kinetics, products and mechanisms of these reactions are examined, starting with a discussion of the original mechanism proposed by Criegee and following with a summary presentation of the complex, free radical-mediated reactions of carbonyl oxide (Criegee) intermediates.
Journal ArticleDOI

Multiphase chemistry at the atmosphere-biosphere interface influencing climate and public health in the anthropocene.

TL;DR: This work addresses air contaminants and their multiphase chemical interactions at the atmosphere−biosphere interface, including human lungs and skin, plant leaves, cryptogamic covers, soil, and aquatic surfaces, and the chemical interactions of reactive oxygen species and reactive nitrogen species, as well as carbonaceous combustion aerosols.
Journal ArticleDOI

Direct kinetic measurement of the reaction of the simplest Criegee intermediate with water vapor

TL;DR: Ultraviolet absorption spectroscopic measurements of the lifetime of the simplest Criegee intermediate, CH2OO, at various relative humidity levels up to 85% at 298 kelvin are reported, implying that reactivity with atmospheric water pairs is a major decay channel for Criegees.
Journal ArticleDOI

High-resolution mass spectrometry analysis of secondary organic aerosol generated by ozonolysis of isoprene

TL;DR: The chemical composition of secondary organic aerosol (SOA) generated from the ozonolysis of isoprene (C5H8) in the presence of an OH scavenger was examined using high-resolution electrospray ionization mass spectrometry (ESI-MS) as discussed by the authors.
References
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Journal ArticleDOI

Gas-Phase Tropospheric Chemistry of Volatile Organic Compounds: 1. Alkanes and Alkenes

TL;DR: The most recent review and evaluation of Atkinson [J. Phys. Chem. Ref. Data, 26, No. 3 (1997) and as mentioned in this paper concerning the gas phase reactions of alkanes and alkenes (including isoprene and monoterpenes) leading to their first generation products are reviewed and evaluated for tropospheric conditions.
Journal ArticleDOI

Water-soluble organics in atmospheric particles: A critical review of the literature and application of thermodynamics to identify candidate compounds

TL;DR: In this paper, the authors identify specific compounds that are likely to contribute to the water-soluble fraction by juxtaposing observations regarding the extraction characteristics and the molecular composition of atmospheric particulate organics with compound-specific solubility and condensibility for a wide variety of organics.
Journal ArticleDOI

Mechanism of Ozonolysis

TL;DR: The formation of ozonides (1,2,4-trioxolanes) from alkenes and ozone can be described as a succession of three [2+3] cycloadditions or cycloreversions involving primary ozone oxides and aldehyde or ketone oxides as decisive intermediates as mentioned in this paper.
Journal ArticleDOI

Calculation of Flame Ionization Detector Relative Response Factors Using the Effective Carbon Number Concept

TL;DR: In this article, an approach for relating flame ionization detector relative response factors to the effective carbon number (ECN) of neat and derivatized components is presented. But this approach can be used for detecting polycyclic aromatic hydrocarbons and oxygenated organics.
Book

Composition Chemistry, and Climate of the Atmosphere

TL;DR: The history of air pollution and its role in climate change can be found in this paper, where the changing composition of the Earth's atmosphere's atmosphere is discussed and an overview of the sources of pollution and sources of sources of ozone depletion is given.
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