Issue 28, 2017

Exploring the chemical kinetics of partially oxidized intermediates by combining experiments, theory, and kinetic modeling

Abstract

Partially oxidized intermediates play a central role in combustion and atmospheric chemistry. In this perspective, we focus on the chemical kinetics of alkoxy radicals, peroxy radicals, and Criegee intermediates, which are key species in both combustion and atmospheric environments. These reactive intermediates feature a broad spectrum of chemical diversity. Their reactivity is central to our understanding of how volatile organic compounds are degraded in the atmosphere and converted into secondary organic aerosol. Moreover, they sensitively determine ignition timing in internal combustion engines. The intention of this perspective article is to provide the reader with information about the general mechanisms of reactions initiated by addition of atomic and molecular oxygen to alkyl radicals and ozone to alkenes. We will focus on critical branching points in the subsequent reaction mechanisms and discuss them from a consistent point of view. As a first example of our integrated approach, we will show how experiment, theory, and kinetic modeling have been successfully combined in the first infrared detection of Criegee intermediates during the gas phase ozonolysis. As a second example, we will examine the ignition timing of n-heptane/air mixtures at low and intermediate temperatures. Here, we present a reduced, fuel size independent kinetic model of the complex chemistry initiated by peroxy radicals that has been successfully applied to simulate standard n-heptane combustion experiments.

Graphical abstract: Exploring the chemical kinetics of partially oxidized intermediates by combining experiments, theory, and kinetic modeling

Article information

Article type
Perspective
Submitted
27 4月 2017
Accepted
21 6月 2017
First published
06 7月 2017

Phys. Chem. Chem. Phys., 2017,19, 18128-18146

Exploring the chemical kinetics of partially oxidized intermediates by combining experiments, theory, and kinetic modeling

K. Hoyermann, F. Mauß, M. Olzmann, O. Welz and T. Zeuch, Phys. Chem. Chem. Phys., 2017, 19, 18128 DOI: 10.1039/C7CP02759A

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements