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Reactivity of Polycyclic Aromatic Hydrocarbon Soot Precursors: Kinetics and Equilibria.

Accepted version
Peer-reviewed

Type

Article

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Authors

Menon, Angiras 

Abstract

The thermodynamics and kinetics of cross-linking reactions between PAHs of various reactive edge types that are observed in soot precursors are explored using density functional theory. The forward rate constants confirm that reactions involving aryl σ-radicals are faster than others, but rate constants for reactions between aryl σ-radicals and localized π-radicals can be as large or even larger than for two aryl σ-radicals. However, rates for all cross-linking reactions between small PAHs are likely too slow to explain soot formation. The equilibrium constants show that reactions involving σ and π-radical PAHs are the most favorable at flame temperatures. Equilibrium constants for larger PAHs show that the ability to form bonded-and-stacked structures results in enhanced equilibrium constants for the reaction of two large localized π-radicals compared to those for other edge types. This suggests that combined physical and chemical interactions between larger π-radical PAHs could be important in flame environments.

Description

Keywords

34 Chemical Sciences, 3406 Physical Chemistry, 3407 Theoretical and Computational Chemistry, 51 Physical Sciences, 5102 Atomic, Molecular and Optical Physics

Journal Title

J Phys Chem A

Conference Name

Journal ISSN

1089-5639
1520-5215

Volume Title

124

Publisher

American Chemical Society (ACS)

Rights

All rights reserved
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