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Title: Changes in Reactivity as Chemistry Becomes Confined to an Interface. The Case of Free Radical Oxidation of C 30H 62 Alkane by OH

Abstract

Here, we examine in a simple organic aerosol the transition between heterogeneous chemistry under well-mixed conditions to chemistry under interfacial confinement. A single reaction mechanism, shown to reproduce observed OH oxidation chemistry for liquid and semisolid C 30H 62, is used in reaction-diffusion simulations to explore reactivity over a broad viscosity range. The results show that when internal mixing of the aerosol is fast and the particle interface is enriched in C-H groups, ketone and alcohol products, formed via peroxy radical disproportionation, predominate. As viscosity increases the reactions become confined to a shell at the gas-aerosol interface. The confinement is accompanied by emergence of acyloxy reaction pathways that are particularly active when the shell is 1 nm or less. We quantify this trend using a reaction-diffusion index, allowing the parts of the mechanism that control reactivity as viscosity increases to be identified.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1457004
Grant/Contract Number:
AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 9; Journal Issue: 5; Related Information: © 2018 American Chemical Society.; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Houle, Frances A., Wiegel, Aaron A., and Wilson, Kevin R.. Changes in Reactivity as Chemistry Becomes Confined to an Interface. The Case of Free Radical Oxidation of C30H62 Alkane by OH. United States: N. p., 2018. Web. doi:10.1021/acs.jpclett.8b00172.
Houle, Frances A., Wiegel, Aaron A., & Wilson, Kevin R.. Changes in Reactivity as Chemistry Becomes Confined to an Interface. The Case of Free Radical Oxidation of C30H62 Alkane by OH. United States. doi:10.1021/acs.jpclett.8b00172.
Houle, Frances A., Wiegel, Aaron A., and Wilson, Kevin R.. Wed . "Changes in Reactivity as Chemistry Becomes Confined to an Interface. The Case of Free Radical Oxidation of C30H62 Alkane by OH". United States. doi:10.1021/acs.jpclett.8b00172.
@article{osti_1457004,
title = {Changes in Reactivity as Chemistry Becomes Confined to an Interface. The Case of Free Radical Oxidation of C30H62 Alkane by OH},
author = {Houle, Frances A. and Wiegel, Aaron A. and Wilson, Kevin R.},
abstractNote = {Here, we examine in a simple organic aerosol the transition between heterogeneous chemistry under well-mixed conditions to chemistry under interfacial confinement. A single reaction mechanism, shown to reproduce observed OH oxidation chemistry for liquid and semisolid C30H62, is used in reaction-diffusion simulations to explore reactivity over a broad viscosity range. The results show that when internal mixing of the aerosol is fast and the particle interface is enriched in C-H groups, ketone and alcohol products, formed via peroxy radical disproportionation, predominate. As viscosity increases the reactions become confined to a shell at the gas-aerosol interface. The confinement is accompanied by emergence of acyloxy reaction pathways that are particularly active when the shell is 1 nm or less. We quantify this trend using a reaction-diffusion index, allowing the parts of the mechanism that control reactivity as viscosity increases to be identified.},
doi = {10.1021/acs.jpclett.8b00172},
journal = {Journal of Physical Chemistry Letters},
number = 5,
volume = 9,
place = {United States},
year = {Wed Feb 14 00:00:00 EST 2018},
month = {Wed Feb 14 00:00:00 EST 2018}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on February 14, 2019
Publisher's Version of Record

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Cited by: 1 work
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