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Kinetic regimes and limiting cases of gas uptake and heterogeneous reactions in atmospheric aerosols and clouds: a general classification scheme

Berkemeier, T. and Huisman, A. J. and Ammann, M. and Shiraiwa, M. and Koop, T. and Pöschl, U. (2013) Kinetic regimes and limiting cases of gas uptake and heterogeneous reactions in atmospheric aerosols and clouds: a general classification scheme. Atmospheric Chemistry and Physics, 13 (14). pp. 6663-6686. ISSN 1680-7316. http://resolver.caltech.edu/CaltechAUTHORS:20130903-110327038

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Abstract

Heterogeneous reactions are important to atmospheric chemistry and are therefore an area of intense research. In multiphase systems such as aerosols and clouds, chemical reactions are usually strongly coupled to a complex sequence of mass transport processes and results are often not easy to interpret. Here we present a systematic classification scheme for gas uptake by aerosol or cloud particles which distinguishes two major regimes: a reaction-diffusion regime and a mass transfer regime. Each of these regimes includes four distinct limiting cases, characterised by a dominant reaction location (surface or bulk) and a single rate-limiting process: chemical reaction, bulk diffusion, gas-phase diffusion or mass accommodation. The conceptual framework enables efficient comparison of different studies and reaction systems, going beyond the scope of previous classification schemes by explicitly resolving interfacial transport processes and surface reactions limited by mass transfer from the gas phase. The use of kinetic multi-layer models instead of resistor model approaches increases the flexibility and enables a broader treatment of the subject, including cases which do not fit into the strict limiting cases typical of most resistor model formulations. The relative importance of different kinetic parameters such as diffusion, reaction rate and accommodation coefficients in this system is evaluated by a quantitative global sensitivity analysis. We outline the characteristic features of each limiting case and discuss the potential relevance of different regimes and limiting cases for various reaction systems. In particular, the classification scheme is applied to three different datasets for the benchmark system of oleic acid reacting with ozone in order to demonstrate utility and highlight potential issues. In light of these results, future directions of research needed to elucidate the multiphase chemical kinetics in this and other reaction systems are discussed.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.5194/acp-13-6663-2013 DOIArticle
http://www.atmos-chem-phys.net/13/6663/2013/acp-13-6663-2013.htmlPublisherArticle
ORCID:
AuthorORCID
Shiraiwa, M.0000-0003-2532-5373
Additional Information:© 2013 Author(s). This work is distributed under the Creative Commons Attribution 3.0 License. Published by Copernicus Publications on behalf of the European Geosciences Union. Received: 30 November 2012 – Published in Atmos. Chem. Phys. Discuss.: 9 January 2013 Revised: 17 May 2013 – Accepted: 30 May 2013 – Published: 15 July 2013. T. Berkemeier acknowledges support from the European Union Lifelong Learning Programme. A. J. Huisman was supported by the United States National Science Foundation under award no. IRFP 1006117 and by ETH Zürich. M. Ammann appreciated support by the Swiss National Science Foundation (grant no. 130175). M. Shiraiwa is supported by the Japan Society for the Promotion of Science (JSPS) Postdoctoral Fellowship for Research Abroad and the EU project PEGASOS (grant no. 265148). Any opinions, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the US National Science Foundation. T. Berkemeier and A. J. Huisman thank U. Krieger and T. Peter for their support and for many useful conversations. T. Berkemeier would like to thank P. Ziemann, G. Smith, C. Chan and A. Lee for providing original datasets. The service charges for this open access publication have been covered by the Max Planck Society. Edited by: V. F. McNeill.
Funders:
Funding AgencyGrant Number
European Union Lifelong Learning ProgrammeUNSPECIFIED
NSFOISE-1006117
ETH Zürich UNSPECIFIED
Swiss National Science Foundation (SNSF)130175
Japan Society for the Promotion of Science (JSPS)UNSPECIFIED
European Commission PEGASOS265148
Record Number:CaltechAUTHORS:20130903-110327038
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20130903-110327038
Official Citation:Berkemeier, T., Huisman, A. J., Ammann, M., Shiraiwa, M., Koop, T., and Pöschl, U.: Kinetic regimes and limiting cases of gas uptake and heterogeneous reactions in atmospheric aerosols and clouds: a general classification scheme, Atmos. Chem. Phys., 13, 6663-6686, doi:10.5194/acp-13-6663-2013, 2013
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:41054
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:18 Sep 2013 17:14
Last Modified:02 May 2017 23:04

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