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Thermodynamics of the formation of sulfuric acid dimers in the binary (H_2SO_4–H_2O) and ternary (H_2SO_4–H_2O–NH_3) system

Kürten, A. and Flagan, R. C. (2015) Thermodynamics of the formation of sulfuric acid dimers in the binary (H_2SO_4–H_2O) and ternary (H_2SO_4–H_2O–NH_3) system. Atmospheric Chemistry and Physics, 15 (18). pp. 10701-10721. ISSN 1680-7316. http://resolver.caltech.edu/CaltechAUTHORS:20151030-143827681

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Abstract

Sulfuric acid is an important gas influencing atmospheric new particle formation (NPF). Both the binary (H_2SO_4–H_2O) system and the ternary system involving ammonia (H_2SO_4–H_2O–NH_3) may be important in the free troposphere. An essential step in the nucleation of aerosol particles from gas-phase precursors is the formation of a dimer, so an understanding of the thermodynamics of dimer formation over a wide range of atmospheric conditions is essential to describe NPF. We have used the CLOUD chamber to conduct nucleation experiments for these systems at temperatures from 208 to 248 K. Neutral monomer and dimer concentrations of sulfuric acid were measured using a chemical ionization mass spectrometer (CIMS). From these measurements, dimer evaporation rates in the binary system were derived for temperatures of 208 and 223 K. We compare these results to literature data from a previous study that was conducted at higher temperatures but is in good agreement with the present study. For the ternary system the formation of H_2SO_4·NH_3 is very likely an essential step in the formation of sulfuric acid dimers, which were measured at 210, 223, and 248 K. We estimate the thermodynamic properties (dH and dS) of the H_2SO_4·NH_3 cluster using a simple heuristic model and the measured data. Furthermore, we report the first measurements of large neutral sulfuric acid clusters containing as many as 10 sulfuric acid molecules for the binary system using chemical ionization–atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometry.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.5194/acp-15-10701-2015DOIArticle
http://www.atmos-chem-phys.net/15/10701/2015/acp-15-10701-2015.htmlPublisherArticle
ORCID:
AuthorORCID
Flagan, R. C.0000-0001-5690-770X
Alternate Title:Thermodynamics of the formation of sulfuric acid dimers in the binary (H2SO4–H2O) and ternary (H2SO4–H2O–NH3) system
Additional Information:© 2015 Author(s) 2015. This work is distributed under the Creative Commons Attribution 3.0 License. Published by Copernicus Publications on behalf of the European Geosciences Union. Received: 26 March 2015 – Published in Atmos. Chem. Phys. Discuss.: 18 May 2015. Revised: 2 September 2015 – Accepted: 8 September 2015 – Published: 25 September 2015. We would like to thank CERN for supporting CLOUD with important technical and financial resources, and for providing a particle beam from the CERN Proton Synchrotron. This research was funded by the European Commission Seventh Framework Programme (Marie Curie Initial Training Network “CLOUD-ITN”, grant no. 215072), the German Federal Ministry of Education and Research (project nos. 01LK0902A and 01LK1222A), the European Research Council Advanced Grant “ATMNUCLE” (project no. 227463), the Academy of Finland (project nos. 1133872, 1118615, and 272041), the Swiss National Science Foundation (project nos. 200020_135307 and 206620_141278), the US National Science Foundation (grants AGS-1439551 and AGS-1447056), the Austrian Science Fund (project nos. P19546 and L593), and the Davidow foundation. We thank the tofTools team for providing tools for mass spectrometry analysis.
Funders:
Funding AgencyGrant Number
European Commission Seventh Framework ProgrammeCLOUD-ITN 215072
Bundesministerium für Bildung und Forschung (BMBF)01LK0902A
Bundesministerium für Bildung und Forschung (BMBF)01LK1222A
European Research Council (ERC)ATMNUCLE 227463
Academy of Finland1133872
Academy of Finland1118615
Academy of Finland272041
Swiss National Science Foundation (SNSF)200020_135307
Swiss National Science Foundation (SNSF)206620_141278
NSFAGS-1439551
NSFAGS-1447056
Fonds zur Förderung der wissenschaftlichen Forschung (FWF)P19546
Fonds zur Förderung der wissenschaftlichen Forschung (FWF)L593
Davidow FoundationUNSPECIFIED
Record Number:CaltechAUTHORS:20151030-143827681
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20151030-143827681
Official Citation:Kürten, A., Münch, S., Rondo, L., Bianchi, F., Duplissy, J., Jokinen, T., Junninen, H., Sarnela, N., Schobesberger, S., Simon, M., Sipilä, M., Almeida, J., Amorim, A., Dommen, J., Donahue, N. M., Dunne, E. M., Flagan, R. C., Franchin, A., Kirkby, J., Kupc, A., Makhmutov, V., Petäjä, T., Praplan, A. P., Riccobono, F., Steiner, G., Tomé, A., Tsagkogeorgas, G., Wagner, P. E., Wimmer, D., Baltensperger, U., Kulmala, M., Worsnop, D. R., and Curtius, J.: Thermodynamics of the formation of sulfuric acid dimers in the binary (H2SO4–H2O) and ternary (H2SO4–H2O–NH3) system, Atmos. Chem. Phys., 15, 10701-10721, doi:10.5194/acp-15-10701-2015, 2015
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:61749
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:02 Nov 2015 21:50
Last Modified:02 Nov 2015 21:50

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