Thermodynamics of the formation of sulfuric acid dimers in the binary (H2SO4-H2O) and ternary (H2SO4-H2O-NH3) system

A. Kürten; S. Münch; L. Rondo; F. Bianchi; J. Duplissy; T. Jokinen; H. Junninen; N. Sarnela; S. Schobesberger; M. Simon; M. Sipilä; J. Almeida; A. Amorim; J. Dommen; N. M. Donahue; E. M. Dunne; R. C. Flagan; A. Franchin; J. Kirkby; A. Kupc; V. Makhmutov; T. Petäjä; A. P. Praplan; F. Riccobono; Gerhard Steiner; A. Tome; G. Tsagkogeorgas; Paul Wagner; D. Wimmer; U. Baltensperger; Markku Kulmala; D. R. Worsnop; J. Curtius

doi:10.5194/acp-15-10701-2015

Thermodynamics of the formation of sulfuric acid dimers in the binary (H2SO4-H2O) and ternary (H2SO4-H2O-NH3) system

A. Kürten (Corresponding author)
, S. Münch
, L. Rondo
, F. Bianchi
, J. Duplissy
, T. Jokinen
, H. Junninen
, N. Sarnela
, S. Schobesberger
, M. Simon
, M. Sipilä
, J. Almeida
, A. Amorim
, J. Dommen
, N. M. Donahue
, E. M. Dunne
, R. C. Flagan
, A. Franchin
, J. Kirkby
, A. Kupc

V. Makhmutov, T. Petäjä, A. P. Praplan, F. Riccobono, Gerhard Steiner, A. Tome, G. Tsagkogeorgas, Paul Wagner, D. Wimmer, U. Baltensperger, Markku Kulmala, D. R. Worsnop, J. Curtius

Aerosol Physics and Environmental Physics

Publications: Contribution to journal › Article › Peer Reviewed

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.

Original language	English
Pages (from-to)	10701-10721
Number of pages	21
Journal	Atmospheric Chemistry and Physics
Volume	15
Issue number	18
Early online date	18 May 2015
DOIs	https://doi.org/10.5194/acp-15-10701-2015
Publication status	Published - 25 Sept 2015

Funding

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.

Austrian Fields of Science 2012

103037 Environmental physics
103039 Aerosol physics

Keywords

PRENUCLEATION MOLECULAR CLUSTERS
ATMOSPHERIC AEROSOL NUCLEATION
IONIZATION MASS-SPECTROMETER
PARTICLE FORMATION
GAS-PHASE
UPPER TROPOSPHERE
CLOUD EXPERIMENT
PEM-TROPICS
ION
AMMONIA

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http://phaidra.univie.ac.at/o:446490Licence: CC BY 3.0

Cite this

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., ... Curtius, J. (2015). Thermodynamics of the formation of sulfuric acid dimers in the binary (H2SO4-H2O) and ternary (H2SO4-H2O-NH3) system. Atmospheric Chemistry and Physics, 15(18), 10701-10721. https://doi.org/10.5194/acp-15-10701-2015

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title = "Thermodynamics of the formation of sulfuric acid dimers in the binary (H2SO4-H2O) and ternary (H2SO4-H2O-NH3) system",

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. ",

keywords = "PRENUCLEATION MOLECULAR CLUSTERS, ATMOSPHERIC AEROSOL NUCLEATION, IONIZATION MASS-SPECTROMETER, PARTICLE FORMATION, GAS-PHASE, UPPER TROPOSPHERE, CLOUD EXPERIMENT, PEM-TROPICS, ION, AMMONIA",

author = "A. K{\"u}rten and S. M{\"u}nch and L. Rondo and F. Bianchi and J. Duplissy and T. Jokinen and H. Junninen and N. Sarnela and S. Schobesberger and M. Simon and M. Sipil{\"a} and J. Almeida and A. Amorim and J. Dommen and Donahue, \{N. M.\} and Dunne, \{E. M.\} and Flagan, \{R. C.\} and A. Franchin and J. Kirkby and A. Kupc and V. Makhmutov and T. Pet{\"a}j{\"a} and Praplan, \{A. P.\} and F. Riccobono and Gerhard Steiner and A. Tome and G. Tsagkogeorgas and Paul Wagner and D. Wimmer and U. Baltensperger and Markku Kulmala and Worsnop, \{D. R.\} and J. Curtius",

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doi = "10.5194/acp-15-10701-2015",

language = "English",

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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, NM, Dunne, EM, Flagan, RC, Franchin, A, Kirkby, J, Kupc, A, Makhmutov, V, Petäjä, T, Praplan, AP, Riccobono, F, Steiner, G, Tome, A, Tsagkogeorgas, G, Wagner, P, Wimmer, D, Baltensperger, U, Kulmala, M, Worsnop, DR & Curtius, J 2015, 'Thermodynamics of the formation of sulfuric acid dimers in the binary (H2SO4-H2O) and ternary (H2SO4-H2O-NH3) system', Atmospheric Chemistry and Physics, vol. 15, no. 18, pp. 10701-10721. https://doi.org/10.5194/acp-15-10701-2015

TY - JOUR

T1 - Thermodynamics of the formation of sulfuric acid dimers in the binary (H2SO4-H2O) and ternary (H2SO4-H2O-NH3) system

AU - Kürten, A.

AU - Münch, S.

AU - Rondo, L.

AU - Bianchi, F.

AU - Duplissy, J.

AU - Jokinen, T.

AU - Junninen, H.

AU - Sarnela, N.

AU - Schobesberger, S.

AU - Simon, M.

AU - Sipilä, M.

AU - Almeida, J.

AU - Amorim, A.

AU - Dommen, J.

AU - Donahue, N. M.

AU - Dunne, E. M.

AU - Flagan, R. C.

AU - Franchin, A.

AU - Kirkby, J.

AU - Kupc, A.

AU - Makhmutov, V.

AU - Petäjä, T.

AU - Praplan, A. P.

AU - Riccobono, F.

AU - Steiner, Gerhard

AU - Tome, A.

AU - Tsagkogeorgas, G.

AU - Wagner, Paul

AU - Wimmer, D.

AU - Baltensperger, U.

AU - Kulmala, Markku

AU - Worsnop, D. R.

AU - Curtius, J.

PY - 2015/9/25

Y1 - 2015/9/25

N2 - 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.

AB - 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.

KW - PRENUCLEATION MOLECULAR CLUSTERS

KW - ATMOSPHERIC AEROSOL NUCLEATION

KW - IONIZATION MASS-SPECTROMETER

KW - PARTICLE FORMATION

KW - GAS-PHASE

KW - UPPER TROPOSPHERE

KW - CLOUD EXPERIMENT

KW - PEM-TROPICS

KW - ION

KW - AMMONIA

UR - https://www.scopus.com/pages/publications/84942778692

U2 - 10.5194/acp-15-10701-2015

DO - 10.5194/acp-15-10701-2015

M3 - Article

SN - 1680-7316

VL - 15

SP - 10701

EP - 10721

JO - Atmospheric Chemistry and Physics

JF - Atmospheric Chemistry and Physics

IS - 18

ER -

Thermodynamics of the formation of sulfuric acid dimers in the binary (H2SO4-H2O) and ternary (H2SO4-H2O-NH3) system

Abstract

Funding

Austrian Fields of Science 2012

Keywords

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