Thermodynamics of the formation of sulfuric acid dimers in the binary (H<sub>2</sub>SO<sub>4</sub>–H<sub>2</sub>O) and ternary (H<sub>2</sub>SO<sub>4</sub>–H<sub>2</sub>O–NH<sub>3</sub>) system
Sulfuric acid is an important gas influencing atmospheric new particle formation (NPF). Both the binary (H<sub>2</sub>SO<sub>4</sub>–H<sub>2</sub>O) system and the ternary system involving ammonia (H<sub>2</sub>SO<sub>4</sub>–H<sub>2&...
| Main Authors: | , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Copernicus Publications
2015-09-01
|
| Series: | Atmospheric Chemistry and Physics |
| Online Access: | http://www.atmos-chem-phys.net/15/10701/2015/acp-15-10701-2015.pdf |
| id |
doaj-846a76561268477ab7186ecbb4852fa9 |
|---|---|
| record_format |
Article |
| collection |
DOAJ |
| language |
English |
| format |
Article |
| sources |
DOAJ |
| author |
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 G. Steiner A. Tomé G. Tsagkogeorgas P. E. Wagner D. Wimmer U. Baltensperger M. Kulmala D. R. Worsnop J. Curtius |
| spellingShingle |
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 G. Steiner A. Tomé G. Tsagkogeorgas P. E. Wagner D. Wimmer U. Baltensperger M. Kulmala D. R. Worsnop J. Curtius Thermodynamics of the formation of sulfuric acid dimers in the binary (H<sub>2</sub>SO<sub>4</sub>–H<sub>2</sub>O) and ternary (H<sub>2</sub>SO<sub>4</sub>–H<sub>2</sub>O–NH<sub>3</sub>) system Atmospheric Chemistry and Physics |
| author_facet |
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 G. Steiner A. Tomé G. Tsagkogeorgas P. E. Wagner D. Wimmer U. Baltensperger M. Kulmala D. R. Worsnop J. Curtius |
| author_sort |
A. Kürten |
| title |
Thermodynamics of the formation of sulfuric acid dimers in the binary (H<sub>2</sub>SO<sub>4</sub>–H<sub>2</sub>O) and ternary (H<sub>2</sub>SO<sub>4</sub>–H<sub>2</sub>O–NH<sub>3</sub>) system |
| title_short |
Thermodynamics of the formation of sulfuric acid dimers in the binary (H<sub>2</sub>SO<sub>4</sub>–H<sub>2</sub>O) and ternary (H<sub>2</sub>SO<sub>4</sub>–H<sub>2</sub>O–NH<sub>3</sub>) system |
| title_full |
Thermodynamics of the formation of sulfuric acid dimers in the binary (H<sub>2</sub>SO<sub>4</sub>–H<sub>2</sub>O) and ternary (H<sub>2</sub>SO<sub>4</sub>–H<sub>2</sub>O–NH<sub>3</sub>) system |
| title_fullStr |
Thermodynamics of the formation of sulfuric acid dimers in the binary (H<sub>2</sub>SO<sub>4</sub>–H<sub>2</sub>O) and ternary (H<sub>2</sub>SO<sub>4</sub>–H<sub>2</sub>O–NH<sub>3</sub>) system |
| title_full_unstemmed |
Thermodynamics of the formation of sulfuric acid dimers in the binary (H<sub>2</sub>SO<sub>4</sub>–H<sub>2</sub>O) and ternary (H<sub>2</sub>SO<sub>4</sub>–H<sub>2</sub>O–NH<sub>3</sub>) system |
| title_sort |
thermodynamics of the formation of sulfuric acid dimers in the binary (h<sub>2</sub>so<sub>4</sub>–h<sub>2</sub>o) and ternary (h<sub>2</sub>so<sub>4</sub>–h<sub>2</sub>o–nh<sub>3</sub>) system |
| publisher |
Copernicus Publications |
| series |
Atmospheric Chemistry and Physics |
| issn |
1680-7316 1680-7324 |
| publishDate |
2015-09-01 |
| description |
Sulfuric acid is an important gas influencing atmospheric new particle
formation (NPF). Both the binary (H<sub>2</sub>SO<sub>4</sub>–H<sub>2</sub>O) system and the
ternary system involving ammonia (H<sub>2</sub>SO<sub>4</sub>–H<sub>2</sub>O–NH<sub>3</sub>) 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<sub>2</sub>SO<sub>4</sub>·NH<sub>3</sub> 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 (d<i>H</i> and d<i>S</i>) of the H<sub>2</sub>SO<sub>4</sub>·NH<sub>3</sub> 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. |
| url |
http://www.atmos-chem-phys.net/15/10701/2015/acp-15-10701-2015.pdf |
| work_keys_str_mv |
AT akurten thermodynamicsoftheformationofsulfuricaciddimersinthebinaryhsub2subsosub4subhsub2suboandternaryhsub2subsosub4subhsub2subonhsub3subsystem AT smunch thermodynamicsoftheformationofsulfuricaciddimersinthebinaryhsub2subsosub4subhsub2suboandternaryhsub2subsosub4subhsub2subonhsub3subsystem AT lrondo thermodynamicsoftheformationofsulfuricaciddimersinthebinaryhsub2subsosub4subhsub2suboandternaryhsub2subsosub4subhsub2subonhsub3subsystem AT fbianchi thermodynamicsoftheformationofsulfuricaciddimersinthebinaryhsub2subsosub4subhsub2suboandternaryhsub2subsosub4subhsub2subonhsub3subsystem AT jduplissy thermodynamicsoftheformationofsulfuricaciddimersinthebinaryhsub2subsosub4subhsub2suboandternaryhsub2subsosub4subhsub2subonhsub3subsystem AT tjokinen thermodynamicsoftheformationofsulfuricaciddimersinthebinaryhsub2subsosub4subhsub2suboandternaryhsub2subsosub4subhsub2subonhsub3subsystem AT hjunninen thermodynamicsoftheformationofsulfuricaciddimersinthebinaryhsub2subsosub4subhsub2suboandternaryhsub2subsosub4subhsub2subonhsub3subsystem AT nsarnela thermodynamicsoftheformationofsulfuricaciddimersinthebinaryhsub2subsosub4subhsub2suboandternaryhsub2subsosub4subhsub2subonhsub3subsystem AT sschobesberger thermodynamicsoftheformationofsulfuricaciddimersinthebinaryhsub2subsosub4subhsub2suboandternaryhsub2subsosub4subhsub2subonhsub3subsystem AT msimon thermodynamicsoftheformationofsulfuricaciddimersinthebinaryhsub2subsosub4subhsub2suboandternaryhsub2subsosub4subhsub2subonhsub3subsystem AT msipila thermodynamicsoftheformationofsulfuricaciddimersinthebinaryhsub2subsosub4subhsub2suboandternaryhsub2subsosub4subhsub2subonhsub3subsystem AT jalmeida thermodynamicsoftheformationofsulfuricaciddimersinthebinaryhsub2subsosub4subhsub2suboandternaryhsub2subsosub4subhsub2subonhsub3subsystem AT aamorim thermodynamicsoftheformationofsulfuricaciddimersinthebinaryhsub2subsosub4subhsub2suboandternaryhsub2subsosub4subhsub2subonhsub3subsystem AT jdommen thermodynamicsoftheformationofsulfuricaciddimersinthebinaryhsub2subsosub4subhsub2suboandternaryhsub2subsosub4subhsub2subonhsub3subsystem AT nmdonahue thermodynamicsoftheformationofsulfuricaciddimersinthebinaryhsub2subsosub4subhsub2suboandternaryhsub2subsosub4subhsub2subonhsub3subsystem AT emdunne thermodynamicsoftheformationofsulfuricaciddimersinthebinaryhsub2subsosub4subhsub2suboandternaryhsub2subsosub4subhsub2subonhsub3subsystem AT rcflagan thermodynamicsoftheformationofsulfuricaciddimersinthebinaryhsub2subsosub4subhsub2suboandternaryhsub2subsosub4subhsub2subonhsub3subsystem AT afranchin thermodynamicsoftheformationofsulfuricaciddimersinthebinaryhsub2subsosub4subhsub2suboandternaryhsub2subsosub4subhsub2subonhsub3subsystem AT jkirkby thermodynamicsoftheformationofsulfuricaciddimersinthebinaryhsub2subsosub4subhsub2suboandternaryhsub2subsosub4subhsub2subonhsub3subsystem AT akupc thermodynamicsoftheformationofsulfuricaciddimersinthebinaryhsub2subsosub4subhsub2suboandternaryhsub2subsosub4subhsub2subonhsub3subsystem AT vmakhmutov thermodynamicsoftheformationofsulfuricaciddimersinthebinaryhsub2subsosub4subhsub2suboandternaryhsub2subsosub4subhsub2subonhsub3subsystem AT tpetaja thermodynamicsoftheformationofsulfuricaciddimersinthebinaryhsub2subsosub4subhsub2suboandternaryhsub2subsosub4subhsub2subonhsub3subsystem AT appraplan thermodynamicsoftheformationofsulfuricaciddimersinthebinaryhsub2subsosub4subhsub2suboandternaryhsub2subsosub4subhsub2subonhsub3subsystem AT friccobono thermodynamicsoftheformationofsulfuricaciddimersinthebinaryhsub2subsosub4subhsub2suboandternaryhsub2subsosub4subhsub2subonhsub3subsystem AT gsteiner thermodynamicsoftheformationofsulfuricaciddimersinthebinaryhsub2subsosub4subhsub2suboandternaryhsub2subsosub4subhsub2subonhsub3subsystem AT atome thermodynamicsoftheformationofsulfuricaciddimersinthebinaryhsub2subsosub4subhsub2suboandternaryhsub2subsosub4subhsub2subonhsub3subsystem AT gtsagkogeorgas thermodynamicsoftheformationofsulfuricaciddimersinthebinaryhsub2subsosub4subhsub2suboandternaryhsub2subsosub4subhsub2subonhsub3subsystem AT pewagner thermodynamicsoftheformationofsulfuricaciddimersinthebinaryhsub2subsosub4subhsub2suboandternaryhsub2subsosub4subhsub2subonhsub3subsystem AT dwimmer thermodynamicsoftheformationofsulfuricaciddimersinthebinaryhsub2subsosub4subhsub2suboandternaryhsub2subsosub4subhsub2subonhsub3subsystem AT ubaltensperger thermodynamicsoftheformationofsulfuricaciddimersinthebinaryhsub2subsosub4subhsub2suboandternaryhsub2subsosub4subhsub2subonhsub3subsystem AT mkulmala thermodynamicsoftheformationofsulfuricaciddimersinthebinaryhsub2subsosub4subhsub2suboandternaryhsub2subsosub4subhsub2subonhsub3subsystem AT drworsnop thermodynamicsoftheformationofsulfuricaciddimersinthebinaryhsub2subsosub4subhsub2suboandternaryhsub2subsosub4subhsub2subonhsub3subsystem AT jcurtius thermodynamicsoftheformationofsulfuricaciddimersinthebinaryhsub2subsosub4subhsub2suboandternaryhsub2subsosub4subhsub2subonhsub3subsystem |
| _version_ |
1725212620541132800 |
| spelling |
doaj-846a76561268477ab7186ecbb4852fa92020-11-25T01:00:40ZengCopernicus PublicationsAtmospheric Chemistry and Physics1680-73161680-73242015-09-011518107011072110.5194/acp-15-10701-2015Thermodynamics of the formation of sulfuric acid dimers in the binary (H<sub>2</sub>SO<sub>4</sub>–H<sub>2</sub>O) and ternary (H<sub>2</sub>SO<sub>4</sub>–H<sub>2</sub>O–NH<sub>3</sub>) systemA. Kürten0S. Münch1L. Rondo2F. Bianchi3J. Duplissy4T. Jokinen5H. Junninen6N. Sarnela7S. Schobesberger8M. Simon9M. Sipilä10J. Almeida11A. Amorim12J. Dommen13N. M. Donahue14E. M. Dunne15R. C. Flagan16A. Franchin17J. Kirkby18A. Kupc19V. Makhmutov20T. Petäjä21A. P. Praplan22F. Riccobono23G. Steiner24A. Tomé25G. Tsagkogeorgas26P. E. Wagner27D. Wimmer28U. Baltensperger29M. Kulmala30D. R. Worsnop31J. Curtius32Institute for Atmospheric and Environmental Sciences, Goethe University Frankfurt am Main, Frankfurt am Main, GermanyInstitute for Atmospheric and Environmental Sciences, Goethe University Frankfurt am Main, Frankfurt am Main, GermanyInstitute for Atmospheric and Environmental Sciences, Goethe University Frankfurt am Main, Frankfurt am Main, GermanyLaboratory of Atmospheric Chemistry, Paul Scherrer Institute, Villigen, SwitzerlandCERN (European Organization for Nuclear Research), Geneva, SwitzerlandDepartment of Physics, University of Helsinki, Helsinki, FinlandDepartment of Physics, University of Helsinki, Helsinki, FinlandDepartment of Physics, University of Helsinki, Helsinki, FinlandDepartment of Physics, University of Helsinki, Helsinki, FinlandInstitute for Atmospheric and Environmental Sciences, Goethe University Frankfurt am Main, Frankfurt am Main, GermanyDepartment of Physics, University of Helsinki, Helsinki, FinlandCERN (European Organization for Nuclear Research), Geneva, SwitzerlandLaboratory for Systems, Instrumentation, and Modeling in Science and Technology for Space and the Environment (SIM), University of Lisbon and University of Beira Interior, Lisbon, PortugalLaboratory of Atmospheric Chemistry, Paul Scherrer Institute, Villigen, SwitzerlandCenter for Atmospheric Particle Studies, Carnegie Mellon University, Pittsburgh, USASchool of Earth and Environment, University of Leeds, Leeds, UKDivision of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, USADepartment of Physics, University of Helsinki, Helsinki, FinlandInstitute for Atmospheric and Environmental Sciences, Goethe University Frankfurt am Main, Frankfurt am Main, GermanyAerosol Physics and Environmental Physics, University of Vienna, Vienna, AustriaSolar and Cosmic Ray Research Laboratory, Lebedev Physical Institute, Moscow, RussiaDepartment of Physics, University of Helsinki, Helsinki, FinlandLaboratory of Atmospheric Chemistry, Paul Scherrer Institute, Villigen, SwitzerlandLaboratory of Atmospheric Chemistry, Paul Scherrer Institute, Villigen, SwitzerlandDepartment of Physics, University of Helsinki, Helsinki, FinlandLaboratory for Systems, Instrumentation, and Modeling in Science and Technology for Space and the Environment (SIM), University of Lisbon and University of Beira Interior, Lisbon, PortugalLeibniz Institute for Tropospheric Research, Leipzig, GermanyAerosol Physics and Environmental Physics, University of Vienna, Vienna, AustriaInstitute for Atmospheric and Environmental Sciences, Goethe University Frankfurt am Main, Frankfurt am Main, GermanyLaboratory of Atmospheric Chemistry, Paul Scherrer Institute, Villigen, SwitzerlandDepartment of Physics, University of Helsinki, Helsinki, FinlandDepartment of Physics, University of Helsinki, Helsinki, FinlandInstitute for Atmospheric and Environmental Sciences, Goethe University Frankfurt am Main, Frankfurt am Main, GermanySulfuric acid is an important gas influencing atmospheric new particle formation (NPF). Both the binary (H<sub>2</sub>SO<sub>4</sub>–H<sub>2</sub>O) system and the ternary system involving ammonia (H<sub>2</sub>SO<sub>4</sub>–H<sub>2</sub>O–NH<sub>3</sub>) 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<sub>2</sub>SO<sub>4</sub>·NH<sub>3</sub> 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 (d<i>H</i> and d<i>S</i>) of the H<sub>2</sub>SO<sub>4</sub>·NH<sub>3</sub> 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.http://www.atmos-chem-phys.net/15/10701/2015/acp-15-10701-2015.pdf |