Chemical equilibria of aqueous ammonium–carboxylate systems in aqueous bulk, close to and at the water–air interface
Previous studies have shown that the water–air interface and a number of water molecule layers just below it, the surface region, have significantly different physico-chemical properties, such as lower relative permittivity and density, than bulk water. The properties in the surface region of water...
- Autores:
-
Topel, Önder
Bajnóczi, Éva G.
Werner, Josephina
Björneholm, Olle
Persson, Ingmar
Salamnca Blanco, Yina
- Tipo de recurso:
- Fecha de publicación:
- 2019
- Institución:
- Universidad El Bosque
- Repositorio:
- Repositorio U. El Bosque
- Idioma:
- eng
- OAI Identifier:
- oai:repositorio.unbosque.edu.co:20.500.12495/1715
- Palabra clave:
- Agua - Composición
Rayos X
Ácidos carboxílicos
- Rights
- License
- Attribution 4.0 International
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dc.title.spa.fl_str_mv |
Chemical equilibria of aqueous ammonium–carboxylate systems in aqueous bulk, close to and at the water–air interface |
title |
Chemical equilibria of aqueous ammonium–carboxylate systems in aqueous bulk, close to and at the water–air interface |
spellingShingle |
Chemical equilibria of aqueous ammonium–carboxylate systems in aqueous bulk, close to and at the water–air interface Agua - Composición Rayos X Ácidos carboxílicos |
title_short |
Chemical equilibria of aqueous ammonium–carboxylate systems in aqueous bulk, close to and at the water–air interface |
title_full |
Chemical equilibria of aqueous ammonium–carboxylate systems in aqueous bulk, close to and at the water–air interface |
title_fullStr |
Chemical equilibria of aqueous ammonium–carboxylate systems in aqueous bulk, close to and at the water–air interface |
title_full_unstemmed |
Chemical equilibria of aqueous ammonium–carboxylate systems in aqueous bulk, close to and at the water–air interface |
title_sort |
Chemical equilibria of aqueous ammonium–carboxylate systems in aqueous bulk, close to and at the water–air interface |
dc.creator.fl_str_mv |
Topel, Önder Bajnóczi, Éva G. Werner, Josephina Björneholm, Olle Persson, Ingmar Salamnca Blanco, Yina |
dc.contributor.author.none.fl_str_mv |
Topel, Önder Bajnóczi, Éva G. Werner, Josephina Björneholm, Olle Persson, Ingmar Salamnca Blanco, Yina |
dc.contributor.orcid.none.fl_str_mv |
Salamnca Blanco, Yina [0000-0002-4580-4622] |
dc.subject.armarc.spa.fl_str_mv |
Agua - Composición Rayos X Ácidos carboxílicos |
topic |
Agua - Composición Rayos X Ácidos carboxílicos |
description |
Previous studies have shown that the water–air interface and a number of water molecule layers just below it, the surface region, have significantly different physico-chemical properties, such as lower relative permittivity and density, than bulk water. The properties in the surface region of water favor weakly hydrated species as neutral molecules, while ions requiring strong hydration and shielding of their charge are disfavored. In this study the equilibria NH4+(aq) + RCOO−(aq) ⇌ NH3(aq) + RCOOH(aq) are investigated for R = CnH2n+1, n = 0–8, as open systems, where ammonia and small carboxylic acids in the gas phase above the water surface are removed from the system by a gentle controlled flow of nitrogen to mimic the transport of volatile compounds from water droplets into air. It is shown that this non-equilibrium transport of chemicals can be sufficiently large to cause a change of the chemical content of the aqueous bulk. Furthermore, X-ray photoelectron spectroscopy (XPS) has been used to determine the relative concentration of alkyl carboxylic acids and their conjugated alkyl carboxylates in aqueous surfaces using a micro-jet. These studies confirm that neutral alkyl carboxylic acids are accumulated in the surface region, while charged species, as alkyl carboxylates, are depleted. The XPS studies show also that the hydrophobic alkyl chains are oriented upwards into regions with lower relative permittivity and density, thus perpendicular to the aqueous surface. These combined results show that there are several chemical equilibria between the aqueous bulk and the surface region. The analytical studies show that the release of mainly ammonia is dependent on its concentration in the surface region, as long as the solubility of the carboxylic acid in the surface region is sufficiently high to avoid a precipitation in/on the water–air interface. However, for n-octyl- and n-nonylcarboxylic acid the solubility is sufficiently low to cause precipitation. The combined analytical and surface speciation studies in this work show that the equilibria involving the surface region are fast. The results from this study increase the knowledge about the distribution of chemical species in the surface region at and close to the water–air interface, and the transport of chemicals from water to air in open systems. |
publishDate |
2019 |
dc.date.accessioned.none.fl_str_mv |
2019-09-16T20:34:39Z |
dc.date.available.none.fl_str_mv |
2019-09-16T20:34:39Z |
dc.date.issued.none.fl_str_mv |
2019 |
dc.type.spa.fl_str_mv |
article |
dc.type.coarversion.fl_str_mv |
http://purl.org/coar/version/c_970fb48d4fbd8a85 |
dc.type.coar.fl_str_mv |
http://purl.org/coar/resource_type/c_6501 |
dc.type.local.spa.fl_str_mv |
artículo |
dc.identifier.issn.none.fl_str_mv |
1463-9076 |
dc.identifier.uri.none.fl_str_mv |
http://hdl.handle.net/20.500.12495/1715 |
dc.identifier.doi.none.fl_str_mv |
http://dx.doi.org/10.1039/C9CP02449B |
dc.identifier.instname.spa.fl_str_mv |
instname:Universidad El Bosque |
dc.identifier.reponame.spa.fl_str_mv |
reponame:Repositorio Institucional Universidad El Bosque |
dc.identifier.repourl.none.fl_str_mv |
repourl:https://repositorio.unbosque.edu.co |
identifier_str_mv |
1463-9076 instname:Universidad El Bosque reponame:Repositorio Institucional Universidad El Bosque repourl:https://repositorio.unbosque.edu.co |
url |
http://hdl.handle.net/20.500.12495/1715 http://dx.doi.org/10.1039/C9CP02449B |
dc.language.iso.none.fl_str_mv |
eng |
language |
eng |
dc.relation.ispartofseries.spa.fl_str_mv |
Physical Chemistry Chemical Physics, 1463-9076, Vol. 21, 2019, p. 12434-12445 |
dc.relation.uri.none.fl_str_mv |
https://pubs.rsc.org/en/content/articlelanding/2019/cp/c9cp02449b#!divAbstract |
dc.rights.*.fl_str_mv |
Attribution 4.0 International |
dc.rights.coar.fl_str_mv |
http://purl.org/coar/access_right/c_abf2 |
dc.rights.uri.*.fl_str_mv |
http://creativecommons.org/licenses/by/4.0/ |
dc.rights.local.spa.fl_str_mv |
Acceso abierto |
dc.rights.accessrights.none.fl_str_mv |
http://purl.org/coar/access_right/c_abf445 |
dc.rights.creativecommons.none.fl_str_mv |
2019 |
rights_invalid_str_mv |
Attribution 4.0 International http://creativecommons.org/licenses/by/4.0/ Acceso abierto http://purl.org/coar/access_right/c_abf445 2019 http://purl.org/coar/access_right/c_abf2 |
dc.format.mimetype.none.fl_str_mv |
application/pdf |
dc.publisher.spa.fl_str_mv |
Royal Society of Chemistry |
dc.publisher.journal.spa.fl_str_mv |
Physical Chemistry Chemical Physics |
institution |
Universidad El Bosque |
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Topel, ÖnderBajnóczi, Éva G.Werner, JosephinaBjörneholm, OllePersson, IngmarSalamnca Blanco, YinaSalamnca Blanco, Yina [0000-0002-4580-4622]2019-09-16T20:34:39Z2019-09-16T20:34:39Z20191463-9076http://hdl.handle.net/20.500.12495/1715http://dx.doi.org/10.1039/C9CP02449Binstname:Universidad El Bosquereponame:Repositorio Institucional Universidad El Bosquerepourl:https://repositorio.unbosque.edu.coapplication/pdfengRoyal Society of ChemistryPhysical Chemistry Chemical PhysicsPhysical Chemistry Chemical Physics, 1463-9076, Vol. 21, 2019, p. 12434-12445https://pubs.rsc.org/en/content/articlelanding/2019/cp/c9cp02449b#!divAbstractAttribution 4.0 Internationalhttp://creativecommons.org/licenses/by/4.0/Acceso abiertohttp://purl.org/coar/access_right/c_abf4452019http://purl.org/coar/access_right/c_abf2Chemical equilibria of aqueous ammonium–carboxylate systems in aqueous bulk, close to and at the water–air interfacearticleartículohttp://purl.org/coar/version/c_970fb48d4fbd8a85http://purl.org/coar/resource_type/c_6501Agua - ComposiciónRayos XÁcidos carboxílicosPrevious studies have shown that the water–air interface and a number of water molecule layers just below it, the surface region, have significantly different physico-chemical properties, such as lower relative permittivity and density, than bulk water. The properties in the surface region of water favor weakly hydrated species as neutral molecules, while ions requiring strong hydration and shielding of their charge are disfavored. In this study the equilibria NH4+(aq) + RCOO−(aq) ⇌ NH3(aq) + RCOOH(aq) are investigated for R = CnH2n+1, n = 0–8, as open systems, where ammonia and small carboxylic acids in the gas phase above the water surface are removed from the system by a gentle controlled flow of nitrogen to mimic the transport of volatile compounds from water droplets into air. It is shown that this non-equilibrium transport of chemicals can be sufficiently large to cause a change of the chemical content of the aqueous bulk. Furthermore, X-ray photoelectron spectroscopy (XPS) has been used to determine the relative concentration of alkyl carboxylic acids and their conjugated alkyl carboxylates in aqueous surfaces using a micro-jet. These studies confirm that neutral alkyl carboxylic acids are accumulated in the surface region, while charged species, as alkyl carboxylates, are depleted. The XPS studies show also that the hydrophobic alkyl chains are oriented upwards into regions with lower relative permittivity and density, thus perpendicular to the aqueous surface. These combined results show that there are several chemical equilibria between the aqueous bulk and the surface region. The analytical studies show that the release of mainly ammonia is dependent on its concentration in the surface region, as long as the solubility of the carboxylic acid in the surface region is sufficiently high to avoid a precipitation in/on the water–air interface. However, for n-octyl- and n-nonylcarboxylic acid the solubility is sufficiently low to cause precipitation. The combined analytical and surface speciation studies in this work show that the equilibria involving the surface region are fast. The results from this study increase the knowledge about the distribution of chemical species in the surface region at and close to the water–air interface, and the transport of chemicals from water to air in open systems.ORIGINALBlanco Y.S., Topel Ö., Bajnóczi É.G., Werner J., Björneholm O., Persson I._2019.pdfBlanco Y.S., Topel Ö., Bajnóczi É.G., Werner J., Björneholm O., Persson I._2019.pdfapplication/pdf3219302https://repositorio.unbosque.edu.co/bitstreams/05ea92e1-0bb5-4a13-9592-a7a9df04f626/download921945c1788e587db6eeb086bcc297fcMD51CC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; charset=utf-8908https://repositorio.unbosque.edu.co/bitstreams/4641e82d-0c5e-49e6-ad52-a994627179ca/download0175ea4a2d4caec4bbcc37e300941108MD52LICENSElicense.txtlicense.txttext/plain; charset=utf-81748https://repositorio.unbosque.edu.co/bitstreams/cab2ccea-9159-43bb-a4ab-062af9f52794/download8a4605be74aa9ea9d79846c1fba20a33MD53THUMBNAILBlanco Y.S., Topel Ö., Bajnóczi É.G., Werner J., Björneholm O., Persson I._2019.pdf.jpgBlanco Y.S., Topel Ö., Bajnóczi É.G., Werner J., Björneholm O., Persson I._2019.pdf.jpgIM Thumbnailimage/jpeg13372https://repositorio.unbosque.edu.co/bitstreams/50c1af4c-cffb-4785-a0e0-fd7f3498c6ff/download66769b186b43f209ad4c283f60a7f18eMD54TEXTBlanco Y.S., Topel Ö., Bajnóczi É.G., Werner J., Björneholm O., Persson I._2019.pdf.txtBlanco Y.S., Topel Ö., Bajnóczi É.G., Werner J., Björneholm O., Persson I._2019.pdf.txtExtracted texttext/plain74448https://repositorio.unbosque.edu.co/bitstreams/e67fa4c7-4dec-4d33-aab0-a849175f62e6/download6224ce401ce1dd9ea5cd926cd75cdec0MD5520.500.12495/1715oai:repositorio.unbosque.edu.co:20.500.12495/17152024-02-07 09:11:03.396http://creativecommons.org/licenses/by/4.0/Attribution 4.0 Internationalopen.accesshttps://repositorio.unbosque.edu.coRepositorio Institucional Universidad El Bosquebibliotecas@biteca.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 |