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...

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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
Acceso en línea:
http://hdl.handle.net/20.500.12495/1715
http://dx.doi.org/10.1039/C9CP02449B
Palabra clave:
Agua - Composición
Rayos X
Ácidos carboxílicos
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License
Attribution 4.0 International
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network_name_str Repositorio U. El Bosque
repository_id_str
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
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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
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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
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dc.rights.uri.*.fl_str_mv http://creativecommons.org/licenses/by/4.0/
dc.rights.local.spa.fl_str_mv Acceso abierto
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dc.rights.creativecommons.none.fl_str_mv 2019
rights_invalid_str_mv Attribution 4.0 International
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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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spelling 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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