Pressure-induced transformations in LiCl–H2O at 77 K
- Autores
- Ruiz, G. N.; Bove, L. E.; Corti, Horacio Roberto; Loerting, T.
- Año de publicación
- 2014
- Idioma
- inglés
- Tipo de recurso
- artículo
- Estado
- versión publicada
- Descripción
- A systematic study of the properties of high-density amorphous ice (HDA) in the presence of increasing amounts of salt is missing, especially because it is challenging to avoid ice crystallization upon cooling the pressurized liquid. In order to be able to study HDA also in the presence of small amounts of salt, we have investigated the transformation behaviour of quenched aqueous LiCl solutions (mole fraction x < 0.25) upon pressurization in a piston-cylinder setup at 77 K. The sample properties were characterized by in situ dilatometry under high pressure conditions and after recovery by ex situ powder X-ray diffraction (XRD) and differential scanning calorimetry (DSC) at ambient pressure. Two regimes can be identified, with a rather sharp switch at about x = 0.12. At x < 0.12 the samples show the phenomenology also known for pure water samples. They are composed mainly of hexagonal ice (Ih) and experience pressure-induced amorphization to HDA at P > 1 GPa. The observed densification is consistent with the idea that a freeze concentrated LiCl solution of x = 0.14 (R = 6) segregates, which transforms to the glassy state upon cooling, and that the densification is only due to the Ih → HDA transition. Also the XRD patterns and DSC scans are almost unaffected by the presence of the segregated glassy LiCl solution. Upon heating at ambient pressure HDA experiences the polyamorphic transition to low-density amorphous ice (LDA) at ∼120 K, even at x ∼ 0.10. Based on the latent heat evolved in the transition we suggest that almost all water in the sample transforms to an LDA-like state, even the water in the vicinity of the ions. The glassy LiCl solution acts as a spectator that does not shift the transformation temperature significantly and experiences a glass-to-liquid transition at ∼140 K prior to the crystallization to cubic ice. By contrast, at x > 0.12 the phenomenology completely changes and is now dominated by the salt. Hexagonal ice no longer forms upon quenching the LiCl solution, but instead LDA forms. A broad pressure-induced transformation at >0.6 GPa can be attributed to the densification of LDA, the glassy LiCl solution and/or glassy hydrates.
Fil: Ruiz, G. N.. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Innsbruck; Austria
Fil: Bove, L. E.. Universite Pierre et Marie Curie; Francia. Ecole Polytechnique Federale de Lausanne; Suiza
Fil: Corti, Horacio Roberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Comisión Nacional de Energía Atómica; Argentina
Fil: Loerting, T.. Universidad de Innsbruck; Austria - Materia
-
LiCl
Presión
Agua
Transformación - Nivel de accesibilidad
- acceso abierto
- Condiciones de uso
- https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
- Repositorio
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/35800
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Pressure-induced transformations in LiCl–H2O at 77 KRuiz, G. N.Bove, L. E.Corti, Horacio RobertoLoerting, T.LiClPresiónAguaTransformaciónhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1A systematic study of the properties of high-density amorphous ice (HDA) in the presence of increasing amounts of salt is missing, especially because it is challenging to avoid ice crystallization upon cooling the pressurized liquid. In order to be able to study HDA also in the presence of small amounts of salt, we have investigated the transformation behaviour of quenched aqueous LiCl solutions (mole fraction x < 0.25) upon pressurization in a piston-cylinder setup at 77 K. The sample properties were characterized by in situ dilatometry under high pressure conditions and after recovery by ex situ powder X-ray diffraction (XRD) and differential scanning calorimetry (DSC) at ambient pressure. Two regimes can be identified, with a rather sharp switch at about x = 0.12. At x < 0.12 the samples show the phenomenology also known for pure water samples. They are composed mainly of hexagonal ice (Ih) and experience pressure-induced amorphization to HDA at P > 1 GPa. The observed densification is consistent with the idea that a freeze concentrated LiCl solution of x = 0.14 (R = 6) segregates, which transforms to the glassy state upon cooling, and that the densification is only due to the Ih → HDA transition. Also the XRD patterns and DSC scans are almost unaffected by the presence of the segregated glassy LiCl solution. Upon heating at ambient pressure HDA experiences the polyamorphic transition to low-density amorphous ice (LDA) at ∼120 K, even at x ∼ 0.10. Based on the latent heat evolved in the transition we suggest that almost all water in the sample transforms to an LDA-like state, even the water in the vicinity of the ions. The glassy LiCl solution acts as a spectator that does not shift the transformation temperature significantly and experiences a glass-to-liquid transition at ∼140 K prior to the crystallization to cubic ice. By contrast, at x > 0.12 the phenomenology completely changes and is now dominated by the salt. Hexagonal ice no longer forms upon quenching the LiCl solution, but instead LDA forms. A broad pressure-induced transformation at >0.6 GPa can be attributed to the densification of LDA, the glassy LiCl solution and/or glassy hydrates.Fil: Ruiz, G. N.. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Innsbruck; AustriaFil: Bove, L. E.. Universite Pierre et Marie Curie; Francia. Ecole Polytechnique Federale de Lausanne; SuizaFil: Corti, Horacio Roberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Comisión Nacional de Energía Atómica; ArgentinaFil: Loerting, T.. Universidad de Innsbruck; AustriaRoyal Society of Chemistry2014-07info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/35800Ruiz, G. N.; Bove, L. E.; Corti, Horacio Roberto; Loerting, T.; Pressure-induced transformations in LiCl–H2O at 77 K; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 16; 34; 7-2014; 18553-185621463-9076CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1039/c4cp01786binfo:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/Content/ArticleLanding/2014/CP/C4CP01786Binfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:59:48Zoai:ri.conicet.gov.ar:11336/35800instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 09:59:48.493CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse |
dc.title.none.fl_str_mv |
Pressure-induced transformations in LiCl–H2O at 77 K |
title |
Pressure-induced transformations in LiCl–H2O at 77 K |
spellingShingle |
Pressure-induced transformations in LiCl–H2O at 77 K Ruiz, G. N. LiCl Presión Agua Transformación |
title_short |
Pressure-induced transformations in LiCl–H2O at 77 K |
title_full |
Pressure-induced transformations in LiCl–H2O at 77 K |
title_fullStr |
Pressure-induced transformations in LiCl–H2O at 77 K |
title_full_unstemmed |
Pressure-induced transformations in LiCl–H2O at 77 K |
title_sort |
Pressure-induced transformations in LiCl–H2O at 77 K |
dc.creator.none.fl_str_mv |
Ruiz, G. N. Bove, L. E. Corti, Horacio Roberto Loerting, T. |
author |
Ruiz, G. N. |
author_facet |
Ruiz, G. N. Bove, L. E. Corti, Horacio Roberto Loerting, T. |
author_role |
author |
author2 |
Bove, L. E. Corti, Horacio Roberto Loerting, T. |
author2_role |
author author author |
dc.subject.none.fl_str_mv |
LiCl Presión Agua Transformación |
topic |
LiCl Presión Agua Transformación |
purl_subject.fl_str_mv |
https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
dc.description.none.fl_txt_mv |
A systematic study of the properties of high-density amorphous ice (HDA) in the presence of increasing amounts of salt is missing, especially because it is challenging to avoid ice crystallization upon cooling the pressurized liquid. In order to be able to study HDA also in the presence of small amounts of salt, we have investigated the transformation behaviour of quenched aqueous LiCl solutions (mole fraction x < 0.25) upon pressurization in a piston-cylinder setup at 77 K. The sample properties were characterized by in situ dilatometry under high pressure conditions and after recovery by ex situ powder X-ray diffraction (XRD) and differential scanning calorimetry (DSC) at ambient pressure. Two regimes can be identified, with a rather sharp switch at about x = 0.12. At x < 0.12 the samples show the phenomenology also known for pure water samples. They are composed mainly of hexagonal ice (Ih) and experience pressure-induced amorphization to HDA at P > 1 GPa. The observed densification is consistent with the idea that a freeze concentrated LiCl solution of x = 0.14 (R = 6) segregates, which transforms to the glassy state upon cooling, and that the densification is only due to the Ih → HDA transition. Also the XRD patterns and DSC scans are almost unaffected by the presence of the segregated glassy LiCl solution. Upon heating at ambient pressure HDA experiences the polyamorphic transition to low-density amorphous ice (LDA) at ∼120 K, even at x ∼ 0.10. Based on the latent heat evolved in the transition we suggest that almost all water in the sample transforms to an LDA-like state, even the water in the vicinity of the ions. The glassy LiCl solution acts as a spectator that does not shift the transformation temperature significantly and experiences a glass-to-liquid transition at ∼140 K prior to the crystallization to cubic ice. By contrast, at x > 0.12 the phenomenology completely changes and is now dominated by the salt. Hexagonal ice no longer forms upon quenching the LiCl solution, but instead LDA forms. A broad pressure-induced transformation at >0.6 GPa can be attributed to the densification of LDA, the glassy LiCl solution and/or glassy hydrates. Fil: Ruiz, G. N.. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Innsbruck; Austria Fil: Bove, L. E.. Universite Pierre et Marie Curie; Francia. Ecole Polytechnique Federale de Lausanne; Suiza Fil: Corti, Horacio Roberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Comisión Nacional de Energía Atómica; Argentina Fil: Loerting, T.. Universidad de Innsbruck; Austria |
description |
A systematic study of the properties of high-density amorphous ice (HDA) in the presence of increasing amounts of salt is missing, especially because it is challenging to avoid ice crystallization upon cooling the pressurized liquid. In order to be able to study HDA also in the presence of small amounts of salt, we have investigated the transformation behaviour of quenched aqueous LiCl solutions (mole fraction x < 0.25) upon pressurization in a piston-cylinder setup at 77 K. The sample properties were characterized by in situ dilatometry under high pressure conditions and after recovery by ex situ powder X-ray diffraction (XRD) and differential scanning calorimetry (DSC) at ambient pressure. Two regimes can be identified, with a rather sharp switch at about x = 0.12. At x < 0.12 the samples show the phenomenology also known for pure water samples. They are composed mainly of hexagonal ice (Ih) and experience pressure-induced amorphization to HDA at P > 1 GPa. The observed densification is consistent with the idea that a freeze concentrated LiCl solution of x = 0.14 (R = 6) segregates, which transforms to the glassy state upon cooling, and that the densification is only due to the Ih → HDA transition. Also the XRD patterns and DSC scans are almost unaffected by the presence of the segregated glassy LiCl solution. Upon heating at ambient pressure HDA experiences the polyamorphic transition to low-density amorphous ice (LDA) at ∼120 K, even at x ∼ 0.10. Based on the latent heat evolved in the transition we suggest that almost all water in the sample transforms to an LDA-like state, even the water in the vicinity of the ions. The glassy LiCl solution acts as a spectator that does not shift the transformation temperature significantly and experiences a glass-to-liquid transition at ∼140 K prior to the crystallization to cubic ice. By contrast, at x > 0.12 the phenomenology completely changes and is now dominated by the salt. Hexagonal ice no longer forms upon quenching the LiCl solution, but instead LDA forms. A broad pressure-induced transformation at >0.6 GPa can be attributed to the densification of LDA, the glassy LiCl solution and/or glassy hydrates. |
publishDate |
2014 |
dc.date.none.fl_str_mv |
2014-07 |
dc.type.none.fl_str_mv |
info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion http://purl.org/coar/resource_type/c_6501 info:ar-repo/semantics/articulo |
format |
article |
status_str |
publishedVersion |
dc.identifier.none.fl_str_mv |
http://hdl.handle.net/11336/35800 Ruiz, G. N.; Bove, L. E.; Corti, Horacio Roberto; Loerting, T.; Pressure-induced transformations in LiCl–H2O at 77 K; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 16; 34; 7-2014; 18553-18562 1463-9076 CONICET Digital CONICET |
url |
http://hdl.handle.net/11336/35800 |
identifier_str_mv |
Ruiz, G. N.; Bove, L. E.; Corti, Horacio Roberto; Loerting, T.; Pressure-induced transformations in LiCl–H2O at 77 K; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 16; 34; 7-2014; 18553-18562 1463-9076 CONICET Digital CONICET |
dc.language.none.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
info:eu-repo/semantics/altIdentifier/doi/10.1039/c4cp01786b info:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/Content/ArticleLanding/2014/CP/C4CP01786B |
dc.rights.none.fl_str_mv |
info:eu-repo/semantics/openAccess https://creativecommons.org/licenses/by-nc-sa/2.5/ar/ |
eu_rights_str_mv |
openAccess |
rights_invalid_str_mv |
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/ |
dc.format.none.fl_str_mv |
application/pdf application/pdf application/pdf |
dc.publisher.none.fl_str_mv |
Royal Society of Chemistry |
publisher.none.fl_str_mv |
Royal Society of Chemistry |
dc.source.none.fl_str_mv |
reponame:CONICET Digital (CONICET) instname:Consejo Nacional de Investigaciones Científicas y Técnicas |
reponame_str |
CONICET Digital (CONICET) |
collection |
CONICET Digital (CONICET) |
instname_str |
Consejo Nacional de Investigaciones Científicas y Técnicas |
repository.name.fl_str_mv |
CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas |
repository.mail.fl_str_mv |
dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar |
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1844613771915427840 |
score |
13.070432 |