Heat capacity and glass transition in P2O5-H 2O solutions: Support for Mishima's conjecture on solvent water at low temperature

Autores
Corti, Horacio Roberto; Nores Pondal, Federico Jose; Angell, C. Austen
Año de publicación
2011
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The P2O5-water system has the widest range of continuously glass-forming compositions known for any glassformer + water binary system. Despite the great range of structures explored by the glasses and liquids in this system, the glass transition temperature (Tg) itself varies in a simple monotonic fashion. However the values of Tg reported in the literature show wide disagreement, linked to the different methods of measurement employed. In this work we use differential scanning calorimetry (DSC) to obtain both Tg itself and the jump in heat capacity that occurs as the metastable equilibrium of the supercooled liquid relieves the non-ergodic glassy state. Our study covers the molar ratio range of H2O/P2O5 from 1.5 to 14 (corresponding to the mass fraction of P2O5 between 0.36 and 0.84), which includes the compositions corresponding to pyrophosphoric acid (H 4P2O7) and orthophosphoric acid (H 3PO4). The theoretical model of Couchman and Karasz predicts very well the glass transition temperatures of the P2O 5-H2O system over the whole composition range if the relatively large heat capacity change associated with water in aqueous solutions at the glass transition temperature is adopted, instead of the vanishingly small value observed for vapor deposited or hyperquenched pure water. Therefore, solvent water in this ambient pressure P2O5-H 2O system behaves like a different liquid, more closely resembling a high-density liquid (HDL) polyamorph, as suggested by Mishima for electrolytes at high pressures.
Fil: Corti, Horacio Roberto. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina. 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
Fil: Nores Pondal, Federico Jose. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Angell, C. Austen. Arizona State University; Estados Unidos
Materia
Phosphoric acid
Aqueous solutions
Glass transition
Supercooled
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/193412
Acceder
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network_name_str CONICET Digital (CONICET)
spelling Heat capacity and glass transition in P2O5-H 2O solutions: Support for Mishima's conjecture on solvent water at low temperatureCorti, Horacio RobertoNores Pondal, Federico JoseAngell, C. AustenPhosphoric acidAqueous solutionsGlass transitionSupercooledhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The P2O5-water system has the widest range of continuously glass-forming compositions known for any glassformer + water binary system. Despite the great range of structures explored by the glasses and liquids in this system, the glass transition temperature (Tg) itself varies in a simple monotonic fashion. However the values of Tg reported in the literature show wide disagreement, linked to the different methods of measurement employed. In this work we use differential scanning calorimetry (DSC) to obtain both Tg itself and the jump in heat capacity that occurs as the metastable equilibrium of the supercooled liquid relieves the non-ergodic glassy state. Our study covers the molar ratio range of H2O/P2O5 from 1.5 to 14 (corresponding to the mass fraction of P2O5 between 0.36 and 0.84), which includes the compositions corresponding to pyrophosphoric acid (H 4P2O7) and orthophosphoric acid (H 3PO4). The theoretical model of Couchman and Karasz predicts very well the glass transition temperatures of the P2O 5-H2O system over the whole composition range if the relatively large heat capacity change associated with water in aqueous solutions at the glass transition temperature is adopted, instead of the vanishingly small value observed for vapor deposited or hyperquenched pure water. Therefore, solvent water in this ambient pressure P2O5-H 2O system behaves like a different liquid, more closely resembling a high-density liquid (HDL) polyamorph, as suggested by Mishima for electrolytes at high pressures.Fil: Corti, Horacio Roberto. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina. 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; ArgentinaFil: Nores Pondal, Federico Jose. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Angell, C. Austen. Arizona State University; Estados UnidosRoyal Society of Chemistry2011-09info: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/11336/193412Corti, Horacio Roberto; Nores Pondal, Federico Jose; Angell, C. Austen; Heat capacity and glass transition in P2O5-H 2O solutions: Support for Mishima's conjecture on solvent water at low temperature; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 13; 44; 9-2011; 19741-197481463-9076CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1039/C1CP22185Jinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:20:34Zoai:ri.conicet.gov.ar:11336/193412instacron: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 10:20:35.051CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Heat capacity and glass transition in P2O5-H 2O solutions: Support for Mishima's conjecture on solvent water at low temperature
title Heat capacity and glass transition in P2O5-H 2O solutions: Support for Mishima's conjecture on solvent water at low temperature
spellingShingle Heat capacity and glass transition in P2O5-H 2O solutions: Support for Mishima's conjecture on solvent water at low temperature
Corti, Horacio Roberto
Phosphoric acid
Aqueous solutions
Glass transition
Supercooled
title_short Heat capacity and glass transition in P2O5-H 2O solutions: Support for Mishima's conjecture on solvent water at low temperature
title_full Heat capacity and glass transition in P2O5-H 2O solutions: Support for Mishima's conjecture on solvent water at low temperature
title_fullStr Heat capacity and glass transition in P2O5-H 2O solutions: Support for Mishima's conjecture on solvent water at low temperature
title_full_unstemmed Heat capacity and glass transition in P2O5-H 2O solutions: Support for Mishima's conjecture on solvent water at low temperature
title_sort Heat capacity and glass transition in P2O5-H 2O solutions: Support for Mishima's conjecture on solvent water at low temperature
dc.creator.none.fl_str_mv Corti, Horacio Roberto
Nores Pondal, Federico Jose
Angell, C. Austen
author Corti, Horacio Roberto
author_facet Corti, Horacio Roberto
Nores Pondal, Federico Jose
Angell, C. Austen
author_role author
author2 Nores Pondal, Federico Jose
Angell, C. Austen
author2_role author
author
dc.subject.none.fl_str_mv Phosphoric acid
Aqueous solutions
Glass transition
Supercooled
topic Phosphoric acid
Aqueous solutions
Glass transition
Supercooled
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The P2O5-water system has the widest range of continuously glass-forming compositions known for any glassformer + water binary system. Despite the great range of structures explored by the glasses and liquids in this system, the glass transition temperature (Tg) itself varies in a simple monotonic fashion. However the values of Tg reported in the literature show wide disagreement, linked to the different methods of measurement employed. In this work we use differential scanning calorimetry (DSC) to obtain both Tg itself and the jump in heat capacity that occurs as the metastable equilibrium of the supercooled liquid relieves the non-ergodic glassy state. Our study covers the molar ratio range of H2O/P2O5 from 1.5 to 14 (corresponding to the mass fraction of P2O5 between 0.36 and 0.84), which includes the compositions corresponding to pyrophosphoric acid (H 4P2O7) and orthophosphoric acid (H 3PO4). The theoretical model of Couchman and Karasz predicts very well the glass transition temperatures of the P2O 5-H2O system over the whole composition range if the relatively large heat capacity change associated with water in aqueous solutions at the glass transition temperature is adopted, instead of the vanishingly small value observed for vapor deposited or hyperquenched pure water. Therefore, solvent water in this ambient pressure P2O5-H 2O system behaves like a different liquid, more closely resembling a high-density liquid (HDL) polyamorph, as suggested by Mishima for electrolytes at high pressures.
Fil: Corti, Horacio Roberto. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina. 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
Fil: Nores Pondal, Federico Jose. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Angell, C. Austen. Arizona State University; Estados Unidos
description The P2O5-water system has the widest range of continuously glass-forming compositions known for any glassformer + water binary system. Despite the great range of structures explored by the glasses and liquids in this system, the glass transition temperature (Tg) itself varies in a simple monotonic fashion. However the values of Tg reported in the literature show wide disagreement, linked to the different methods of measurement employed. In this work we use differential scanning calorimetry (DSC) to obtain both Tg itself and the jump in heat capacity that occurs as the metastable equilibrium of the supercooled liquid relieves the non-ergodic glassy state. Our study covers the molar ratio range of H2O/P2O5 from 1.5 to 14 (corresponding to the mass fraction of P2O5 between 0.36 and 0.84), which includes the compositions corresponding to pyrophosphoric acid (H 4P2O7) and orthophosphoric acid (H 3PO4). The theoretical model of Couchman and Karasz predicts very well the glass transition temperatures of the P2O 5-H2O system over the whole composition range if the relatively large heat capacity change associated with water in aqueous solutions at the glass transition temperature is adopted, instead of the vanishingly small value observed for vapor deposited or hyperquenched pure water. Therefore, solvent water in this ambient pressure P2O5-H 2O system behaves like a different liquid, more closely resembling a high-density liquid (HDL) polyamorph, as suggested by Mishima for electrolytes at high pressures.
publishDate 2011
dc.date.none.fl_str_mv 2011-09
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/11336/193412
Corti, Horacio Roberto; Nores Pondal, Federico Jose; Angell, C. Austen; Heat capacity and glass transition in P2O5-H 2O solutions: Support for Mishima's conjecture on solvent water at low temperature; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 13; 44; 9-2011; 19741-19748
1463-9076
CONICET Digital
CONICET
url http://hdl.handle.net/11336/193412
identifier_str_mv Corti, Horacio Roberto; Nores Pondal, Federico Jose; Angell, C. Austen; Heat capacity and glass transition in P2O5-H 2O solutions: Support for Mishima's conjecture on solvent water at low temperature; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 13; 44; 9-2011; 19741-19748
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/C1CP22185J
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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score 13.070432

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