The role of sulfate groups in controlling CaCO3 polymorphism

The nucleation and growth of CaCO3 phases from aqueous solutions with SO4 2-:CO3 2- ratios from 0 to 1.62 and a pH ∼ 10.9 were studied experimentally in batch reactors at 25 ºC. The mineralogy, morphology and composition of the precipitates were characterized by X-ray diffraction, Fourier transform...

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Detalhes bibliográficos
Autores: Fernández Díaz, María Lourdes, Fernández González, Ángeles, Prieto Rubio, Manuel
Formato: artículo
Fecha de publicación:2010
País:España
Recursos:Universidad Complutense de Madrid (UCM)
Repositorio:Docta Complutense
Idioma:inglés
OAI Identifier:oai:docta.ucm.es:20.500.14352/43359
Acesso em linha:https://hdl.handle.net/20.500.14352/43359
Access Level:acceso abierto
Palavra-chave:548:73
549.6
Sulfates
X-ray diffraction
Cristalografía (Geología)
Mineralogía (Geología)
2506.11 Mineralogía
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oai_identifier_str oai:docta.ucm.es:20.500.14352/43359
network_acronym_str ES
network_name_str España
repository_id_str
spelling The role of sulfate groups in controlling CaCO3 polymorphismFernández Díaz, María LourdesFernández González, ÁngelesPrieto Rubio, Manuel548:73549.6SulfatesX-ray diffractionCristalografía (Geología)Mineralogía (Geología)2506.11 MineralogíaThe nucleation and growth of CaCO3 phases from aqueous solutions with SO4 2-:CO3 2- ratios from 0 to 1.62 and a pH ∼ 10.9 were studied experimentally in batch reactors at 25 ºC. The mineralogy, morphology and composition of the precipitates were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy and microanalyses. The solids recovered after short reaction times (5 min to 1 h) consisted of a mixture of calcite and vaterite, with a S content that linearly correlates with the SO4 2-:CO32- ratio in the aqueous solution. The solvent-mediated transformation of vaterite to calcite subsequently occurred. After 24 h of equilibration, calcite was the only phase present in the precipitate for aqueous solutions with SO4 2-:CO3 2- ≤ 1. For SO4 2-:CO3 2- > 1, vaterite persisted as a major phase for a longer time (>250 h for SO4 2-:CO3 2- = 1.62). To study the role of sulfate in stabilizing vaterite, we performed a molecular simulation of the substitution of sulfate for carbonate groups into the crystal structure of vaterite, aragonite and calcite. The results obtained show that the incorporation of small amounts (<3 mole%) of sulfate is energetically favorable in the vaterite structure, unfavorable in calcite and very unfavorable in aragonite. The computer modeling provided thermodynamic information, which, combined with kinetic arguments, allowed us to put forward a plausible explanation for the observed crystallization behavior.Elsevier Science LtdUniversidad Complutense de Madrid20102010-01-0120102010-01-01journal articlehttp://purl.org/coar/resource_type/c_6501info:eu-repo/semantics/articleapplication/pdfhttps://hdl.handle.net/20.500.14352/43359reponame:Docta Complutenseinstname:Universidad Complutense de Madrid (UCM)Inglésengopen accesshttp://purl.org/coar/access_right/c_abf2Atribución-NoComercial-SinDerivadas 3.0 Españahttps://creativecommons.org/licenses/by-nc-nd/3.0/es/info:eu-repo/semantics/openAccessoai:docta.ucm.es:20.500.14352/433592026-06-02T12:44:21Z
dc.title.none.fl_str_mv The role of sulfate groups in controlling CaCO3 polymorphism
title The role of sulfate groups in controlling CaCO3 polymorphism
spellingShingle The role of sulfate groups in controlling CaCO3 polymorphism
Fernández Díaz, María Lourdes
548:73
549.6
Sulfates
X-ray diffraction
Cristalografía (Geología)
Mineralogía (Geología)
2506.11 Mineralogía
title_short The role of sulfate groups in controlling CaCO3 polymorphism
title_full The role of sulfate groups in controlling CaCO3 polymorphism
title_fullStr The role of sulfate groups in controlling CaCO3 polymorphism
title_full_unstemmed The role of sulfate groups in controlling CaCO3 polymorphism
title_sort The role of sulfate groups in controlling CaCO3 polymorphism
dc.creator.none.fl_str_mv Fernández Díaz, María Lourdes
Fernández González, Ángeles
Prieto Rubio, Manuel
author Fernández Díaz, María Lourdes
author_facet Fernández Díaz, María Lourdes
Fernández González, Ángeles
Prieto Rubio, Manuel
author_role author
author2 Fernández González, Ángeles
Prieto Rubio, Manuel
author2_role author
author
dc.contributor.none.fl_str_mv Universidad Complutense de Madrid
dc.subject.none.fl_str_mv 548:73
549.6
Sulfates
X-ray diffraction
Cristalografía (Geología)
Mineralogía (Geología)
2506.11 Mineralogía
topic 548:73
549.6
Sulfates
X-ray diffraction
Cristalografía (Geología)
Mineralogía (Geología)
2506.11 Mineralogía
description The nucleation and growth of CaCO3 phases from aqueous solutions with SO4 2-:CO3 2- ratios from 0 to 1.62 and a pH ∼ 10.9 were studied experimentally in batch reactors at 25 ºC. The mineralogy, morphology and composition of the precipitates were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy and microanalyses. The solids recovered after short reaction times (5 min to 1 h) consisted of a mixture of calcite and vaterite, with a S content that linearly correlates with the SO4 2-:CO32- ratio in the aqueous solution. The solvent-mediated transformation of vaterite to calcite subsequently occurred. After 24 h of equilibration, calcite was the only phase present in the precipitate for aqueous solutions with SO4 2-:CO3 2- ≤ 1. For SO4 2-:CO3 2- > 1, vaterite persisted as a major phase for a longer time (>250 h for SO4 2-:CO3 2- = 1.62). To study the role of sulfate in stabilizing vaterite, we performed a molecular simulation of the substitution of sulfate for carbonate groups into the crystal structure of vaterite, aragonite and calcite. The results obtained show that the incorporation of small amounts (<3 mole%) of sulfate is energetically favorable in the vaterite structure, unfavorable in calcite and very unfavorable in aragonite. The computer modeling provided thermodynamic information, which, combined with kinetic arguments, allowed us to put forward a plausible explanation for the observed crystallization behavior.
publishDate 2010
dc.date.none.fl_str_mv 2010
2010-01-01
2010
2010-01-01
dc.type.none.fl_str_mv journal article
http://purl.org/coar/resource_type/c_6501
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://hdl.handle.net/20.500.14352/43359
url https://hdl.handle.net/20.500.14352/43359
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
Atribución-NoComercial-SinDerivadas 3.0 España
https://creativecommons.org/licenses/by-nc-nd/3.0/es/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
Atribución-NoComercial-SinDerivadas 3.0 España
https://creativecommons.org/licenses/by-nc-nd/3.0/es/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Elsevier Science Ltd
publisher.none.fl_str_mv Elsevier Science Ltd
dc.source.none.fl_str_mv reponame:Docta Complutense
instname:Universidad Complutense de Madrid (UCM)
instname_str Universidad Complutense de Madrid (UCM)
reponame_str Docta Complutense
collection Docta Complutense
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15.198674

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