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Excess heat capacity and entropy of mixing along the hydroxyapatite-chlorapatite and hydroxyapatite-fluorapatite binaries

The heat capacity, C(p), of synthetic hydroxyapatite [Ca(5)(PO(4))(3)OH–OH-Ap], as well as of ten compositions along the OH-Ap-chlorapatite (Cl-Ap) join and 12 compositions along the OH-Ap-fluorapatite (F-Ap) join have been measured using relaxation calorimetry (heat capacity option of the Physical...

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Autores principales: Dachs, Edgar, Benisek, Artur, Harlov, Daniel, Wilke, Max
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Springer Berlin Heidelberg 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8553719/
https://www.ncbi.nlm.nih.gov/pubmed/34744262
http://dx.doi.org/10.1007/s00269-021-01167-1
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author Dachs, Edgar
Benisek, Artur
Harlov, Daniel
Wilke, Max
author_facet Dachs, Edgar
Benisek, Artur
Harlov, Daniel
Wilke, Max
author_sort Dachs, Edgar
collection PubMed
description The heat capacity, C(p), of synthetic hydroxyapatite [Ca(5)(PO(4))(3)OH–OH-Ap], as well as of ten compositions along the OH-Ap-chlorapatite (Cl-Ap) join and 12 compositions along the OH-Ap-fluorapatite (F-Ap) join have been measured using relaxation calorimetry (heat capacity option of the Physical Properties Measurement System—PPMS) and differential scanning calorimetry (DSC) in the temperature range of 5–764 K. Apatites along the Cl-OH and F-OH joins were synthesized at 1100 °C and 300 MPa in an internally heated gas pressure vessel via an exchange process between synthetic fluorapatite or chlorapatite crystals (200–500 μm size) and a series of Ca(OH)(2)-H(2)O solutions with specific compositions and amounts relative to the starting apatite. The standard third-law entropy of OH-Ap, derived from the low-temperature heat capacity measurements, is S° = 386.3 ± 2.5 J mol(−1) K(−1), which is ~ 1% lower than that resulting from low-temperature adiabatic calorimetry data on OH-Ap from the 1950’s. The heat capacity of OH-Ap above 298.15 K shows a hump-shaped anomaly centred around 442 K. Based on published structural and calorimetric work, this feature is interpreted to result from a monoclinic to hexagonal phase transition. Super ambient C(p) up to this transition can be represented by the polynomial: [Formula: see text] . The DSC data above this transition were combined with heat capacities computed using density functional theory and can be given by the C(p) polynomial: [Formula: see text] . Positive excess heat capacities of mixing, ∆C(p)(ex), in the order of 1–2 J mol(−1) K(−1), occur in both solid solutions at around 70 K. They are significant at these conditions exceeding the 2σ-uncertainty of the data. This positive ∆C(p)(ex) is compensated by a negative ∆C(p)(ex) of the same order at around 250 K in both binaries. At higher temperatures (up to 1200 K), ∆C(p)(ex) is zero within error for all solid solution members. As a consequence, the calorimetric entropies, S(cal), show no deviation from ideal mixing behaviour within a 2σ-uncertainty for both joins. Excess entropies of mixing, ∆S(ex), are thus zero for the OH-Ap–F-Ap, as well as for the OH-Ap–Cl-Ap join. The C(p)–T behaviour of the OH-Ap endmember is discussed in relation to that of the F- and Cl-endmembers. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s00269-021-01167-1.
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spelling pubmed-85537192021-11-04 Excess heat capacity and entropy of mixing along the hydroxyapatite-chlorapatite and hydroxyapatite-fluorapatite binaries Dachs, Edgar Benisek, Artur Harlov, Daniel Wilke, Max Phys Chem Miner Original Paper The heat capacity, C(p), of synthetic hydroxyapatite [Ca(5)(PO(4))(3)OH–OH-Ap], as well as of ten compositions along the OH-Ap-chlorapatite (Cl-Ap) join and 12 compositions along the OH-Ap-fluorapatite (F-Ap) join have been measured using relaxation calorimetry (heat capacity option of the Physical Properties Measurement System—PPMS) and differential scanning calorimetry (DSC) in the temperature range of 5–764 K. Apatites along the Cl-OH and F-OH joins were synthesized at 1100 °C and 300 MPa in an internally heated gas pressure vessel via an exchange process between synthetic fluorapatite or chlorapatite crystals (200–500 μm size) and a series of Ca(OH)(2)-H(2)O solutions with specific compositions and amounts relative to the starting apatite. The standard third-law entropy of OH-Ap, derived from the low-temperature heat capacity measurements, is S° = 386.3 ± 2.5 J mol(−1) K(−1), which is ~ 1% lower than that resulting from low-temperature adiabatic calorimetry data on OH-Ap from the 1950’s. The heat capacity of OH-Ap above 298.15 K shows a hump-shaped anomaly centred around 442 K. Based on published structural and calorimetric work, this feature is interpreted to result from a monoclinic to hexagonal phase transition. Super ambient C(p) up to this transition can be represented by the polynomial: [Formula: see text] . The DSC data above this transition were combined with heat capacities computed using density functional theory and can be given by the C(p) polynomial: [Formula: see text] . Positive excess heat capacities of mixing, ∆C(p)(ex), in the order of 1–2 J mol(−1) K(−1), occur in both solid solutions at around 70 K. They are significant at these conditions exceeding the 2σ-uncertainty of the data. This positive ∆C(p)(ex) is compensated by a negative ∆C(p)(ex) of the same order at around 250 K in both binaries. At higher temperatures (up to 1200 K), ∆C(p)(ex) is zero within error for all solid solution members. As a consequence, the calorimetric entropies, S(cal), show no deviation from ideal mixing behaviour within a 2σ-uncertainty for both joins. Excess entropies of mixing, ∆S(ex), are thus zero for the OH-Ap–F-Ap, as well as for the OH-Ap–Cl-Ap join. The C(p)–T behaviour of the OH-Ap endmember is discussed in relation to that of the F- and Cl-endmembers. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s00269-021-01167-1. Springer Berlin Heidelberg 2021-10-28 2021 /pmc/articles/PMC8553719/ /pubmed/34744262 http://dx.doi.org/10.1007/s00269-021-01167-1 Text en © The Author(s) 2021 https://creativecommons.org/licenses/by/4.0/Open AccessThis article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article's Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) .
spellingShingle Original Paper
Dachs, Edgar
Benisek, Artur
Harlov, Daniel
Wilke, Max
Excess heat capacity and entropy of mixing along the hydroxyapatite-chlorapatite and hydroxyapatite-fluorapatite binaries
title Excess heat capacity and entropy of mixing along the hydroxyapatite-chlorapatite and hydroxyapatite-fluorapatite binaries
title_full Excess heat capacity and entropy of mixing along the hydroxyapatite-chlorapatite and hydroxyapatite-fluorapatite binaries
title_fullStr Excess heat capacity and entropy of mixing along the hydroxyapatite-chlorapatite and hydroxyapatite-fluorapatite binaries
title_full_unstemmed Excess heat capacity and entropy of mixing along the hydroxyapatite-chlorapatite and hydroxyapatite-fluorapatite binaries
title_short Excess heat capacity and entropy of mixing along the hydroxyapatite-chlorapatite and hydroxyapatite-fluorapatite binaries
title_sort excess heat capacity and entropy of mixing along the hydroxyapatite-chlorapatite and hydroxyapatite-fluorapatite binaries
topic Original Paper
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8553719/
https://www.ncbi.nlm.nih.gov/pubmed/34744262
http://dx.doi.org/10.1007/s00269-021-01167-1
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