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Deviation from van’t Hoff Behavior of Solids at Low Temperature

[Image: see text] As a sequel to results obtained on the low-temperature behavior of liquids, a similar study is presented for solids. A molecule in a solid interacts with the other molecules of the crystal so that it is subjected to a specific multimolecular potential, kT(0). At temperature T <...

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Autores principales: Sluyters, Jan H., Sluyters-Rehbach, Margaretha
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2017
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5452043/
https://www.ncbi.nlm.nih.gov/pubmed/28580439
http://dx.doi.org/10.1021/acsomega.7b00169
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author Sluyters, Jan H.
Sluyters-Rehbach, Margaretha
author_facet Sluyters, Jan H.
Sluyters-Rehbach, Margaretha
author_sort Sluyters, Jan H.
collection PubMed
description [Image: see text] As a sequel to results obtained on the low-temperature behavior of liquids, a similar study is presented for solids. A molecule in a solid interacts with the other molecules of the crystal so that it is subjected to a specific multimolecular potential, kT(0). At temperature T < T(0), the molecules are localized, and at T > T(0), they can participate in processes like self-diffusion and evaporation. As a consequence, the van’t Hoff equation is disobeyed at a low temperature and properties like vapor pressure, diffusion rate, or reactivity are zero below the specific temperature, T(0), which here can be interpreted as a temperature of thermal stability of the solid. To account for this view, the van’t Hoff equation, represented by the green curve in the figure, is extended with a suitable pre-exponential factor, leading to the red curve. Three examples, taken from the literature, are analyzed to demonstrate its applicability. These examples are: the thermal dissociation of calcium carbonate, the sublimation equilibrium pressure of naphthalene, and that of ice. For some other solids, equilibria and dynamic properties, X(T), are examined by means of extrapolations in the X(T) versus T domain, showing the presence of an arrest temperature, which coincides, within experimental accuracy, with the T(0) value obtained from the corresponding vapor pressure. As with liquids, kT(0) is found to be proportional to the molecular pair potential.
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spelling pubmed-54520432017-06-02 Deviation from van’t Hoff Behavior of Solids at Low Temperature Sluyters, Jan H. Sluyters-Rehbach, Margaretha ACS Omega [Image: see text] As a sequel to results obtained on the low-temperature behavior of liquids, a similar study is presented for solids. A molecule in a solid interacts with the other molecules of the crystal so that it is subjected to a specific multimolecular potential, kT(0). At temperature T < T(0), the molecules are localized, and at T > T(0), they can participate in processes like self-diffusion and evaporation. As a consequence, the van’t Hoff equation is disobeyed at a low temperature and properties like vapor pressure, diffusion rate, or reactivity are zero below the specific temperature, T(0), which here can be interpreted as a temperature of thermal stability of the solid. To account for this view, the van’t Hoff equation, represented by the green curve in the figure, is extended with a suitable pre-exponential factor, leading to the red curve. Three examples, taken from the literature, are analyzed to demonstrate its applicability. These examples are: the thermal dissociation of calcium carbonate, the sublimation equilibrium pressure of naphthalene, and that of ice. For some other solids, equilibria and dynamic properties, X(T), are examined by means of extrapolations in the X(T) versus T domain, showing the presence of an arrest temperature, which coincides, within experimental accuracy, with the T(0) value obtained from the corresponding vapor pressure. As with liquids, kT(0) is found to be proportional to the molecular pair potential. American Chemical Society 2017-05-25 /pmc/articles/PMC5452043/ /pubmed/28580439 http://dx.doi.org/10.1021/acsomega.7b00169 Text en Copyright © 2017 American Chemical Society This is an open access article published under a Creative Commons Non-Commercial No Derivative Works (CC-BY-NC-ND) Attribution License (http://pubs.acs.org/page/policy/authorchoice_ccbyncnd_termsofuse.html) , which permits copying and redistribution of the article, and creation of adaptations, all for non-commercial purposes.
spellingShingle Sluyters, Jan H.
Sluyters-Rehbach, Margaretha
Deviation from van’t Hoff Behavior of Solids at Low Temperature
title Deviation from van’t Hoff Behavior of Solids at Low Temperature
title_full Deviation from van’t Hoff Behavior of Solids at Low Temperature
title_fullStr Deviation from van’t Hoff Behavior of Solids at Low Temperature
title_full_unstemmed Deviation from van’t Hoff Behavior of Solids at Low Temperature
title_short Deviation from van’t Hoff Behavior of Solids at Low Temperature
title_sort deviation from van’t hoff behavior of solids at low temperature
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5452043/
https://www.ncbi.nlm.nih.gov/pubmed/28580439
http://dx.doi.org/10.1021/acsomega.7b00169
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