The cohesive entropy of condensed materials, empirical relations and restrictions

Entropy factors of a material are connected through an equation which relates three independent experimental values specific to each material: ΔfS=S-∑inSatoms,i. (Note: our results refer to independently summed ∑1nSatoms,i values rather than calculation by simple difference of the third dependent va...

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Main Author: Glasser, Leslie
Format: Journal Article
Language:English
Published: ACADEMIC PRESS LTD- ELSEVIER SCIENCE LTD 2022
Subjects:
Online Access:http://hdl.handle.net/20.500.11937/88438
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author Glasser, Leslie
author_facet Glasser, Leslie
author_sort Glasser, Leslie
building Curtin Institutional Repository
collection Online Access
description Entropy factors of a material are connected through an equation which relates three independent experimental values specific to each material: ΔfS=S-∑inSatoms,i. (Note: our results refer to independently summed ∑1nSatoms,i values rather than calculation by simple difference of the third dependent value from the other two of these values.) We define the cohesive entropy coefficient, αScoh, through ΔfS=α∑inSatoms,i. Having ready access to a large database of thermodynamic data for solid ionic materials from earlier studies, we have investigated the generalisations that may be made among these entropy quantities for this group of materials. We find that the data points of this three-dimensional system are confined to a fan-shaped tilted plane which has rather strict lateral limits, with the upper limits controlled by the entropies of gaseous elements and the lower limits by the entropies of solid elements. This has the consequence of providing insight into the understanding of entropy values and their limits as a check on experimental determinations. In particular, formation and standard entropies for condensed phases are shown to be proportional to one another with a fixed proportionality constant, the cohesive entropy coefficient, αScoh = -0.831. Evidence is provided that the same restrictions apply to condensed organic materials, and we suggest that these entropy relations are applicable to condensed materials in general.
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spelling curtin-20.500.11937-884382024-04-22T01:00:34Z The cohesive entropy of condensed materials, empirical relations and restrictions Glasser, Leslie Science & Technology Physical Sciences Thermodynamics Chemistry, Physical Chemistry ORGANIC-SUBSTANCES VALUES Entropy factors of a material are connected through an equation which relates three independent experimental values specific to each material: ΔfS=S-∑inSatoms,i. (Note: our results refer to independently summed ∑1nSatoms,i values rather than calculation by simple difference of the third dependent value from the other two of these values.) We define the cohesive entropy coefficient, αScoh, through ΔfS=α∑inSatoms,i. Having ready access to a large database of thermodynamic data for solid ionic materials from earlier studies, we have investigated the generalisations that may be made among these entropy quantities for this group of materials. We find that the data points of this three-dimensional system are confined to a fan-shaped tilted plane which has rather strict lateral limits, with the upper limits controlled by the entropies of gaseous elements and the lower limits by the entropies of solid elements. This has the consequence of providing insight into the understanding of entropy values and their limits as a check on experimental determinations. In particular, formation and standard entropies for condensed phases are shown to be proportional to one another with a fixed proportionality constant, the cohesive entropy coefficient, αScoh = -0.831. Evidence is provided that the same restrictions apply to condensed organic materials, and we suggest that these entropy relations are applicable to condensed materials in general. 2022 Journal Article http://hdl.handle.net/20.500.11937/88438 10.1016/j.jct.2022.106760 English http://creativecommons.org/licenses/by-nc-nd/4.0/ ACADEMIC PRESS LTD- ELSEVIER SCIENCE LTD fulltext
spellingShingle Science & Technology
Physical Sciences
Thermodynamics
Chemistry, Physical
Chemistry
ORGANIC-SUBSTANCES
VALUES
Glasser, Leslie
The cohesive entropy of condensed materials, empirical relations and restrictions
title The cohesive entropy of condensed materials, empirical relations and restrictions
title_full The cohesive entropy of condensed materials, empirical relations and restrictions
title_fullStr The cohesive entropy of condensed materials, empirical relations and restrictions
title_full_unstemmed The cohesive entropy of condensed materials, empirical relations and restrictions
title_short The cohesive entropy of condensed materials, empirical relations and restrictions
title_sort cohesive entropy of condensed materials, empirical relations and restrictions
topic Science & Technology
Physical Sciences
Thermodynamics
Chemistry, Physical
Chemistry
ORGANIC-SUBSTANCES
VALUES
url http://hdl.handle.net/20.500.11937/88438