Effective Volumes of Waters of Crystallization: Ionic Systems

© 2019 American Chemical Society. We investigate the effective molecular volumes of waters of crystallization for 182 ionic materials as a function of their degree of hydration (the "effective" volume being the difference per water of hydration between the formula unit volumes of hydrates,...

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Main Author: Glasser, Leslie
Format: Journal Article
Language:English
Published: AMER CHEMICAL SOC 2019
Subjects:
Online Access:http://hdl.handle.net/20.500.11937/76279
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author Glasser, Leslie
author_facet Glasser, Leslie
author_sort Glasser, Leslie
building Curtin Institutional Repository
collection Online Access
description © 2019 American Chemical Society. We investigate the effective molecular volumes of waters of crystallization for 182 ionic materials as a function of their degree of hydration (the "effective" volume being the difference per water of hydration between the formula unit volumes of hydrates, including the parent anhydrate). We establish a median effective H2O molecular volume of 0.024(2) nm3, a value which is somewhat smaller than the ambient molecular volume of liquid water, 0.0299 nm3. The effective water of crystallization volumes increase slightly as the degree of hydration increases toward an apparent upper limit of about 18 water molecules, as is also observed in the behavior of the Gibbs energies of hydration. Our data include not only common ionic solids with inorganic anions but also organic anions and the zwitterionic l-amino acids; their effective volumes are commensurate with the values for the common ionic solids and thus also close to the molecular volume of liquid water. We provide two examples of the application of these principles to organic systems, yielding similar values for the effective volume of hydration. We demonstrate how these volumes may be used in the prediction of various thermodynamic values of hydrates and their parent anhydrates.
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spelling curtin-20.500.11937-762792019-09-17T03:11:47Z Effective Volumes of Waters of Crystallization: Ionic Systems Glasser, Leslie Science & Technology Physical Sciences Technology Chemistry, Multidisciplinary Crystallography Materials Science, Multidisciplinary Chemistry Materials Science STANDARD ABSOLUTE ENTROPY CRYSTAL-STRUCTURES DIFFERENCE RULE THERMODYNAMIC DATA LATTICE HYDRATION DENSITY PREDICTION ENERGIES S-298(O) © 2019 American Chemical Society. We investigate the effective molecular volumes of waters of crystallization for 182 ionic materials as a function of their degree of hydration (the "effective" volume being the difference per water of hydration between the formula unit volumes of hydrates, including the parent anhydrate). We establish a median effective H2O molecular volume of 0.024(2) nm3, a value which is somewhat smaller than the ambient molecular volume of liquid water, 0.0299 nm3. The effective water of crystallization volumes increase slightly as the degree of hydration increases toward an apparent upper limit of about 18 water molecules, as is also observed in the behavior of the Gibbs energies of hydration. Our data include not only common ionic solids with inorganic anions but also organic anions and the zwitterionic l-amino acids; their effective volumes are commensurate with the values for the common ionic solids and thus also close to the molecular volume of liquid water. We provide two examples of the application of these principles to organic systems, yielding similar values for the effective volume of hydration. We demonstrate how these volumes may be used in the prediction of various thermodynamic values of hydrates and their parent anhydrates. 2019 Journal Article http://hdl.handle.net/20.500.11937/76279 10.1021/acs.cgd.9b00290 English AMER CHEMICAL SOC restricted
spellingShingle Science & Technology
Physical Sciences
Technology
Chemistry, Multidisciplinary
Crystallography
Materials Science, Multidisciplinary
Chemistry
Materials Science
STANDARD ABSOLUTE ENTROPY
CRYSTAL-STRUCTURES
DIFFERENCE RULE
THERMODYNAMIC DATA
LATTICE
HYDRATION
DENSITY
PREDICTION
ENERGIES
S-298(O)
Glasser, Leslie
Effective Volumes of Waters of Crystallization: Ionic Systems
title Effective Volumes of Waters of Crystallization: Ionic Systems
title_full Effective Volumes of Waters of Crystallization: Ionic Systems
title_fullStr Effective Volumes of Waters of Crystallization: Ionic Systems
title_full_unstemmed Effective Volumes of Waters of Crystallization: Ionic Systems
title_short Effective Volumes of Waters of Crystallization: Ionic Systems
title_sort effective volumes of waters of crystallization: ionic systems
topic Science & Technology
Physical Sciences
Technology
Chemistry, Multidisciplinary
Crystallography
Materials Science, Multidisciplinary
Chemistry
Materials Science
STANDARD ABSOLUTE ENTROPY
CRYSTAL-STRUCTURES
DIFFERENCE RULE
THERMODYNAMIC DATA
LATTICE
HYDRATION
DENSITY
PREDICTION
ENERGIES
S-298(O)
url http://hdl.handle.net/20.500.11937/76279