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    Effective Volumes of Waters of Crystallization: Ionic Systems

    Access Status
    Fulltext not available
    Authors
    Glasser, Leslie
    Date
    2019
    Type
    Journal Article
    
    Metadata
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    Citation
    Glasser, L. 2019. Effective Volumes of Waters of Crystallization: Ionic Systems. Crystal Growth and Design. 19 (6): pp. 3397-3401.
    Source Title
    Crystal Growth and Design
    DOI
    10.1021/acs.cgd.9b00290
    ISSN
    1528-7483
    Faculty
    Faculty of Science and Engineering
    School
    School of Molecular and Life Sciences (MLS)
    URI
    http://hdl.handle.net/20.500.11937/76279
    Collection
    • Curtin Research Publications
    Abstract

    © 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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