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Bond valence and bond energy

  • Barry R. Bickmore EMAIL logo , Owen Craven , Matthew C.F. Wander , Hannah Checketts , Joshua Whitmer , Christopher Shurtleff , David Yeates , Kiersten Ernstrom , Charles Andros and Hannah Thompson
Published/Copyright: April 3, 2017
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American Mineralogist
From the journal American Mineralogist Volume 102 Issue 4

Abstract

The relationship between bond valence and structural energy has never been fully explored, although several predictive models have assumed some simple relationship between the two. Some of these models relate energy only to bond valence, while others also take into account other factors, such as bond character. We examined periodic trends in bond dissociation energies as a function of their ionicity, covalency, and metallicity, defined in terms of the electronegativity values of the atoms involved. A statistical model was optimized to describe these trends, allowing us to generate rough bond energy vs. bond valence curves. The shapes of these curves vary dramatically as a function of bond character, and are strongly influenced by the lone-pair bond-weakening effect. The curve shapes can be used to rationalize several chemical trends, including the preferred structures of compounds with different bond types, the prevalence of peroxide and persulfide minerals, preferred bond lengths in oxides, and the pKa values of (hydr)oxy-acids. The last is perhaps the most important, because some valence-based acidity models are in current use, despite the fact that some aspects of their rationale are unclear.

Keywords: Bond valence; energy; ionicity; metallicity; covalency; lone-pair bond-weakening effect; acidity

Acknowledgments

The authors gratefully acknowledge support for this research from the National Science Foundation (EAR-1424682) and the College of Physical and Mathematical Sciences undergraduate mentoring program at Brigham Young University. I.D. Brown and an anonymous reviewer provided very helpful comments on the original manuscript.

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Received: 2016-8-22
Accepted: 2016-11-17
Published Online: 2017-4-3
Published in Print: 2017-4-1

© 2017 by Walter de Gruyter Berlin/Boston

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https://doi.org/10.2138/am-2017-5938
Keywords for this article
Bond valence; energy; ionicity; metallicity; covalency; lone-pair bond-weakening effect; acidity

Articles in the same Issue

  1. Review: Minerals in the Human Body
  2. Mineral precipitation and dissolution in the kidney
  3. Special Collection: Nanominerals and Mineral Nanoparticles
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  5. Special Collection: Apatite: A Common Mineral, Uncommonly Versatile
  6. Column anion arrangements in chemically zoned ternary chlorapatite and fluorapatite from Kurokura, Japan
  7. Special Collection: Apatite: A Common Mineral, Uncommonly Versatile
  8. Magmatic graphite inclusions in Mn-Fe-rich fluorapatite of perphosphorus granites (the Belvís pluton, Variscan Iberian Belt)
  9. Special Collection: Apatite: A Common Mineral, Uncommonly Versatile
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  12. A comparison of olivine-melt thermometers based on DMg and DNi: The effects of melt composition, temperature, and pressure with applications to MORBs and hydrous arc basalts
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  36. Tourmaline-rich features in the Heemskirk and Pieman Heads granites from western Tasmania, Australia: Characteristics, origins, and implications for tin mineralization
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