Book contents
- Frontmatter
- Contents
- Preface to the first edition
- Preface to the second edition
- 1 Introduction
- 2 Outline of crystal field theory
- 3 Energy level diagrams and crystal field spectra of transition metal ions
- 4 Measurements of absorption spectra of minerals
- 5 Crystal field spectra of transition metal ions in minerals
- 6 Crystal chemistry of transition metal-bearing minerals
- 7 Thermodynamic properties influenced by crystal field energies
- 8 Trace element geochemistry: distribution of transition metals in the Earth's crust
- 9 Mantle geochemistry of the transition elements: optical spectra at elevated temperatures and pressures
- 10 Remote-sensing compositions of planetary surfaces: applications of reflectance spectra
- 11 Covalent bonding of the transition elements
- Appendices
- References
- Subject index
7 - Thermodynamic properties influenced by crystal field energies
Published online by Cambridge University Press: 23 November 2009
- Frontmatter
- Contents
- Preface to the first edition
- Preface to the second edition
- 1 Introduction
- 2 Outline of crystal field theory
- 3 Energy level diagrams and crystal field spectra of transition metal ions
- 4 Measurements of absorption spectra of minerals
- 5 Crystal field spectra of transition metal ions in minerals
- 6 Crystal chemistry of transition metal-bearing minerals
- 7 Thermodynamic properties influenced by crystal field energies
- 8 Trace element geochemistry: distribution of transition metals in the Earth's crust
- 9 Mantle geochemistry of the transition elements: optical spectra at elevated temperatures and pressures
- 10 Remote-sensing compositions of planetary surfaces: applications of reflectance spectra
- 11 Covalent bonding of the transition elements
- Appendices
- References
- Subject index
Summary
These observations (non-linear heats of hydration) suggest the following hypothesis: In the absence of crystal-field effects the thermodynamic properties – – would evolve steadily along the transition series.
L. E. Orgel, Journ. Chem. Soc., p. 4756 (1952).Introduction
One of the most successful applications of crystal field theory to transition metal chemistry, and the one that heralded the re-discovery of the theory by Orgel in 1952, has been the rationalization of observed thermodynamic properties of transition metal ions. Examples include explanations of trends in heats of hydration and lattice energies of transition metal compounds. These and other thermodynamic properties which are influenced by crystal field stabilization energies, including ideal solid-solution behaviour and distribution coefficients of transition metals between coexisting phases, are described in this chapter.
Influence of CFSE on thermodynamic data
Graphical correlations
Crystal field stabilization energies derived spectroscopically from absorption bands in the visible to near-infrared region, including the crystal field spectral measurements of minerals described in chapter 5, are enthalpy terms and, as such, might be expected to contribute to bulk properties such as lattice energies and solvation energies of transition metal compounds. If cations were spherically symmetrical and no preferential filling of 3d orbitals occurred, a given thermodynamic quantity would be expected to display smooth periodic variation in a series of transition metal compounds as a result of contraction of the cations.
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- Information
- Mineralogical Applications of Crystal Field Theory , pp. 272 - 299Publisher: Cambridge University PressPrint publication year: 1993