Short-range order in fused salts. I. Coordination states of nickel(II) in molten zinc chloride-potassium chloride mixtures

Charles Angell, D. M. Gruen

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Abstract

Absorption spectra of Ni(II) in molten KCl-ZnCl2 mixtures have been obtained as a function of temperature and of melt composition in the range 4000-40,000 cm-1. Spectra have been obtained over the entire composition range from pure liquid ZnCl2 to pure liquid KCl. The extremes in the temperature range studied were 250 to 900°. Observed spectral changes have been interpreted to indicate the existence of (a) a two-species equilibrium involving Ni(II) in octahedral and distorted tetrahedral sites, and (b) transformation by a continuous distortion mechanism of an octahedral Ni(II) species to a highly distorted tetrahedral species. The effect of Cl- polarization by Zn(II) and of volume changes on the coordination behavior of Ni(II) is discussed. A simple technique for handling and weighing small samples of highly hygroscopic materials is described.

Original languageEnglish (US)
Pages (from-to)1601-1609
Number of pages9
JournalJournal of Physical Chemistry
Volume70
Issue number5
StatePublished - 1966
Externally publishedYes

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Fused salts
zinc chlorides
Zinc chloride
potassium chlorides
Potassium Chloride
Nickel
Potassium
Molten materials
nickel
salts
Liquids
Weighing
liquids
Chemical analysis
Absorption spectra
Polarization
absorption spectra
Temperature
temperature
polarization

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

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abstract = "Absorption spectra of Ni(II) in molten KCl-ZnCl2 mixtures have been obtained as a function of temperature and of melt composition in the range 4000-40,000 cm-1. Spectra have been obtained over the entire composition range from pure liquid ZnCl2 to pure liquid KCl. The extremes in the temperature range studied were 250 to 900°. Observed spectral changes have been interpreted to indicate the existence of (a) a two-species equilibrium involving Ni(II) in octahedral and distorted tetrahedral sites, and (b) transformation by a continuous distortion mechanism of an octahedral Ni(II) species to a highly distorted tetrahedral species. The effect of Cl- polarization by Zn(II) and of volume changes on the coordination behavior of Ni(II) is discussed. A simple technique for handling and weighing small samples of highly hygroscopic materials is described.",
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T1 - Short-range order in fused salts. I. Coordination states of nickel(II) in molten zinc chloride-potassium chloride mixtures

AU - Angell, Charles

AU - Gruen, D. M.

PY - 1966

Y1 - 1966

N2 - Absorption spectra of Ni(II) in molten KCl-ZnCl2 mixtures have been obtained as a function of temperature and of melt composition in the range 4000-40,000 cm-1. Spectra have been obtained over the entire composition range from pure liquid ZnCl2 to pure liquid KCl. The extremes in the temperature range studied were 250 to 900°. Observed spectral changes have been interpreted to indicate the existence of (a) a two-species equilibrium involving Ni(II) in octahedral and distorted tetrahedral sites, and (b) transformation by a continuous distortion mechanism of an octahedral Ni(II) species to a highly distorted tetrahedral species. The effect of Cl- polarization by Zn(II) and of volume changes on the coordination behavior of Ni(II) is discussed. A simple technique for handling and weighing small samples of highly hygroscopic materials is described.

AB - Absorption spectra of Ni(II) in molten KCl-ZnCl2 mixtures have been obtained as a function of temperature and of melt composition in the range 4000-40,000 cm-1. Spectra have been obtained over the entire composition range from pure liquid ZnCl2 to pure liquid KCl. The extremes in the temperature range studied were 250 to 900°. Observed spectral changes have been interpreted to indicate the existence of (a) a two-species equilibrium involving Ni(II) in octahedral and distorted tetrahedral sites, and (b) transformation by a continuous distortion mechanism of an octahedral Ni(II) species to a highly distorted tetrahedral species. The effect of Cl- polarization by Zn(II) and of volume changes on the coordination behavior of Ni(II) is discussed. A simple technique for handling and weighing small samples of highly hygroscopic materials is described.

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