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Issue 2, 2015
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An in situ spectroscopic study of the local structure of oxyfluoride melts: NMR insights into the speciation in molten LiF–LaF3–Li2O systems

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Abstract

The local structure of molten LaF3–LiF–Li2O has been investigated by high temperature NMR spectroscopy. The 139La and 19F chemical shifts have been measured as a function of temperature and composition. The NMR spectra show that Li2O reacts completely with LaF3 to form a LaOF compound in the solid state below the melting temperature of the sample. LaOF is not completely dissolved in the fluoride melt and solid LaOF is observed in the 19F spectra for Li2O concentrations above 10 mol%. We discuss the local environment of lanthanum ions in molten LaF3–LiF–Li2O and compare the results to those with the LaF3–LiF–CaO system. The analysis of the temperature and Li2O concentration dependences of the 139La and 19F chemical shifts suggests that several kinds of lanthanum oxyfluoride long-lived LaOxFy3−xy units are present in the melt.

Graphical abstract: An in situ spectroscopic study of the local structure of oxyfluoride melts: NMR insights into the speciation in molten LiF–LaF3–Li2O systems

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Publication details

The article was received on 28 Mar 2014, accepted on 25 Apr 2014 and first published on 28 Apr 2014


Article type: Paper
DOI: 10.1039/C4DT00926F
Citation: Dalton Trans., 2015,44, 522-529
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    An in situ spectroscopic study of the local structure of oxyfluoride melts: NMR insights into the speciation in molten LiF–LaF3–Li2O systems

    A. Rollet, H. Matsuura and C. Bessada, Dalton Trans., 2015, 44, 522
    DOI: 10.1039/C4DT00926F

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