An X-ray Determinative Method for the Divalent Cation Ratio in the Triphylite-Lithiophilite Series

André-Mathieu Fransolet*, Diano Antenucci, Jean-Marie Speetjens and Pierre Tarte
Institut de Minéralogie, Université de Liège, 9 Place du Vingt-Août, B-4000 Liège, Belgium
Départment de Chimie Générale, Université de Liège, Sart Tilman, B-4000 Liège, Belgium
*Research Associate FNRS, Belgium.

Abstract: The powder diffractograms of twenty wet chemically analysed samples in the isomorphous triphylite-lithiophilite series and five synthesized members with Fe/(Fe + Mn) = 1, 0.75, 0.50, 0.25, and 0.0, were recorded. Their unit cell dimensions were accurately refined in order to find a reliable method for semi-quantitative determination of the divalent cation content of these minerals. A multivariate best fit analysis based on Kummell’s procedure shows the marked influence of Fe2+ and Mg2+ on the cell dimensions, as well as that of small amounts of Fe3+ substituting for Mn2+, following LiMn2+ → □ Fe3+. The best representation of the correlation between chemical composition and cell parameters is given by the equations:

a = 6.1041 − 0.0245 Fetot − 0.049 Mg2+

b = 10.4511 − Fetot − 0.082 Mg2+

c = 4.7400 − 0.0130(Fe2+ + Mg2+) − 0.025 Fe3+.

No evidence of non-linearity has been found for the variation of the three cell dimensions with the chemical composition. Assuming the absence of appreciable amounts of Mg2+, the following set of equations is proposed: Fetot = 41(6.104–a); Fetot = 35(10.451–b); Fetot = 77(4.740–c) in which the c dimension gives a relatively poor estimate.

Two sets of determinative graphs were constructed, one based on the cell parameter variation, and the other on the 311, 222, and 142 reflection angular positions, v. the total iron content of these minerals. These two methods, whose reliability is examined, can be used for determination of the divalent cation content, provided the samples contain less than about 0.5 wt.% Na2O, 0.5 wt.% CaO, and 3 wt. % Fe2O3, and are homogeneous.

Mineralogical Magazine; September 1984 v. 48; no. 348; p. 373-381; DOI: 10.1180/minmag.1984.048.348.07
© 1984, The Mineralogical Society
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