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Cation substitution in synthetic meridianiite (MgSO4·11H2O) II: variation in unit-cell parameters determined from X-ray powder diffraction data

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Abstract

We have prepared aqueous MgSO4 solutions doped with various divalent metal cations (Ni2+, Zn2+, Mn2+, Cu2+, Fe2+, and Co2+) in proportions up to and including the pure end-members. These liquids have been solidified into fine-grained polycrystalline blocks of metal sulfate hydrate + ice by rapid quenching in liquid nitrogen. In a companion paper (Fortes et al., in Phys Chem Min 39) we reported the identification of various phases using X-ray powder diffraction, including meridianiite-structured undecahydrates, melanterite- and epsomite-structured heptahydrates, novel enneahydrates and a new octahydrate. In this work we report the changes in unit-cell parameters of these crystalline products where they exist over sufficient dopant concentrations. We find that there is a linear relationship between the rate of change in unit-cell volume as a function of dopant concentration and the ionic radius of the dopant cation; large ions such as Mn2+ produce a substantial inflation of the hydrates’ unit-cell volume, whereas smaller ions such as Ni2+ produce a modest reduction in unit-cell volume. Indeed, when the data for all hydrates are normalised (i.e., divided by the number of formula units per unit-cell, Z, and the hydration number, n), we find a quantitatively similar relationship for different values of n. Conversely, there is no relationship between the degree of unit-cell inflation or deflation and the limit to which a given cation will substitute into a certain hydrate structure; for example, Co2+ and Zn2+ affect the unit-cell volume of MgSO4·11H2O to a very similar degree, yet the solubility limits inferred in our companion paper are >60 mol. % Co2+ and <30 mol. % Zn2+.

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Notes

  1. For the sake of brevity, the various species will be referred to by cation and hydration state, such that MgSO4·11H2O becomes Mg11 and CuSO4·5H2O, for example, becomes Cu5.

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Acknowledgments

The authors thank Neil Hughes for assistance with the design and construction of the Peltier cold stage, and Kevin Knight for the use of the cryogenic pestle and mortar. This work was supported in part by Master’s student funds from the UCL Department of Earth Sciences (F. Browning), and in part by the Science and Technology Facilities Council, Fellowship number PP/E006515/1 (A. D. Fortes).

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Authors and Affiliations

  1. Department of Earth Sciences, University College London, Gower Street, London, WC1E 6BT, UK

    A. Dominic Fortes, Frank Browning & Ian G. Wood

  2. Centre for Planetary Sciences at UCL/Birkbeck, Gower Street, London, WC1E 6BT, UK

    A. Dominic Fortes, Frank Browning & Ian G. Wood

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  1. A. Dominic Fortes
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  2. Frank Browning
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Correspondence to A. Dominic Fortes.

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Fortes, A.D., Browning, F. & Wood, I.G. Cation substitution in synthetic meridianiite (MgSO4·11H2O) II: variation in unit-cell parameters determined from X-ray powder diffraction data. Phys Chem Minerals 39, 443–454 (2012). https://doi.org/10.1007/s00269-012-0498-8

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