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The crystal structure and thermal expansion tensor of MgSO4–11D2O(meridianiite) determined by neutron powder diffraction

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Abstract

We have collected high-resolution neutron powder diffraction patterns from MgSO4·11D2O over the temperature range 4.2–250 K. The crystal is triclinic, space-group \( \text{P} \bar{1} \) (Z = 2) with a = 6.72746(6) Å, b = 6.78141(6) Å, c = 17.31803(13) Å, α = 88.2062(6)°, β = 89.4473(8)°, γ = 62.6075(5)°, and V = 701.140(6) Å3 at 4.2 K, and a = 6.75081(3) Å, b = 6.81463(3) Å, c = 17.29241(6) Å, α = 88.1183(3)°, β = 89.4808(3)°, γ = 62.6891(3)°, and V = 706.450(3) Å3 at 250 K. Structures were refined to wRp = 3.99 and 2.84% at 4.2 and 250 K, respectively. The temperature dependence of the lattice parameters over the intervening range have been fitted with a modified Einstein oscillator model which was used to obtain the coefficients of the thermal expansion tensor. The volume thermal expansion, αV, is considerably smaller than ice Ih at all temperatures, and smaller even than MgSO4·7D2O (although ∂αV/∂T is very similar for both sulfates); MgSO4·11D2O exhibits negative αV below 55 K (compared to 70 K in D2O ice Ih and 20 K in MgSO4·7D2O) The relationship between the magnitude and orientation of the principal axes of the expansion tensor and the main structural elements are discussed.

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Notes

  1. At the time of the neutron study (November 2004) it was still thought that Fritzsche’s salt was a dodecahydrate and we prepared our sample accordingly; as a result, our sample consisted of MgSO4·11D2O + water ice.

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Acknowledgments

The authors wish to thank the STFC ISIS facility for beam time, and technical support staff for invaluable assistance. We are grateful to Ronald Peterson and Ruiyao Wang for sharing their structural data with us prior to publication. We also thank Christine McCarthy, David Hogenboom, and Andrew Dougherty for informative discussions about their work on MS11, and thank Lidunka Vočadlo for contributions to the data analysis. Giovanni Ferraris and one anonymous reviewer provided useful comments, which improved the manuscript. This work was funded by the Science and Technology Facilities Council (STFC), U. K., grant numbers PPA/P/S/2003/00247 and PP/E006515/1.

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Authors and Affiliations

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

    A. D. Fortes & I. G. Wood

  2. ISIS Facility, Rutherford Appleton Laboratory, Chilton, Didcot, Oxfordshire, OX11 0LA, UK

    K. S. Knight

  3. The Natural History Museum, Cromwell Road, London, SW7 5BD, UK

    K. S. Knight

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  1. A. D. Fortes
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Correspondence to A. D. Fortes.

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Fortes, A.D., Wood, I.G. & Knight, K.S. The crystal structure and thermal expansion tensor of MgSO4–11D2O(meridianiite) determined by neutron powder diffraction. Phys Chem Minerals 35, 207–221 (2008). https://doi.org/10.1007/s00269-008-0214-x

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