Isothermal equation of state and high‐pressure phase transitions of synthetic meridianiite (MgSO4·11D2O) determined by neutron powder diffraction and quasielastic neutron spectroscopy. Issue 1 (1st February 2017)

• Record Type: Journal Article
• Authors: Fortes, A. Dominic; Fernandez-Alonso, Felix; Tucker, Matthew; Wood, Ian G.
• Is Part Of: Acta crystallographica. Volume 73:Issue 1(2017:Feb.)
• Page Start: 33
• Page End: 46
• Publication Date: 2017-02-01
• Subjects: meridianiite -- undecahydrate -- enneahydrate -- equation of state -- neutron diffraction -- quasielastic neutron scattering
• DOI: 10.1107/S2052520616018254
• Languages: English
• ISSNs: 2052-5206

Abstract

Abstract : We report high‐pressure neutron powder diffraction measurements of the most hydrated phase in the MgSO4 –H2 O system, magnesium sulfate undecahydrate, including an analysis of the elastic strain tensor and observations concerning phase changes that occur at high pressure. Abstract : We have collected neutron powder diffraction data from MgSO4 ·11D2 O (the deuterated analogue of meridianiite), a highly hydrated sulfate salt that is thought to be a candidate rock‐forming mineral in some icy satellites of the outer solar system. Our measurements, made using the PEARL/HiPr and OSIRIS instruments at the ISIS neutron spallation source, covered the range 0.1 < P < 800 MPa and 150 < T < 280 K. The refined unit‐cell volumes as a function of P and T are parameterized in the form of a Murnaghan integrated linear equation of state having a zero‐pressure volume V 0 = 706.23 (8) Å 3, zero‐pressure bulk modulus K 0 = 19.9 (4) GPa and its first pressure derivative, K ′ = 9 (1). The structure's compressibility is highly anisotropic, as expected, with the three principal directions of the unit‐strain tensor having compressibilities of 9.6 × 10 −3, 3.4 × 10 −2 and 3.4 × 10 −3 GPa −1, the most compressible direction being perpendicular to the long axis of a discrete hexadecameric water cluster, (D2 O)16 . At high pressure we observed two different phase transitions. First, warming of MgSO4 ·11D2 O at 545 MPa resulted in a change in the diffraction pattern at 275 K consistent with partial (peritectic) melting; quasielastic neutron spectra collected simultaneously evince the onset of the reorientational motion of D2 O molecules with characteristic time‐scales of 20–30 ps, longer than those found in bulk liquid water at the same temperature and commensurate with the lifetime of solvent‐separated ion pairs in aqueous MgSO4 . Second, at ∼ 0.9 GPa, 240 K, MgSO4 ·11D2 O decomposed into high‐pressure water ice phase VI and MgSO4 ·9D2 O, a recently discovered phase that has hitherto only been formed at ambient pressure by quenching small droplets of MgSO4 (aq) in liquid nitrogen. The fate of the high‐pressure enneahydrate on further compression and warming is not clear from the neutron diffraction data, but its occurrence indicates that it may also be a rock‐forming mineral in the deep mantles of large icy satellites.