Issue 21, 2023

A total scattering study of prenucleation structures in saturated aqueous magnesium sulfate – observation of extended clusters

Abstract

Through a combination of X-ray and neutron total scattering and Empirical Potential Structure Refinement (EPSR) we explore the prenucleation structures of saturated aqueous magnesium sulfate. The atomistic model we present reveals a system characterised by isolated octahedral aquo magnesium species Mg(H2O)6, magnesium sulfate pairs (Mg(H2O)5SO4) and extended clusters built from corner-sharing MgO6 and SO4 polyhedra. Many of these features are directly observed in the crystal structures of the known solid form hydrates, including isolated polyhedra, corner sharing chains and rings, and it is only for the extended 3D polyhedral networks of the lower hydrates (mono- & di-) that no proto structures are observed in 2M solution. Looking at the average first solvation shell of the sulfate anion we see a complex and flexible environment that commonly includes water molecules brought into proximity by a coordinated hydrated magnesium. What emerges is a high probability that 10 water molecules will be observed in a combined tetrahedral/octahedral arrangement with a further 7 taking up more dispersed positions giving an average coordination of 17. The tendency for ions to aggregate into clusters allows areas of bulk water to exist that exhibit subtle differences in structure to that of pure water.

Graphical abstract: A total scattering study of prenucleation structures in saturated aqueous magnesium sulfate – observation of extended clusters

Supplementary files

Article information

Article type
Paper
Submitted
14 Mar 2023
Accepted
12 May 2023
First published
13 May 2023
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2023,25, 14898-14906

A total scattering study of prenucleation structures in saturated aqueous magnesium sulfate – observation of extended clusters

D. J. M. Irving, M. E. Light, M. P. Rhodes, T. Threlfall and T. F. Headen, Phys. Chem. Chem. Phys., 2023, 25, 14898 DOI: 10.1039/D3CP01157G

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements