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Additive Molar Volumes in Amorphous Ca/Sr Carbonate Solid Solutions

Mergelsberg, Sebastian T.·Prange, Micah P.·Kerisit, Sebastien N.
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Abstract

The development of predictive models of minor element incorporation in crystalline carbonate end products requires an understanding of the fundamental controls on metastable intermediate phase composition. In this study, we used small-angle X-ray scattering (SAXS), X-ray pair distribution function (PDF), thermogravimetric analysis (TGA), inductively coupled plasma mass spectrometry (ICP-MS), and transmission electron microscopy (TEM) to determine the composition-dependent density of an amorphous calcium–strontium carbonate (ACSC) solid solution. The amorphous calcium carbonate (ACC) and strontium carbonate (ASC) measured densities were ρ ACC = 2.19 ± 0.04 g/cm 3 and ρ ASC = 2.97 ± 0.05 g/cm 3 . Throughout our work, the experiments showed a dependence of the water content of the amorphous solid solution on the Sr mole fraction. An equation that relates the molar volume to the average cation radius, the carbonate ion radius, and the water volume was parameterized for hydrated crystalline carbonates and predicted well the molar volume of the ACSC solid solution. This finding indicates that, as for hydrated crystalline carbonates, the molar volumes of amorphous carbonates are additive and that water is a structural component of ACSC. Ab initio molecular dynamics (AIMD) simulations of the ACSC solid solutions showed strong linear correlations between calculated molar volumes and Sr and H 2 O contents, thus supporting the experimental results. In conclusion, our findings highlight the need to consider the full CaCO 3 –MeCO 3 –H 2 O ternary when quantifying metal cation incorporation in ACC.

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRYAb initio molecular dynamicsCalciteCationsInorganic carbon compoundsScattering

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Mergelsberg, Sebastian T., Prange, Micah P., Kerisit, Sebastien N.. 2024-02-23. Additive Molar Volumes in Amorphous Ca/Sr Carbonate Solid Solutions. https://doi.org/10.1021/acs.jpcc.3c08311

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