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Revisiting immiscibility through DFT chemical descriptors

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Abstract

The notion of fluids immiscibility is examined from the field observations (i.e. rock samples or measurements in drill holes) and experimental point of view, as well as from usual thermodynamics and theoretical hard-soft and acid–base and density functional theory concepts. Basically, fluids immiscibility relates to a difference in chemical potentials between the elements in presence, i.e. some differences in the first derivative of their free energy. The latter usually plots as a quartic curve with upward concave curvature. However, it can develop a local maximum, inducing immiscibility. The theoretical chemistry concepts consider in addition to chemical potential, the second derivatives of the energy, as hardness and electrophilicity, or polarizability and magnetizability. Those are due to external field components, electric or magnetic, whereas the two former derivatives depend directly on the quantitative changes in the electronic cloud. Those descriptors give insights to reactions evolution during the reaction path. Their introduction in the definition of fluids immiscibility is examined, documenting chemical reactions and path reflecting an open system. Mapping the values of molecule polarizability shows a linear trend from silica to fayalite and leucite, i.e. magnesian and alkali-alumino silicates. A local positive anomaly in polarizability, due to the near-by influence of phosphorous controls the extent of the immiscibility area. The technique could easily be applied in other fields to control hydrophilicity or hydrophobicity.

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Acknowledgements

This paper came out from discussions about ore generation in a magmatic context, with colleagues, Antonin Richard and Laurent Truche, both at GeoRessources, Nancy. Interestingly, the lab, former CREGU, has been founded by Bernard Poty, partly for studying fluid inclusions, when he came back from US and invented the Chaixmeca stage in 1972. Later on, I was introduced to theoretical chemistry by Pratim K Chattaraj at IIT Kharagpur, India. He encouraged me to continue in this way. Fruitful discussions about the Skaergaard, initially with late Alexander McBirney, and later with Marian Holness and Troels Nielsen guided my reflections. Three anonymous reviewers are acknowledged for their valuable comments about DFT and cDFT.

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  1. GéoRessources, UMR 7539, Université de Lorraine, BP 70239, 54506, Vandoeuvre/Nancy Cédex, France

    Jean-Louis Vigneresse

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Vigneresse, JL. Revisiting immiscibility through DFT chemical descriptors. Theor Chem Acc 139, 142 (2020). https://doi.org/10.1007/s00214-020-02652-6

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