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Linear Free-Energy Relationships (LFER) and Solvation Thermodynamics: The Case of Water and Aqueous Systems

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Abstract

The Abraham solvation parameter model, known alternatively as the Linear Solvation-Energy Relationships (LSER) model, is critically examined for its capacity to predict the hydration free-energy for a variety of solutes. The very linearity of the LSER approach is reconsidered as regards the hydrogen-bonding contribution to solvation free energy. This is done by combining the equation-of-state solvation thermodynamics with the statistical thermodynamics of hydrogen bonding. Thus, this hydrogen-bonding contribution is placed on a firm thermodynamic basis and the predictive calculations are now possible with known acidity and basicity, A and B, molecular descriptors. The LFER coefficients are now expressed in terms of the A and B descriptors. The methodology for the derivation of the new linear equations for the hydrogen-bonding contribution to solvation free energy is presented along with examples of calculations. The implication for the exchange of information on intermolecular interactions between diverse Quantitative Structure–Property Relationships (QSPR) and other approaches is discussed. The proposed changes and descriptor adjustments augments the LSER capacity for solvent screening and use in numerous applications in the broader chemical, biochemical and environmental sector. A critical discussion of perspectives and the challenging issues is also presented.

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Acknowledgements

This research is supported by ASPIRE, the technology program management pillar of Abu Dhabi’s Advanced Technology Research Council (ATRC), via the ASPIRE “AARE (ASPIRE Awards for Research Excellence)” and through grant no. AARE20-246 to Ioannis Zuburtikudis of Abu Dhabi University.

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Authors and Affiliations

  1. Department of Chemical Engineering, Aristotle University of Thessaloniki, 54624, Thessaloniki, Greece

    Costas Panayiotou

  2. Department of Chemical Engineering, Abu Dhabi University, Abu Dhabi, UAE

    Hadil Abu Khalifeh & Ioannis Zuburtikudis

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  1. Costas Panayiotou
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  2. Hadil Abu Khalifeh
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  3. Ioannis Zuburtikudis
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CP: Concept / formalism development, Calculations, Manuscript preparation IZ: Financial support, calculations, Manuscript preparation HAK: Literature search, calculations, Manuscript preparation All authors reviewed the manuscript

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Correspondence to Costas Panayiotou or Ioannis Zuburtikudis.

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Panayiotou, C., Abu Khalifeh, H. & Zuburtikudis, I. Linear Free-Energy Relationships (LFER) and Solvation Thermodynamics: The Case of Water and Aqueous Systems. J Solution Chem 53, 228–255 (2024). https://doi.org/10.1007/s10953-023-01290-3

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