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Interaction balance theory
Gabriel M Silva1, Xiaodong Liang1, Georgios M Kontogeorgis1
1Center for Energy Resources Engineering, Department of Chemical and Biochemical Engineering, Technical University of Denmark, Kgs. Lyngby, Denmark.
The Journal of Chemical Physics
|July 27, 2026
Summary
A new interaction balance theory quantifies electrolyte non-ideality by linking ionic interactions to activity coefficients. This framework aids in classifying electrolytes and predicting their thermodynamic properties.
Area of Science:
- Physical Chemistry
- Thermodynamics
- Solution Chemistry
Background:
- Electrolyte thermodynamics presents challenges in classifying electrolytes and predicting properties.
- Understanding ionic interactions is crucial for accurate solution behavior modeling.
Purpose of the Study:
- Introduce the interaction balance theory to link microscopic ionic interactions with macroscopic activity coefficients.
- Enable decomposition of intermolecular interactions and systematic analysis of non-ideality sources.
- Provide a quantitative classification of electrolytes.
Main Methods:
- Developed the interaction balance theory framework.
- Applied the theory to sodium halides (NaF, NaCl, NaBr, NaI) in various solvents.
- Analyzed contributions of Coulombic, short-range, and solvent-mediated interactions.
- Correlated interaction decompositions with salt solubility.
Main Results:
- The theory successfully captures distinct intermolecular behaviors of sodium halides.
- Differentiated contributions of various forces (Coulombic, repulsion, solvent-mediated).
- Linked interaction decompositions to observed salt solubilities.
- Identified the activity coefficient minimum as an equilibrium point for cumulative forces.
Conclusions:
- The interaction balance theory offers a quantitative method for interpreting electrolyte data.
- It disentangles the origins of system non-ideality.
- Provides guidance for developing thermodynamic models by highlighting dominant interactions.
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