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Formation of Charge Carriers in Liquids
Dennis C Prieve1, Benjamin A Yezer1, Aditya S Khair1
1Department of Chemical Engineering, Carnegie Mellon University, Pittsburgh, PA, 15213, United States.
Advances in Colloid and Interface Science
|January 12, 2017
Summary
The Fuoss theory explains electrolyte conductivity by relating dissociation to solvent properties and ion-pair size. This model accurately describes true electrolytes, water-in-oil microemulsions, and charged alcohol mixtures.
Area of Science:
- Physical Chemistry
- Electrochemistry
- Colloid Science
Background:
- Historical contributions to electrolyte conductivity by Faraday, Arrhenius, Kohlrausch, Bjerrum, Debye, Hückel, and Onsager.
- The 1933 Fuoss & Kraus theory on solvent effects on electrolyte dissociation equilibria.
- Charge-fluctuation theory for water-in-oil microemulsions and potential electrolytes.
Purpose of the Study:
- To review the Fuoss & Kraus theory and its predictions for electrolyte dissociation.
- To examine the application of charge-fluctuation theory to microemulsions and charged systems.
- To analyze the exponential dependence of ion-pair dissociation on the Bjerrum length (λB) and ion-pair size (a).
Main Methods:
- Review of historical and foundational theories in electrolyte conductivity.
- Analysis of the Fuoss & Kraus theory and its predictions regarding solvent effects.
- Examination of experimental data for true electrolytes, microemulsions, and alcohol mixtures.
Main Results:
- The Fuoss & Kraus theory predicts exponential decay of dissociation equilibrium constants with λB/a.
- Experimental evidence supports the dependence of conductivity on λB for solvents.
- Charge-fluctuation theory and Fuoss theory model conductivity in microemulsions and alcohol mixtures, showing exponential dependence on λB/a.
Conclusions:
- The Fuoss theory provides a robust framework for understanding electrolyte dissociation across various systems.
- Ion-pair dissociation in true electrolytes, microemulsions, and charged alcohol mixtures exhibits an exponential dependence on the ratio of the Bjerrum length to ion-pair size (λB/a).
- The study highlights the unifying principles governing charge behavior in diverse chemical environments.
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