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Thermodynamics of electrolyte solutions near charged surfaces: Constant surface charge vs constant surface potential

Authors: Dorian Bruch; Christopher Balzer; Zhen-Gang Wang;

Thermodynamics of electrolyte solutions near charged surfaces: Constant surface charge vs constant surface potential

Abstract

Electric double layers are ubiquitous in science and engineering and are of current interest, owing to their applications in the stabilization of colloidal suspensions and as supercapacitors. While the structure and properties of electric double layers in electrolyte solutions near a charged surface are well characterized, there are subtleties in calculating thermodynamic properties from the free energy of a system with charged surfaces. These subtleties arise from the difference in the free energy between systems with constant surface charge and constant surface potential. In this work, we present a systematic, pedagogical framework to properly account for the different specifications on charged bodies in electrolyte solutions. Our approach is fully variational—that is, all free energies, boundary conditions, relevant electrostatic equations, and thermodynamic quantities are systematically derived using variational principles of thermodynamics. We illustrate our approach by considering a simple electrolyte solution between two charged surfaces using the Poisson–Boltzmann theory. Our results highlight the importance of using the proper thermodynamic potential and provide a general framework for calculating thermodynamic properties of electrolyte solutions near charged surfaces. Specifically, we present the calculation of the pressure and the surface tension between two charged surfaces for different boundary conditions, including mixed boundary conditions.

Country
United States
Related Organizations
Keywords

General Physics and Astronomy, Physical and Theoretical Chemistry, 540, 530

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selected citations
These citations are derived from selected sources.
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
6
Top 10%
Average
Top 10%
Green