Abstract
Statistical thermodynamics methods are utilised to characterise aspects of the entropy of formation of a planar electric double layer. The model system consists of a primitive model electrolyte but with off-centre charge cations and centro-symmetric anions, next to a planar, uniformly charged electrode. An expression is developed for the entropy of off-centre charge ions. The theoretically predicted results of this entropy as a function of the electrode surface charge are compared with those from the corresponding Monte Carlo simulations. The entropy change with respect to the absolute value of the surface charge density is seen to be negative (or normal) if the displacement of the cation charge centre is zero or is independent of temperature. However, if the displacement is temperature dependent, the entropy can be positive (or anomalous). In each situation, the simulation data are well reproduced by the predicted results.
GRAPHICAL ABSTRACT
![](/cms/asset/f7480a15-1384-4710-8ee8-8775d9e8954b/tmph_a_2045374_uf0001_oc.jpg)
Availability of data
Data available on request from the authors.
Acknowledgements
SL would like to acknowledge the financial support from the Faculty of Chemistry, Adam Mickiewicz University in Poznań, Poland.
Disclosure statement
No potential conflict of interest was reported by the author(s).