Multiionic and Permittivity‐Related Effects on the Diffuse Electric Double Layer Structure at Solid‐Electrolyte Solution Interfaces

López-Garcı́a, J.J.; Horno, J.; Grosse, Constantino

doi:10.1155/2018/4316894

Cited by 9 publications

(12 citation statements)

References 32 publications

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“…Although the equilibrium properties of the system have been extensively studied in previous papers [22,23], we briefly describe the more important aspects needed for the interpretation of the out of equilibrium system behavior.…”

Section: Resultsmentioning

confidence: 99%

Numerical Solution of the Electrokinetic Equations for Multi-ionic Electrolytes Including Different Ionic Size Related Effects

2018

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One of the main assumptions of the standard electrokinetic model is that ions behave as point-like entities. In a previous work (López-García, et al., 2015) we removed this assumption and analyzed the influence of finite ionic size on the dielectric and electrokinetic properties of colloidal suspensions using both the Bikerman and the Carnahan–Starling equations for the steric interactions. It was shown that these interactions improved upon the standard model predictions so that the surface potential, electrophoretic mobility, and the conductivity and permittivity increment values were increased. In the present study, we extend our preceding works to systems made of three or more ionic species with different ionic sizes. Under these conditions, the Bikerman and Carnahan–Starling expressions cease to be valid since they were deduced for single-size spheres. Fortunately, the Carnahan–Starling expression has been extended to mixtures of spheres of unequal size, namely the “Boublik–Mansoori–Carnahan–Starling–Leland” (BMCSL) equation of state, making it possible to analyze the most general case. It is shown that the BMCSL expression leads to results that differ qualitatively and quantitatively from the standard electrokinetic model.

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Section: Resultsmentioning

confidence: 99%

Numerical Solution of the Electrokinetic Equations for Multi-ionic Electrolytes Including Different Ionic Size Related Effects

2018

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“…Similar effects are observed in colloidal systems and nanoscale solid-liquid interfaces where water confinement and dispersion forces become important. [45][46][47][48][49] The behavior of water in crowded environments is indeed quite different than bulk water. Fundamental spectroscopic studies combined with MD simulations have recently elucidated the nature of slow-water in crowded environments.…”

Section: Donnan Potentialmentioning

confidence: 99%

“…Minimization of free energy, or equivalently, integration of a steady-state Born-modified Poisson-Nernst-Planck (PNP) model with ion-pair binding yield such a generalized Boltzmann distribution as follows. 48,69,70 , = , exp {−…”

Section: Relation With Mean-field Theorymentioning

confidence: 99%

Ion Pairing and Dielectric Decrement in Glycosaminoglycan Brushes

et al. 2021

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Molecular dynamics simulations of hyaluronic acid and heparin brushes are presented that show important effects of ion-pairing, water dielectric decrease, and co-ion exclusion. As in prior studies of macromolecular crowding under physiologically-relevant salt concentrations, our results show equilibria with electroneutrality attained through screening and pairing of brush anionic charges by cations. Most surprising is the reversal of the Donnan potential that would be expected based on electrostatic Boltzmann partitioning alone. Water dielectric decrement within the brush domain is also associated with Born hydration-driven cation exclusion from the brush. We observe that the primary partition energy attracting cations to attain brush electroneutrality is the ion-pairing or salt-bridge energy associated with cation-sulfate and cation-carboxylate solvent-separated and contact ion pairs. Potassium and sodium pairing to glycosaminoglycan carboxylates and sulfates consistently show similar abundance of contact-pairing and solvent-separated pairing. In these crowded macromolecular brushes, ion-pairing, Born-hydration, and electrostatic potential energies all contribute to attain electroneutrality and should therefore contribute in mean-field models to accurately represent brush electrostatics.

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“…We would like to note that similar replacement from the cathode surface of alkaline cations by another alkaline cations due to a difference in their excess polarizabilities in aqueous medium was discussed within the mean-field theory in paper. 27,28 In order to confirm our theoretical findings, we performed MD simulations (for the details of the simulation setup, see the previous section). Although there are some quantitative differences, the qualitative behavior of the system is in good agreement with the theoretical predictions.…”

Section: Resultsmentioning

confidence: 77%

Two-Component Electrolyte Solutions with Dipolar Cations on a Charged Electrode: Theory and Computer Simulations

et al. 2020

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The development of advanced electrochemical devices for energy conversion and storage requires fine tuning of electrode reactions, which can be accomplished by altering the electrode/solution interface structure. Particularly, in case of an alkali-salt electrolyte the electric double layer (EDL) composition can be managed by introducing organic cations (e.g. room temperature ionic liquid cations) that may possess polar fragments. To explore this approach, we develop a theoretical model predicting the 1 arXiv:2007.00378v1 [cond-mat.soft] 1 Jul 2020 efficient replacement of simple (alkali) cations with dipolar (organic) ones within the EDL. For the typical values of the molecular dipole moment (2 − 4 D) the effect manifests itself at the surface charge densities higher than 30 µC/cm 2. We show that the predicted behavior of the system is in qualitative agreement with the molecular dynamics simulation results.

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Multiionic and Permittivity‐Related Effects on the Diffuse Electric Double Layer Structure at Solid‐Electrolyte Solution Interfaces

Cited by 9 publications

References 32 publications

Numerical Solution of the Electrokinetic Equations for Multi-ionic Electrolytes Including Different Ionic Size Related Effects

Numerical Solution of the Electrokinetic Equations for Multi-ionic Electrolytes Including Different Ionic Size Related Effects

Ion Pairing and Dielectric Decrement in Glycosaminoglycan Brushes

Two-Component Electrolyte Solutions with Dipolar Cations on a Charged Electrode: Theory and Computer Simulations

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