A modified Poisson–Boltzmann analysis of the capacitance behavior of the electric double layer at low temperatures

Bhuiyan, L. B.; Outhwaite, C.W.; Henderson, Douglas

doi:10.1063/1.1992427

Cited by 44 publications

(37 citation statements)

References 31 publications

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“…Without a factor in front of b in the small b expression for g d (d/2) that can become increasingly smaller than one as T is decreased, a capacitance anomaly is improbable. It is this factor that produces equation (9) and the low b behavior of the contact product. The PB/GCS and HNC/MSA theories lack such a factor and does not produce (in the case of the PB/GCS theory) or is unlikely (in the case of the HNC/MSA theory) to produce a capacitance anomaly.…”

Section: Discussionmentioning

confidence: 99%

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Application of a recently proposed test to the hypernettedchain approximation for the electric double layer

Henderson¹,

Alawneh²,

Saavedra-Barrera³

et al. 2007

Condens. Matter Phys.

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Bhuiyan, Outhwaite, and Henderson, J. Electroanal. Chem., 2007, 607, 54, have studied the electric double layer formed by a symmetric electrolyte in the restricted primitive model and suggested that an examination of the product of the coion and counterion profiles, normalized to the one when the distance of an ion from the electrode is large, is an interesting and useful test of a theory. This product is identically one in the PoissonBoltzmann theory but simulation results show that, at contact, this product can be greater or smaller than one at small electrode charge but always seems to tend to zero at large electrode charge. In this study we report the results of the hypernetted chain approximation (HNC/MSA version) for this product and find that, at contact, for this theory this product is always greater than the one at small electrode charge but tends to zero at large electrode charge.

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Section: Discussionmentioning

confidence: 99%

“…In addition, nonaqueous low concentration experimental systems can exhibt this behavior [7]. In the past few years, this anomalous behavior has been found in some of the better theories [8][9][10].…”

Section: Introductionmentioning

confidence: 99%

Application of a recently proposed test to the hypernettedchain approximation for the electric double layer

Henderson¹,

Alawneh²,

Saavedra-Barrera³

et al. 2007

Condens. Matter Phys.

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“…At any rate, the surface heterogeneity can have considerable effects on electrokinetic properties or colloidal forces. 16,17 Computer simulations have contributed to a better understanding of EDLs including multivalent ions and related phenomena challenging the classical theory, [18][19][20][21][22][23][24][25] such as charge inversion and attractive electrostatic forces between likecharge particles. [26][27][28][29] Computational methods can also become a valuable tool to shed light on surface heterogeneity effects.…”

Section: Introductionmentioning

confidence: 99%

Effect of the surface charge discretization on electric double layers: A Monte Carlo simulation study

Madurga

Vilaseca

Mas

et al. 2007

The Journal of Chemical Physics

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The structure of the electric double layer in contact with discrete and continuously charged planar surfaces is studied within the framework of the primitive model through Monte Carlo simulations. Three different discretization models are considered together with the case of uniform distribution. The effect of discreteness is analyzed in terms of charge density profiles. For point surface groups, a complete equivalence with the situation of uniformly distributed charge is found if profiles are exclusively analyzed as a function of the distance to the charged surface. However, some differences are observed moving parallel to the surface. Significant discrepancies with approaches that do not account for discreteness are reported if charge sites of finite size placed on the surface are considered.

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“…5,6 Only more developed theories were able to reproduce this behavior. 16,34,[64][65][66] We have calculated the anomalous capacitance behavior for 2:1 and 3:1 electrolytes and found a behavior similar to the 1:1 case if the reduced temperature is scaled appropriately. 31 Alawneh et al 59 have studied the capacitance anomaly for a symmetric 1:1 0.1 M electrolyte near a polarizable electrode.…”

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Behavior of 2:1 and 3:1 Electrolytes at Polarizable Interfaces

et al. 2011

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The behavior of the electrical double layer (DL) is known to be different at polarizable interfaces, specifically, at a metallic electrode (where the dielectric constant of the electrode is infinitely large, ǫ 1 → ∞) and at an air/electrolyte interface (where the dielectric constant of the electrode is ǫ 1 = 1) than is the case for unpolarized interfaces. For the polarized interface, if multivalent ions are present, these ions are attracted/repelled more than is the case for monovalent ions. Therefore, the divalent/trivalent ions (assumed to be cations to be specific) accumulate near the metallic electrode more than for the unpolarized electrode and a charge inversion occurs. In such asymmetric electrolytes, this results in a large potential at zero electrode charge. The behavior is reversed for the air/electrolyte interface. This is more pronounced at low reduced temperatures (or, equivalently, at high ionic couplings). The anomalous capacitance behavior of the DL is seen for the unpolarized electrode, where the temperature derivative of the capacitance is positive at low reduced temperatures (characteristic of electrolytes with ions with high ionic couplings or molten salt DLs at room temperatures) while it is negative at high reduced temperatures (characteristic or aqueous solutions of monovalent salts at room temperatures). At least for the states we consider, this anomalous behavior is enhanced for the * Author for correspondence 1 air/electrolyte interface but vanishes for a metallic electrode. Our Monte Carlo simulations of these phenomena are reported.

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A modified Poisson–Boltzmann analysis of the capacitance behavior of the electric double layer at low temperatures

Cited by 44 publications

References 31 publications

Application of a recently proposed test to the hypernettedchain approximation for the electric double layer

Application of a recently proposed test to the hypernettedchain approximation for the electric double layer

Effect of the surface charge discretization on electric double layers: A Monte Carlo simulation study

Behavior of 2:1 and 3:1 Electrolytes at Polarizable Interfaces

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