Monte Carlo studies of ion size effects in the diffuse double layer

Fawcett, W. Ronald

doi:10.1016/j.electacta.2009.02.025

Cited by 16 publications

(21 citation statements)

References 25 publications

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“…Fawcett and colleagues extended an analytical derivation of the potential drop across the diffuse layer on the basis of definite integrals leading to a Taylor series in the Gouy-Chapman estimate of the same quantity [13,14]. Their model gives an excellent description of Monte Carlo data, and presents the advantage of providing an analytical correction to the Gouy-Chapman model.…”

Section: Standard Double-layer Modelsmentioning

confidence: 99%

Ab Initio Electrochemical Properties of Electrode Surfaces

Dabo

Bonnet

et al. 2010

Fuel Cell Science

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Section: Standard Double-layer Modelsmentioning

confidence: 99%

Ab Initio Electrochemical Properties of Electrode Surfaces

Dabo

Bonnet

et al. 2010

Fuel Cell Science

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“…This may be demonstrated using Monte Carlo (MC) simulations. Beginning with the work of Torrie and Valleau in the early 1980s [84,85], it was shown that the GC estimates of f d are seriously in error especially when polyvalent ions predominate in the diffuse layer [86][87][88]. MC data for a 1:1 electrolyte at various concentrations for an ion size of 300 pm are shown in Fig.…”

Section: The Last 10 Yearsmentioning

confidence: 99%

“…The function Η 0 accounts for the electrostatic part of the effects ion size on the ionic atmosphere. These functions may be estimated from the MC simulations [88].…”

Section: The Last 10 Yearsmentioning

confidence: 99%

Fifty years of studies of double layer effects in electrode kinetics—a personal view

Fawcett

2011

J Solid State Electrochem

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Developments in the treatment of double layer effects in electrode kinetics are outlined. These include discreteness-of-charge effects in the presence of specific adsorption, solvent effects in electron transfer reactions, and effects related to the distribution of charge in polyatomic reactants. The importance of studies at single crystal electrodes is emphasized, and the development of a single crystal ultramicroelectrode described. Finally, a method of improving the estimate of the diffuse layer potential drop on the basis of Monte Carlo simulations is presented.

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“…Other alternative procedures include Monte Carlo, Hypernetted Chain, andyor Mean Spherical Approximation procedures (e.g. see discussions in Gonzales-Tovar and Lozada-Cassou, 1989; Outhwaite and Bhuiyan, 1991; Phillips, 1999;Attard, 2006;Fawcett, 2006Fawcett, , 2009; these procedures can be computationally intensive and in application also may employ theoretical simplifications that are not necessarily applicable to all situations. For example, Fawcett (2006) suggests that both ionic volumes and thicknesses of the diffuse layer can be adjusted in Mean Spherical Approximation applications.…”

Section: Alternatives To Poisson -Boltzmann Chargeypotential Relationmentioning

confidence: 98%

Extending the diffuse layer model of surface acidity constant behaviour: IV. Diffuse layer charge/potential relationships

Loux

2011

Chemical Speciation & Bioavailability

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Most current electrostatic surface complexation models describing ionic binding at the particleywater interface rely on the use of Poisson -Boltzmann (PB) theory for relating diffuse layer charge densities to diffuse layer electrostatic potentials. PB theory is known to contain a number of implicit assumptions whose significance in environmental applications is largely unknown. This study seeks to better quantify the impact of these assumptions by: (1) comparing potentials obtained from planar analytical solutions to the PB with those obtained from Hypernetted Chain (HNC) theory (Attard, 2006), (2) assessing the accuracy of the Ohshima et al. (1982) spherical approximate analytical solution to the PB equation by comparison with published numerical values (Loeb et al., 1961), and (3) comparing interfacial potential estimates obtained from the spherical approximate analytical solution to the PB equation at and adjacent to the particle surface with potential estimates obtained from the Entropic Balanced Surface Potential (EB) model (Loux, 1985;Loux and Anderson, 2001) and published potential estimates obtained from the Hypernetted ChainyMean Spherical Approximation procedure (HNCyMSA; Gonzalez-Tovar and Lozada-Cassou, 1989). EB potential estimates were obtained assuming a surface volume thickness equal to the Bjerrum length (0.357 nm in a room temperature monovalent electrolyte solution). Findings from the study included: (1) the planar, surficial HNC estimates compared favourably with planar surficial PB relationships at charge densities equal to or less than 0.05 C m À 2 , (2) the Ohshima et al. (1982) approximate spherical analytical solution to the PB equation replicated the numerical charge density estimates required to obtain 72 datapoints over an eCykT range of one to four with a maximum error of 3.37% and a coefficient of variation of 0.92%, (3) for a 0.1 mm radius particle in a room temperature 0.01 M (1 : 1) ionic strength solution, potential estimates over a surface charge density range of 0 to 0.3 C m À 2 occurred in the following order: C HNCyMSA;R 4C PB;R 4C HNCyMSA;Rþ0:2125 nm 4C PB;Rþ0:2 nm $ C EB 4C HNCyMSA;Rþ0:425 nm $ C PB;Rþ0:4 nm and (4) with 45 datapoints including both 1 mm and 10 nm radius particles over an ionic strength range of 1.0 to 0.001 M, the PB potential estimates 0.2 nm from the particle surface (C PB;Rþ0:2 nm ) closely tracked the corresponding EB estimates (C EB ) with a 5.3% coefficient of variation. If one assumes that interfacial potential values adjacent to the particle surface are most relevant for describing environmental phenomena and that a 10% coefficient of variation in potential estimates is acceptable, then presumably any of the non-surficial chargeypotential relationships would be useful below an absolute charge density of 0.125 C m À 2 (with monovalent electrolyte solutions).

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Monte Carlo studies of ion size effects in the diffuse double layer

Cited by 16 publications

References 25 publications

Ab Initio Electrochemical Properties of Electrode Surfaces

Ab Initio Electrochemical Properties of Electrode Surfaces

Fifty years of studies of double layer effects in electrode kinetics—a personal view

Extending the diffuse layer model of surface acidity constant behaviour: IV. Diffuse layer charge/potential relationships

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