Influence of the diffuse double layer on steady-state voltammetry

Dickinson, Edmund J. F.; Compton, Richard G.

doi:10.1016/j.jelechem.2011.08.002

Cited by 69 publications

(78 citation statements)

References 34 publications

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“…Non-systematic variation was observed in the values of the kinetic parameters when varying the KCl concentration, which suggests the exclusion of possible Frumkin effects [49,50].…”

Section: Voltammetric Kinetic Studiesmentioning

confidence: 93%

The use of differential pulse voltammetries to discriminate between the Butler–Volmer and the simple Marcus–Hush models for heterogeneous electron transfer: The electro-reduction of europium (III) in aqueous solution

Wang

Laborda

Henstridge

et al. 2012

Journal of Electroanalytical Chemistry

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“…Non-systematic variation was observed in the values of the kinetic parameters when varying the KCl concentration, which suggests the exclusion of possible Frumkin effects [49,50].…”

Section: Voltammetric Kinetic Studiesmentioning

confidence: 93%

The use of differential pulse voltammetries to discriminate between the Butler–Volmer and the simple Marcus–Hush models for heterogeneous electron transfer: The electro-reduction of europium (III) in aqueous solution

Wang

Laborda

Henstridge

et al. 2012

Journal of Electroanalytical Chemistry

Self Cite

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“…More recently, Compton and co-workers have done extensive work involving theory [66][67][68], simulations [37,66,69,70] (and see Chap. 7 of [3] or Chap.…”

Section: Historical Reviewmentioning

confidence: 99%

“…The additional species in their work are sometimes neutral [71,72] and sometimes charged [66,70], depending on the reaction being modeled. Modeling of uncharged and supporting ionic species has also been a feature of other models in the literature [58][59][60].…”

Section: Historical Reviewmentioning

confidence: 99%

Theory of linear sweep voltammetry with diffuse charge: Unsupported electrolytes, thin films, and leaky membranes

Yan

Bazant

Biesheuvel³

et al. 2017

Phys. Rev. E

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Linear sweep and cyclic voltammetry techniques are important tools for electrochemists and have a variety of applications in engineering. Voltammetry has classically been treated with the Randles-Sevcik equation, which assumes an electroneutral supported electrolyte. In this paper, we provide a comprehensive mathematical theory of voltammetry in electrochemical cells with unsupported electrolytes and for other situations where diffuse charge effects play a role, and present analytical and simulated solutions of the time-dependent PoissonNernst-Planck equations with generalized Frumkin-Butler-Volmer boundary conditions for a 1:1 electrolyte and a simple reaction. Using these solutions, we construct theoretical and simulated current-voltage curves for liquid and solid thin films, membranes with fixed background charge, and cells with blocking electrodes. The full range of dimensionless parameters is considered, including the dimensionless Debye screening length (scaled to the electrode separation), Damkohler number (ratio of characteristic diffusion and reaction times), and dimensionless sweep rate (scaled to the thermal voltage per diffusion time). The analysis focuses on the coupling of Faradaic reactions and diffuse charge dynamics, although capacitive charging of the electrical double layers is also studied, for early time transients at reactive electrodes and for nonreactive blocking electrodes. Our work highlights cases where diffuse charge effects are important in the context of voltammetry, and illustrates which regimes can be approximated using simple analytical expressions and which require more careful consideration.

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“…1,4 It includes the correction of the potential at the closest approach of the redox species, which may be varied with the concentration of the supporting electrolyte; well-known examples are cadmium ions, 5 zinc ions, 6 and some aromatic compounds. 7 However, there are some ambiguities in the participation of the specically adsorbed species, [8][9][10][11][12] in charge interactions, 13,14 in modication by nite ionic size, [15][16][17][18] in the geometrical effects [19][20][21][22][23] of the Poisson-Nernst-Planck equation, in simplication of the plane of the closest approach, 24 in complications by ions [25][26][27][28] and by the orientation of the solvent molecules, 29 in charge distribution within a redox species, 30 and in coupling of the charged redox species and supporting electrolyte. 31,32 The Frumkin's correction has recently been reviewed from a theoretical point of view.…”

mentioning

confidence: 99%

Decrease in the double layer capacitance by faradaic current

Aoki¹,

Chen

Zeng

et al. 2017

RSC Adv.

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This study describes the reverse of the well-known double layer effects on charge transfer kinetics in the relationship between a cause and an effect. The reversible redox reaction of a ferrocenyl derivative decreased the capacitive values of the double layer impedance up to negative values, corresponding to an inductive component. This observation was disclosed by the subtraction of the real admittance from the imaginary admittance, which can extract the net double layer capacitance from the Warburg impedance. The inductance-like behavior is caused due to two reasons: (i) the double layer capacitance in the polarized potential domain is determined by the low concentrations of the fieldoriented solvent dipoles that are considered as the conventionally employed redox concentrations and (ii) the double layer capacitance is caused by the orientation of the dipoles in the same direction as that of the electric field, whereas the redox reaction generates charge in the direction opposite to the field. The faradaic effect was demonstrated via the ac-impedance data obtained for the ferrocenyl compound in a KCl solution in the unpolarized potential domain between 1 Hz and 3 kHz frequency. The negative admittance was proportional to the frequency. The theory of negative capacitance was presented by combining the mirror-image surface charge with the Nernst equation.

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Influence of the diffuse double layer on steady-state voltammetry

Cited by 69 publications

References 34 publications

The use of differential pulse voltammetries to discriminate between the Butler–Volmer and the simple Marcus–Hush models for heterogeneous electron transfer: The electro-reduction of europium (III) in aqueous solution

The use of differential pulse voltammetries to discriminate between the Butler–Volmer and the simple Marcus–Hush models for heterogeneous electron transfer: The electro-reduction of europium (III) in aqueous solution

Theory of linear sweep voltammetry with diffuse charge: Unsupported electrolytes, thin films, and leaky membranes

Decrease in the double layer capacitance by faradaic current

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