The Differential Capacity of the Electrical Double Layer. The Role of the Anion

The Impedance Response of a Passive Film Revisited by a Double Modulation Technique

“…The concept of no a priori separation of charging and faradaic currents was introduced by Delahay in the 60’s,, and has been extensively discussed in the literature . Indeed, even if the separation of faradaic and capacitive currents is widely used in the literature for data analysis because it greatly simplifies simulations and fittings, it is questionable in many different cases such as experiments performed in low‐concentrated supporting electrolyte and even the specific adsorption of diluted reactants as shown by the results presented by Grahame for the adsorption of different ions studied with a mercury electrode . Anson et al ,.…”

“…[7][8][9][10][11] Indeed, even if the separation of faradaic and capacitive currents is widely used in the literature for data analysis because it greatly simplifies simulations and fittings, it is questionable in many different cases such as experiments performed in low-concentrated supporting electrolyte and even the specific adsorption of diluted reactants as shown by the results presented by Grahame for the adsorption of different ions studied with a mercury electrode. [12][13][14] Anson et al [7,15] and Feldberg [8] showed that a charge injection to an ideal polarizable electrode results in two relaxations of the double layer corresponding to the charge neutralization on the electrode in the higher frequency domain and to the charge rearrangement in the diffuse layer in a lower frequency range.…”

Integral equation theory for the electrode-electrolyte interface with the central force water model. Results for an aqueous solution of sodium chloride

“…The minimum in the differential capacitance curve has been identified with the beginning of water reorientation in the adsorbed water layer [1]. The asymmetry in the differential capacitance curve with respect to zero surface charge and the existence of a minimum at negative surface charge density are typical of the experimental data for simple electrolytes [10]. It has been argued that the asymmetry is a consequence of ionic polarizability or of ion-specific interaction with the electrode [56].…”

“…Several phenomenological models for the water monolayer employing adjustable parameters for the specific water interaction with the electrode were proposed to account for the experimental data [8,9]. Of particular interest is the pronounced asymmetry of the differential capacitance with respect to the potential of zero charge, which characterizes the interface between an aqueous electrolyte and a mercury electrode [10].…”

The Structure of the Electrical Double Layer at the Metal-Solution Interface

“…The energetics of specific adsorption have been explained in terms of covalent forces (127,128,136,144) between Hg and the halide ion and electrostatic forces. If the idea of covalent binding is correct, adsorbability (20) should increase with increasing bond strength of the Hg-X correlation (see Table I).…”