Capacity differential double-layer

Various methods have been employed for the determination of E of liquid and solid metals. Besides purely electrochemical ones (e.g. measurement of the differential double layer capacity (see also chapter 4.2)) further techniques have been used for the investigation of the surface tension at the solid/electrolyte solution phase boundary. The employed methods can be grouped into several families based on the meas-... 

Measurements of the interfaeial eapacitance (the differential double layer capacity Cdl) have been used widely, the method has been labelled tensammetry [46Bre, 52Bre, 51Dosl, 52Dosl, 63Bre]. Various experimental setups based on arrangements for AC polarography, lock-in-amplifier, impedance measurement etc. have been employed. In all reports evaluated in the lists of data below the authors have apparently taken precautions in order to measure only the value of Cdl-... 

In any event, there is always a strict, equilibrium relation between the charge density, qM, on the electrode sur ce and the total potential difference, E, between the bulk phases of electrode and solution. This relation is often characterized by the differential double-layer capacity, Cd, defined as... 

The current density, will be the sum of the faradaic current density, jF, and the charging current density, c, cf. eqn. (8). The latter is related to the interfacial potential indicated in an implicit way by eqn. (20). The theory of the electrical double layer provides no analytical expression for the relation between E and qM and so, rigorously, this part of the problem would have to be solved numerically using the empirical relationship, which is known for many commonly used indifferent electrolytes. If Cd = dqM/dE is the differential double-layer capacity, we have... 

Fig. 4. Differential double-layer capacity as a function of d.c. potential of the mercury electrode in aqueous solutions of 0.1 M potassium salts, From ref. 20.

In its most simple form, this means without effects such as adsorption or formation of coatings at the electrode surface36. The resistance, Rc, represents electrical conductivity of the electrolyte and is not a property of the electrode itself. The differential double-layer capacity, Cmetal surface of the metal-electrolyte interface, which is in equilibrium with an equal excess of charge but opposite in sign at the side of the electrolyte. 

Area, constant, optical absorption Activity, absorption coefficient Debye length Cyclic voltammogram Capacitance / j,F Double layer capacity / 0.F Differential double layer capacity Integral double layer capacity Concentration / M Surface concentration Bulk concentration / M Diffusion coefficient / cm s ... 

The current transferred from the matrix to the solution is involved either in doublelayer charging or in faradaic electrode reactions. The differential double-layer capacity, defined by... 

Electrochemical techniques such as chronocoulometry, integrated cyclic voltammetry curves, or differentiating double-layer capacity measurements as a function of bulk concentrations can be used to estimate FA however, these types of determinations may still be in error since they measure the total number of surface species, while the number of molecules at active sites which exhibit both the EM and CT effects may be much smaller. Thus, the estimates of Gsers 10 to 10 found at pretreated Ag, for example, may err on the low side if special active sites are involved in SERS. It has been estimated that only 3% of the surface sites are SERS active. " ... 

Figure 2.9, it can be seen that the interfacial capacitance does show a dependence on concentration, particularly at low concentrations. In addition, whilst there is some evidence of the expected step function away from the pzc, the capacitance is not independent of V. Finally, and most destructive, the Helmholtz model most certainly cannot explain the pronounced minimum in the plot at the pzc at low concentration. The first consequence of Figure 2.9 is that it is no longer correct to consider that differentiating the y vs. V plot twice with respect to V gives the absolute double layer capacitance CH where CH is independent of concentration and potential, and only depends on the radius of the solvated and/or unsolvated ion. This implies that the dy/dK (i.e. straight lines joined at the pzc. Thus, in practice, the experimentally obtained capacitance is (ddifferential capacitance. (The value quoted above of 0.05-0,5 Fm 2 for the double-layer was in terms of differential capacitance.) A particular value of (di M/d V) is obtained, and is valid, only at a particular electrolyte concentration and potential. This admits the experimentally observed dependence of the double layer capacity on V and concentration. All subsequent calculations thus use differential capacitances specific to a particular concentration and potential. 

Figure 7. Comparison of (a, solid) electrochemical and (b, dashed) UHV measurements of the H, coverage/potentiaI differential versus potential on Pt(lll).1.) cathodic sweep (25 mV/s) voltammogram in 0.3 M HF from Ref. 20, constant double layer capacity subtracted, b.) dB/d(A ) versus A plot derived from A versus B plot of Ref. 26. Potential scales aligned at zero coverage. Areas under curves correspond to a.) 0.67 and b.) 0.73 M per surface Pt atom.

The PZC may also be seen on differential capacity curves when specific adsorption is absent and the electrolyte concentration is low (< 0.01 M). At this point the capacity of the diffuse part of the double layer is a minimum and can fall below that of the compact or inner layer. As a result the total double layer capacity may... 

Differentiation with respect to the potential yields the double layer capacity C dfidi... 

The simplest model is that of a plate capacitor developed very early by Helmholtz. The idea is that the ions of the electrolyte, which form the excess charge there, can approach the metal surface only up to the distance of the radius which includes the irmer solvation sphere in liquid solutions. Measurements of the differential capacity of smooth electrodes yielded values for the Helmholtz double-layer capacity, Ch, on tlie order of 20 to 30 pF cm . The model of a plate capacitor gives for the differential capacity... 

Fig. 6.1 Symbolic equivalent circuit of an electrode wire heated and polarised inside solutioiL Resistor and capacitor symbols drawn stand for elements of differential size Cdl double layer capacity elements along the wire length, Zf faradaic impedance elements, Rsoi solution resistance elements inside bulk solution. REF symbolises the reference and counter electrodes in common, and POL the polarisation and current measuring circuit From [3], with permissirm...

Fig. V-12. Variation of the integral capacity of the double layer with potential for 1 N sodium sulfate , from differential capacity measurements 0, from the electrocapillary curves O, from direct measurements. (From Ref. 113.)...

Derive the general equation for the differential capacity of the diffuse double layer from the Gouy-Chapman equations. Make a plot of surface charge density tr versus this capacity. Show under what conditions your expressions reduce to the simple Helmholtz formula of Eq. V-17. 

The electrical double layer at Hg, Tl(Ga), In(Ga), and Ga/aliphatic alcohol (MeOH, EtOH) interfaces has been studied by impedance and streaming electrode methods.360,361 In both solvents the value ofis, was independent of cei (0.01 < cucio4 <0.25 M)and v. The Parsons-Zobel plots were linear, with /pz very close to unity. The differential capacity at metal nature, but at a = 0,C,-rises in the order Tl(Ga) < In(Ga) < Ga. Thus, as for other solvents,120 343 the interaction energy of MeOH and EtOH molecules with the surface increases in the given order of metals. The distance of closest approach of solvent molecules and other fundamental characteristics of Ga, In(Ga), Tl(Ga)/MeOH interfaces have been obtained by Emets etal.m... 

Measurement of the differential capacitance C = d /dE of the electrode/solution interface as a function of the electrode potential E results in a curve representing the influence of E on the value of C. The curves show an absolute minimum at E indicating a maximum in the effective thickness of the double layer as assumed in the simple model of a condenser [39Fru]. C is related to the electrocapillary curve and the surface tension according to C = d y/dE. Certain conditions have to be met in order to allow the measured capacity of the electrochemical double to be identified with the differential capacity (see [69Per]). In dilute electrolyte solutions this is generally the case. 

FIG. 8 Inverse differential capacity at the zero surface charge vs. inverse capacity Cj of the diffuse double layer for the water-nitrobenzene (O) and water-1,2-dichloroethane (, ), interface. The diffuse layer capacity was evaluated by the GC ( ) or the MPB (0,)> theory. (From Ref. 22.)... 

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