A

APPENDIX

ELECTRIC DOUBLE LAYER AND CAPACITANCE RESPONSE

A.1. Models of the Electrical Double Layer

A.1.1. The Helmholtz model

In 1853 the first and simplest model of concept of the charge separation at interfaces was
proposed by Helmholtz [1-3], who proposed that the interface between a metallic electrode
and an electrolyte solution behaves like capacitor i.e. it is capable of storing electric charge.
The proposed model was that the electrode possesses a charge density ( q m ) arising from an
excess

(q

negative ) or deficiency ( q m positive ) of electrons at the electrode surface. The

charge on the electrode is exactly balanced in solution by an equal but oppositely charged
amount of ions ( q s ) ; a rigidly held layer exists in a plane parallel to the surface of the
electrode and very close to it (Fig. A.1 (a) and (b)).
This charge originates from the arrangement of electrolyte ions at the interface and/or the
reorientation of dipoles in solvent molecules. A potential difference occurs across the
interface, forming an electric field gradient across the charge separation layer. Ions are
electrostatically repelled or attracted towards the electrode surface and an excess of either
anions or cations is created.
The attracted ion may approach the electrode only so far. The distance is limited by a
monolayer of solvent molecules, which is assumed to exist between the ion and the
electrode. The line drawn through the centre of such ions at a minimum distance from the
electrolyte surface marks the boundary known as the Outer Helmholtz Plane (OHP). The
region within this plane Helmholtz is called the electrical double layer.
However, the interface cannot be represented simply by a parallel-plate capacitor, as shown
experimentally by accurate measurements of real double layer capacitances [4]. The double
layer capacitances are not linear as a function of potential i.e. the numerical value of the
capacity depends on potential. In addition, the electrochemical double layer capacitors are
leaky that is, they can be self-discharged by electrochemical reactions taking place across
the interface. A more appropriate model would be a capacitor and resistor in parallel.
Therefore, an integral capacitance K and a differential capacitance C need to be defined:

K=

and C =

dq
, where q is the charge held by the capacitor and is the
d ( )

potential drop across the interface. The ionic double layer capacity is dependent not only on
the composition but also on the concentration of the electrolyte in a particular system. The
double-layer capacitance per unit area, according to Helmholtz, is given as: CH =

,
4 d

where is the dielectric constant and d is the thickness of the double layer. The model does
not account for the dependence of the measured capacity on potential or solution
concentration, although the different values found in the presence of different electrolytes
could be accounted for by the variation of d with ionic radius. The Helmholtz model of the
double layer seems to be appropriate for polarizable electrodes in sufficiently high
concentrations of electrolyte (> 1 M). At lower electrolyte concentrations (< 0.1 M), new
features appear in the measurement of double layer capacitance as a function of potential
which cannot be explained by the Helmholtz model.

A.1.2. The Gouy-Chapman model

between 1910-1913 Gouy [5,6] and Chapman [7], proposed the diffuse double layer model
that predicted a dependence of the measured capacity on both potential and electrolyte
concentration. They showed that the excess charge density in solution is not exclusively
situated at the OHP, so that the double layer may be of variable thickness. In the their view,
a Helmholtz-type rigid double layer would not form because the attractive and repulsive
electrostatic forces between the field and the charge on the ions are counteracted by random
thermal motion in solution which tends to disperse the excess ions. In this model, the ions are
considered as point charges contained within a single diffuse layer.
The relationship between the excess surface charge density q M on the metal, the differential
capacity CG of the diffuse double layer and the potential, o , at the limit of the diffuse
double layer is shown in Equation A. 1:
zF 0
M
q D =- 8RTc Sin h
= -q
2RT

(A. 1)

Differentiation of Equation A.1 with respect to 0 , leads to the capacitance of the diffuse
layer CG :
CG = zF

2c
zF 0
Cos h

RT
2RT

(A. 2)

C
where F is the Faraday constant, c is the concentration, is the dielectric constant of the
solvent, z is the magnitude of the ionic charge, and 0 is the potential of the outer
Helmholtz plane.
The potential 0 was identified with the potential M on the surface of the metal. That is, the
notion of an inner layer of ions strongly and rigidly adsorbed on the surface of the electrode
as depicted by Helmholtz was incorrect. The model proposed by Gouy and Chapman, (Fig.
A.2) represented substantial improvement over the Helmholtz model in that a dependence of
the differential capacity on both potential and concentration was predicted (Equation A. 2).
In this diffuse layer, the net charge density decreases with distance from the phase boundary.
The Gouy-Chapman model fails to explain the actual capacity-potential curves found
experimentally for all concentrations and measured capacity was much lower than that
calculated from equation A. 2, except in very dilute solutions. The inverted parabolas (Fig.
A.2 (b)) occur only in very dilute solution (< 0.001 M) and at potentials close to the potential
of zero charge. The capacity-potential curves were incorrect and the predicted dependence
on concentration was not observed.

A.1.3. The Stern model

A simple development of the double-layer theory was suggested by Stern in 1924 [8] as a
more realistic way of describing the physical situation at the interface. Stern [8] combined
the two previous models, with some of the ions adhering to the electrode as suggested by
Helmholtz and some forming a Gouy-Chapman type diffuse layer (Figs. A.3 (a) and (b)).
Stern adapted the Gouy-Chapman model to take into account the fact that ions have finite
size, and consequently have a closest approach a to the electrode of the order of the ionic
radius. Thus the potentials are given by: 0 = a p m. . Under all conditions, the interface is
assumed to be neutral i.e. - q m = q s . Stern assumed the charge qs on the solution side resided
partially in a compact layer, qH (the Helmholtz charge), and the remainder qG in a diffusely
region (as in the Gouy-Chapman models) in the solution i.e. qS = qH + qG . There are
therefore two regions of charge separation. When charges are separated, a potential drop
results. In the Stern model, two capacitors are effectively operating in determining the total

(a)

(b)
S

Fig. A.1. (a) The Helmholtz model of the rigid ionic double layer.
(b) The potential profile of the Helmholtz model, where M is the potential at the
metal surface and S is the potential of the bulk solution. Reprinted from [9].
(a)

(b)

S
M

Fig. A.2. (a) The Gouy-Chapman model of the diffuse ionic double layer.
(b) The potential profile for the Gouy-Chapman model. Reprinted from [9].

(a)

(b)

S
M
Fig. A.3.

(a) The Stern model of the ionic structure at the interphase.

(b) The potential profile of the Stern model, where 2 is the potential at the outer
Helmholtz plane (OHP). Reprinted from [9].

E
differential capacity of the interface, CH due to the Helmholtz layer and CG due to the diffuse
layer. The total capacity of the interface C is therefore given by:
1
1
1
=
+
C CH CG

(A. 3)

The two adjacent regions act like capacitors in series. This proved to be a significant result
since it indicates the smaller of the two capacitances determines the overall capacitance. In
very low dilute solutions and close to the potential of zero charge, when qM , 0 and a are
relatively small CG should dominate. Stern also recognised the effect of specific interactions
between ions and suggested a distinction between ions which were adsorbed on the electrode
and those which merely approached it to the distance of the closest approach. This idea was
later developed by Grahame [10].

A.1.4. The Grahame model

In 1947, Grahame [10] proposed that, although the closest approach to the electrode is
occupied by solvent molecules, it may also be possible for some ionic or uncharged species
to penetrate into this region. This could come about if the ion possessed no solvation shell, or
if the solvation shell was lost when the ion came close to the electrode. Ions in direct contact
were deemed to be specifically adsorbed.
This model for the electrode/electrolyte interface (Fig. A.4) proposed the existence of three
regions. First, the inner Helmholtz plane (IHP) (potential 1 ) extends from the electrode to a
plane passing through the centres of the specifically adsorbed ions. Second, the outer
Helmholtz plane (OHP) passes through the centres of hydrated ions at their distance of
closest approach to the electrode. Third, the diffuse layer i.e. the region that lies beyond the
OHP. The potential at the OHP is denoted by 2 . Potential changes linearly with distance up
to the outer Helmholtz plane and then exponentially through the diffuse double layer region.
Diffuse double layer effects decrease with increasing concentration in solution ( equations
A.2, A.3).

A.1.5. The Bockris, Devanathan and Muller model

Clearly, in dipolar solvents, such as water, interactions exist between the electrode and the
dipoles of the water molecules. Furthermore, the concentration of the solvent is always much
higher than that of the solute. In the Gouy-Chapman model, the diffuse part of the double
layer is similar to the ionic environment around an ion, the electrode being thought of as an
infinite radius. One would consequently expect to find a layer of solvent molecules attached

F
to the electrode surface in fixed orientation and a few more layers of solvent in orientation
intermediate between that of the first layer and that in the bulk-like arrangement
corresponding to the primary and secondary solution shells around an ion.
In 1963, Bockris, Devanathan and Muller [11] proposed a model of the double-layer which
clearly takes into account the predominant role of the solvent in the interface. They
suggested that reorientation of solvent molecules would occur depending on the excess
charges at the electrode and the presence or absence of specifically adsorbed ions at the
surface. The proposed variation of the electrostatic potential with distance is qualitatively
similar to that of the Grahame model. At present, this seems to be the best model to
demonstrate the role of the solvent in the double layer.

However, the distribution of

electronic charges on the side of the electrode has not been fully clarified and requires
further analysis using surface analytical techniques. Fig. A.5 shows the effect of water
molecules according to this model. The water molecules cover most of the electrode with an
oriented layer of water molecules. At certain sites, the water molecules are replaced by a
specifically adsorbed ion (usually an anion) that has shed its hydration shell. The plane going
through the centres of these ions is defined as the inner Helmholtz plane. Ions that carry a
primary hydration shell are found next and are situated outside the first layer of water
molecules adsorbed on the electrode surface. The plane going through the centres of these
ions constitutes the outer Helmholtz plane. For contact adsorption of an ion to occur,
chemical work must be done in order to rid the ion of its primary hydration sheath and to
remove one or more of the surface water molecules at the electrode surface. The final state is
then stabilised by the specific interactions between the ion and the surface. These effects are
absent for ions adsorbed in the outer Helmholtz plane where interactions are mainly
electrostatic in origin.
A.2. Capacitance
An electrode-solution interface is analogous to a capacitor composed of two metal sheets
separated by a dielectric material (Fig. A.6 (a), whose behaviour is represented by the
following equation: C = q / E

where C is the capacitance in Farads, q is the charge in

Coulombs and E is the potential across the capacitor in volts. When a potential is applied
across a capacitor, charge accumulates on its metal plates until the charge q satisfies the
equation C = q / E . During this charging process, no current will flow. The charge on the
capacitor arises as a result of an excess of electrons on one plate and a deficiency of
electrons on the other plate (Fig. A.6 (b). The electrode-solution interface behaves as a leaky
capacitor.

(a)

(b)

OHP
IHP

Fig. A.4.

(a) The Grahame model indicating the specific adsorption of ions within
the IHP and hydrated ions at the OHP.
(b) The potential profile of the Grahame model, where 1 is the potential
at the inner Helmholtz plane (IHP). Reprinted from [9].

IHP

OHP

Fig. A.5. The model of Bockris, Devanathan and Muller. Reprinted from [9].

(b)
(a)

(a)

(c)(b)

Fig. A.6.

(a) a capacitor , (b) charging a capacitor with a battery.

(c) The metal-solution interface as a capacitor with a charge on the metal, qM, (1)
negative and (2) positive. Reprinted from [4].

I
At a given potential there will exist a charge on the metal electrode, q M , and a charge in the
solution, q s (A.6 (c)).
Whether or not the charge on the metal is negative or positive with respect to the solution
depends on the potential across the interface and the composition of the solution. However,
at all times q M = q S . The charge on the metal q M represents an excess or deficiency of
electrons and resides in a very thin layer on the metal. The charge in solutions q S is made up
of an excess of cations or anions in the vicinity of the electrode surface. The charges q M and

q S are often divided by the electrode area and denoted as charge densities, M ,

M = q M / A , having the units of C cm 2 .

The entire arrangement of charged species and oriented dipoles existing at the metal-solution
interface is called the electrical double layer. At a particular potential the electrodesolution interface is characterised by a double-layer capacitance, Cd , which has values in the
range of 10 to 40 F/cm2. Unlike real capacitors, whose capacitances are independent of the
voltage across them, Cd is often a function of potential. The capacitance of an interface
characterises its ability to store charge in response to a change in potential. One definition is
based on the small change in charge density that results from a small alteration in potential.
The differential capacitance, Cd , is given by C = ( M / E ) , i.e. by the slope of
d

M vs. E at any point (Fig. A.7 (a)). Since Cd is not constant with E (see Fig. A.7 (b)) for
some experimental examples) its variation leads to the concept of integral capacitance, Ci
defined as the ratio of the total charge density M at potential E to the total potential
difference leading to the accumulation of charge, that is; Ci = M /( E E z ) where

EZ denotes the potential of zero charge (PZC), and Ci is related to Cd via the equation:
E

Ci =

Cd dE

dE . Thus, C

EZ

EZ

is an average of C over the potential range from EZ to E.

d

The differential capacitance is a useful parameter since it is precisely measurable by

impedance techniques [4].

M C /cm2

(a)

E-Ez (v)

M C /cm2

(b)

E-Ez (v)
Fig. A.7.

(a) Schematic plot of charge density versus potential illustrating the

definitions of the integral and differential capacitancies.
(b) Charge density on the electrode versus potential for mercury
immersed in 1 M solutions of the indicated electrolytes at 25 C.
The potentials are plotted with respect to the PZC for each
electrolyte. Reprinted from [4].

K
According to the Helmholtz model, Cd should be a constant, however, in real systems this is
not the case. Fig. (A.8 (a)) shows a dramatic illustration for interfaces between mercury and
sodium fluoride solutions of various concentrations. Cd varies with both potential and
concentration [10]. According to the Gouy-Chapman model, as the electrode becomes more
highly charged, the diffuse layer should become more compact and Cd should increase.
Likewise when the concentration of the electrolyte increases, a similar compression of the
diffuse layer should occur, producing a consequent increase in capacitance. These qualitative
trends are actually represented in the data of Fig. A.8 (a). The predicted differential
capacitance from the Gouy-Chapman theory is shown in Fig. A.8 (b). Thus, Cd varies with
potential, and there is a minimum PZC.
The predicted "V shaped" capacitance function resembles the observed behaviour of mercury
in NaF at low concentrations and at potentials (near to the PZC) (Fig A.8 (a)). However, real
interfaces display a flattening in capacitance at more extreme potentials, and the valley (Vshape) at the PZC disappears altogether at high electrolyte concentrations. Also, the actual
capacitance is normally much lower than the predicted value.
In a real system, according to the Gouy-Chapman-Stern (GCS) model, the capacitance
consists of two components can be expressed as:

1
1
1
=
+
(see Fig. A.9 (a)) where
Cd C H C D

CH is the capacitance of the charges held at the OHP and CD is the capacitance of the truly
diffuse charge. CH is independent of potential but CD is potential dependent. The composite
capacitance, Cd shows a complex behaviour and is governed by the smaller of the two
components. Near the PZC in systems with low electrolyte concentration, the V-shaped
function characteristic of CD is expected. At large concentrations CD becomes so large that it
is no longer contributes to Cd and one sees only the constant capacitance of CH is observed.
Fig. A.9 (c)) shows a schematic representation of this behaviour. In this model there are still
discrepancies in that CH is not truly independent of potential. Various methods can be used
to measure the double layer capacity. The impedance technique is the most common, and is
applicable to most types of electrode, solid or liquid. The electrocapillary measurement
method is only applicable to liquid electrodes (for example, mercury) [12].

Cd, F/cm2

(a)

E-Ez (V)

Cd, F/cm2

(b)

E-Ez , mV
Fig. A.8. (a) differential capacitance versus potential for NaF solutions in contact with
mercury at 25 C. Reprinted from [9].
(b) predicted differential capacitancies from the Gouy-Chapman theory.
Calculated for the indicated concentrations of a 1:1 electrolyte in water at 25
C. Reprinted from [4].

(a)

(b)

Linear profile to x2
X2

mV

2 = 100 mV

Diffuse layer

X, A

(c)

Cd, F/cm2

High electrolyte
concentration

Low electrolyte
concentration

E-Ez, V
Fig. A.9.

(a) a view of the differential capacitance in the GCS model as a series network
of the Helmholtz layer and the diffuse layer capacitances.
(b) Calculated potential profile through the solution side of the double layer,
according to CGS theory.
(c) Schematic representation of the expected behaviour of Cd (according to GCS
theory) as the electrolyte concentration changes. Reprinted from [4].

A.4. References

1. H. L. F. von Helmholtz, Ann. Physik, 89 (1853) 211.

2. H. L. F. von Helmholtz, Ann. Physik, 7 (1879) 337.
3. H. L. F. von Helmholtz, W. Abhandl, Physik. Tech. Reichsaslaldt, 1 (1879) 925.
4. A. J. Bard, L. R. Faulkner, Electrochemical Methods, Fundamentals and

Applications, John Wiley and Sons, New York, 1980.

5. G. Gouy, J. Phys. Radium, 9 (1910) 457.
6. G. Gouy, Compt. Rend., 149 (1910) 654.
7. D. L. Chapman, Phil. Mag., 25 (1913) 475.
8. O. Stern, Z. Electrochem., 30 (1924) 508.
9. E. Gileadi, E. Kirowa-Eisner, J. Penciner, Interfacial Chemistry: An Experimental

Approach, Addison-Wesley, U.S.A, 1975

10. D. C. Grahame, Chem. Rev., 41 (1947) 441.
11. J. OM. Bockris, M. A. V. Devanathan, K. Muller, Proc. Roy. Soc., A 274 (1963).
12. C. M. A. Brett, A. M. O. Brett, Electrochemistry Principles Methods and

Applications, Oxford University Press 1993.