Theories of structure of double layer

Helmholtz–Perrin model (or) Parallel Plate condenser model

Helmholtz considered the double layer consisting of two oppositely charged layers
at a fixed distance a part. It can be compared to a parallel plate condenser of constant
capacity.

Thus, the electrified interface consists of two sheets of charges, one on the
electrode (rigidly held layer) and the other in the solution (layer of oppositely charged
ions). Hence, the term double layer which is compact and rigid.

QM QS

+ ─

+ ─

+ ─

+ ─

+ ─

The charge density on the two sheets are equal in magnitude but opposite in sign
exactly as in parallel plate condenser. Hence, the Helmholtz–Perrin model is also called
parallel plate condenser model.

QM = -QS

where,

QM is the Charge density of metal side.

QS is the Charge density of solution side.

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 According to Helmholtz model, the variation of potential of the double layer with
distance into the solution is linear.

linear
potential

Distance into the solution

The electrical double layer leads to difference of potential between the solid and
the liquid. The potential difference across the two layers is given as,

dv = 4πd/Ɛ dQ

where,

d = distance between two layers.

dQ = charge density on each layer.

Ɛ = dielectric constant of the medium.

This equation is a fundamental equation which is widely employed for a

quantitative analysis of electrokinetic potential.

Limitations:

1) Helmholtz model assumes a fixed layer of oppositely charged ions in solution.

But in solution, due to thermal motion of liquid molecules such a rigid array of
charges at an interface may not exist.

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 2) Helmholtz parallel plate condenser model predicts a constant capacity (C)
[that is, one which does not change with potential] for the electrical double
layer.

C = dQ/dV = Ɛ/4πd

Experimentally it is found that the capacity of the double layer is not constant with cell
potential.

Experimental

constant capacity (Helmholtz model)

Theoretical
capacitance(c)

V(potential)

3) It does not take into account the variation of the properties of double layer with
concentration of electrolyte and temperature.

Hence, the Helmholtz model is not satisfactory in explaining the structure of the
interface. The electrified interface does not behave like a simple double layer.

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Guoy–Chapmann’s model (or) Diffuse charge model

 According to this model, there is an electrical double layer at the interface

which is not sharp but diffuse double layer.
 One layer is fixed on the electrode and the oppositely charged layer is
diffused or mobile on the electrolyte. The solution side of the double layer
is not near one molecule in thickness but extends to some distance into
the liquid phase.
 The ions are spread out into the solution. The distribution of +ve and –ve
charges in this region is not uniform due to thermal agitation and the free
movement of ions present in the solution.
 The electrostatic attraction between opposite charges at the interface try
to bring out orderliness while thermal agitation tends to bring
disorderliness. In this respect, the diffuse double layer theory is similar to
the Dubye–Huckel concept of ionic atmosphere surrounding a given ion.

The diffused charge can be considered as a sheet of charge Qd placed at a

distance Қ-1 from the electrode surface.

QM Qd

+ ─ ─ ─ ─

+ ─ ─ ─ ─

+ Қ-1 ─ ─ ─ ─

+ ────

+ - ─ ─ ─ ─

Ψo Ψx

QM = -Qd

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 The potential change from one layer to another is not linear and it is exponential.
The potential drop in the diffused layer is given as

Ψx = Ψo .e – Қx

where,

Ψx is the potential at a distance x into the solution.

Ψo is the potential at x=0 that at a electrode surface.

Қ-1 is the reciprocal of the thickness of diffused double layer.

Potential

Distence x into the solution

Success of Guoy–Chapmann model

 The properties of the double layer change with electrolyte concentration and
temperature. Guoy and Chapmann made an attempt to relate the charge
density (σ) in the double layer to the solution composition. There is no such
σ factor in Helmholtz-Perrin equation.
 It gives better explanation of electrokinetic phenomenon than Helmholtz–
Perrin model. It is useful in understanding the stability of colloids, and
electrodics (electrode kinitics).

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Validity of Guoy–Chapmann model

1) The account for the fact that the capacitance of the double layer varies with the
potential, and it is not a constant. It predicts that the capacity of an interface
should be hyperbolic cosine of the potential difference across it and this cos.h
function gives inverted parabolas.

Capacitance vs. potential curves should be inverted parabolas. For very dilute
solution and at potential difference near zero, the experimental curves agree with a
theory. But, at higher concentration and at potentials away from that of zero charge,
Guoy–Chapmann theory fails. The experimental and predicted shapes of the curve differ
very much.

Sucess of Guoy capmann model:

Differential
capacity

potential

The calculated capacities on the basis of Guoy-Chapmann model are found to be

several times higher than the experimental value.

C = Ɛ/4πd = Ɛ/4π Қ-1

where C is the capacitance

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 Differential capacity of Hg–NaF inference at the potential of zero charge.

Differential Capacity
mF/cm2
Concentration
(N) Experimental Theoretically
Calculated
0.001 6.0 7.2
0.01 13.1 22.8
0.1 20.7 72.2
1.0 25.7 228.0

C is inversely proportional to the thickness of the double layer (d).

If d is very small the value of C should be very high. In this model, ions are
assumed as point charges and they are assumed to be very close to the metal surface.

Hence the calculated capacitance values are found to be higher than the experimental
values.

C =[ ƐZ2eo2Co/2πkT]1/2

Capacitance

Potential

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Stern theory (or) Stern model of double layer

This theory combines the essentials of both Helmholtz-Perrin and Guoy-

Chapmann theories of electrical double layer. According to this theory, the double layer
has two layers. One layer is fixed on the electrode and the oppositely charged layer
consists of two parts.

One part which is approximately of single ion thickness which remains almost fixed
to the solid surface (Helmholtz view). This is called stern layer. The ions present in the
stern layer are called counter ion. They form a compact layer near the electrode. The
remaining compensating charges are distributed through the electrolyte next to this layer
in the form of diffuse and movable atmosphere [Guoy’s view]. The compensating charges
are thought to be freely movable along with liquid. In this region, we have the combined
effect of electrostatic attraction producing orderliness and thermal agitation producing
disorderliness. The diffused layer between stern layer and electrically neutral part of the
system is referred to as Guoy-Chapmann layer.

To sum up, Stern model suggest that some ions in solution are ‘stuck’ to the
electrode and the remaining are ‘scattered’ in cloud like fashion due to thermal agitation.

+ ────

+ ─────

+ve charged electrode + a ──────

+ ─ ─ ─ ─ ─ ─ liquid

+ ──────

Fixed layer Diffused double layer (or) Guoy - chapmann layer

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Basic assumptions in Stern model

Stern model assumes that ions have a finite size not point charges.

Ions centers can come closer to certain critical distance ‘a’ from the electrode. This
distance ‘a’ is the distance of approach of the ions to the electrode. But, in the diffused
portion of the double layer, the ions are assumed to be point charges.

In the Helmholtz region, the ions are held not only by electrostatic forces of specific
adsorption (or) contact adsorption (or) non-coulombic.

Under all conditions the interface as a whole should be electrically neutral.

QM = -QS

Where,

QM is the net charge density on the metal side.

QS is the net charge density on the solution side.

According to Stem model, the charge QS on the solution side is partially stuck to
the electrode (QH ) and the remaining is diffusedly spread out (QG ).

Therefore QS = QH+QG

There are two regions of charge separation. The first region is from Helmholtz
plane of fixed layer into the bulk of the solution.

Whenever charges are separated potential drop results Stern model suggest that
there should be two potential drops.

1) Potential fall between the electrode surface and the fixed layer.
2) Potential fall between the outer limit of the fixed part of the double layer and
the interior of the bulk of the solution. That is, between the fixed part and

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 the diffused mobile part of the system. It is known as electrokinetic potential
or zeta potential (ζ).

Variation of potential

In the Hemholtz region, theret is a shape and linear change in potential. In the
diffused region, there is a gradual exponential change in the potential.

Zeta potential
P

Helmholtz Guoy - Chapmann

layer diffused layer

Success of Stern model

1) The capacity values calculated on the basis of Stern model agrees well with
experimental value.
2) It also shows that the capacity of interface depends on the electrode
potential and on the concentration of electrolyte solution.
3) According to Stern model, the total capacity of double layer (C) is composed
of the capacitance of the Helmholtz region [CH] and the capacity of Guoy –
Chapmann model [CG] of the double layer in series.

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 CH CG

series

1 1 1
Ctotal CH CG

CH CG
Ctotal
CH CG

Case (1):

At dilute concentrations, the double layer is essentially all diffuse. Therefore Ctotal
is approximately equal to CG.

Ctotal ≈ CG

The double layer has become approximately predicted by Guoy structure.

Case (2):

At high concentrations, the double layer is essentially all fixed.

Ctotal ≈ CH

Thus, at sufficiently concentrated solution, the capacity of the interface is equal to

the capacity of Helmholtz region in concentrated solution. The structure of the layer is
closely similar to the model proposed by Helmholtz. At high concentration, most of the
charge is confined in a region very near to the Helmholtz plane. Most of the charge
squashed on the Helmholtz plane and a very little amount of charges are scattered into
the solution.

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 Stern theory was able to account for the change in sign of the zeta potential that
takes place if capillary active substances are present in the solution.

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