Structure of Electrified Interfaces

(The Electrical Double Layer)

Types of interfaces
Models of M/S interface
Validation of the models

Surface tension varies with potential and electrolyte composition

Ideally-polarizable interface (Hg/Solution)

Electrocapillary phenomena
Lippmann equations
Gibbs adsorption isotherm
Improvements in the M/S model
When M/S interface is mobile

Electrokinetic (4) phenomena

Applications

The interface

M+

X-

M+
M+
M+

XXX-

M+

X-

2- Specific adsorption of ionic species:

Vacuum

Solution

3- Oriented adsorption of polar species:

Vacuum

Liquid

Solution (S)

X-

Metal (M)

M+

Solution (S)

Metal (M)

1- Complete charge transfer from one phase to the other phase:

When two different metals are immersed in an electrolytic solution

Potential difference exists between the terminals of the two metals

When two identical metals are immersed in an electrolytic solution

No potential difference.
The conclusion Potential difference must exist at any M/S interface

The electrical analogue to the M/S interface

Parallel-plate condenser is candidate to describe the M/S interface.

qM = - qS
Is the M/S interface really a parallel-plate condenser?
The answer is the models of the proposed structure of the M/S interface

The decision is based on how capacitance of the M/S interface

varies with
potential and electrolyte composition

1- Helmholtz Model

M/S interface resembles a parallel-plate condenser of two charged

Solution

Metal

layers.

Example:
Fixed positive
charges are created
on the metal

EM

surfaces
due to

EM/S

the natural tendency

0

ES=0

Distance from
metal surface

of the deposition of
metal ions as metal
atoms

to achieve the electrical neutrality

layer of anions in solution is arranged in a row close to the metal surface
Potential difference, EM/S, between the metal and the solution:
EM/S = EM - ES
The capacitance according to the model

C (F m 2 )

o =

o
qM

E M / S 4

8.8510-12 C2N-1m-2

 ~ 5 -78 and ~ 10-10 m (the ionic radii)

C ~ 4-55 Fcm-2
C value is close to the experimental value observed sometimes.
But
The model fails to explain the dependence of C
on potential and electrolyte composition

2- Gouy and Chapman Model

The electrical double layer cannot be fixed in position

due to

the thermal motion of the electrolytic species instead a diffuse layer of

point-charge is proposed in the model

EM/S decays exponentially as the distance from the metal surface

increases
The model does not reflect the general C-EM/S feature
observed experimentally
but

Metal

Solution

it may be accepted when the electrolyte concentration is very low

EM
EM/S
0
Distance from
metal surface

ES=0

3- Stern Model
Stern model is a compromise between Helmholtz and Gouy-Chapman
models
Ions of the first row are fixed and stuck close to the metal surface
and

the rest of the ions are scattered in a cloud-like fashion

Consequently
there must be two layers,
the first row of ions (equivalent to Helmholtz model)
followed by
the diffuse layer (equivalent to Gouy-Chapman model)
Potential difference according to the model
EM/S = EH + EG
EG is the diffuse layer potential and is called zeta potential ( potential)
The presence of

potential is essential for the stability of colloidal

systems
The amount of charges:
qS = qH + qG
The capacitance of the M/S interface
1
1
1

C C H CG

Solution

Metal
EM
EH
EM/S

(EG)
0
Distance from
metal surface

ES

No specific adsorption

Further
The first row ions can be attracted to the metal surface
by
electrostatic attraction
or/and by
forces of specific adsorption

Solution

Metal

Solution

Metal
EM

Distance from
metal surface

EM/S
ES

Distance from
metal surface

ES
EM/S

EM

Specifically adsorbed anions

Specifically adsorbed cations

Validation of models of the structure of the M/S interface

We should search for a surface (or an interfacial) property
Interfacial tension of the Hg/solution interface responses to
variation of EM/S and the solution composition

The phenomenon is known as the Electrocapillarity.

We need to change the amount of charges on the metal surface (by
changing EM/S)
and
analyzing the response of ions in solution close to the surface
by
measuring the interfacial tension
We must ensure that no charges leak (transfer) from the metal to the
solution or vice versa.
The M/S interface that fulfills this requirement is called
ideally polarizable electrode (interface)

Ideally polarizable and ideally non-polarizable electrodes

Polarization occurs whenever the current I 0
The passing current causes EM/S to deviate from its equilibrium value

C
Ideally non-polarizable
electrode

Current

C
R
R

Erev

OO

Ideally polarizable
electrode

The electrocapillary phenomena

Reference
electrode

N2 gas

Potentiometer

Hg capillary electrode
Hg
Electrolyte
Hg manometer

radius of the capillary

r
height of Hg column
h

surface tension force =

2 r cos

gravity force =
r2 h d g

=hrgd

Electrolyte
level

What did Lippmann and other scientists find?

pzc (ecm)

pzc (ecm)

pzc (ecm)

KNO3

KNO3

KNO3
+ amyl alcohol

ICl

Tl

(C3H7)4N+

Br-

-E

-E

-E

(a)

(b)

(c)

Qualitative explanation of electrocapillary curve

pzc

Hg
Solution
-E

Quantitative explanation of electrocapillary curve

By analyzing the thermodynamics of the M/S interface

Deduction of the electrocapillary curve (-E curve).

Thermodynamics of M/S interface

Fundamental thermodynamic equation of the polarizable M/S interface
The general electrocapillary equation
d q M dE

qM
d j i d i
i
n jF

n i n io
i

A
A
Dependence of interfacial tension on electrode potential
The first Lippmann Equation
At constant electrolyte composition d i = 0 and d j = 0:
(

)
E const .

comp .

(dyne / cm )
E (mV )

qM

q M 100(C cm 2 )

The second Lippmann Equation

q
2
M C
2
E
E

q M (C cm 2 )
2

C (F cm 2 )
E ( V )
E 2
Differentiation

Differentiation

ecm

ecm
d/dE=-qM q

ecm

Ideal
Parabola

+
0
-

-E
(a)

-E

-E
(b)

The differential capacitance

(c)

0.1M

C, F

1.0M NaF

0.01M
0.001M

pzc

-E, V

Experimental curves

0.01M NaF

C, F

C, F

0.001M

pzc -E, V
Gouy-Chapman
model

pzc

-E, V

Helmholtz model

Dependence of surface tension on the solution composition

Gibbs adsorption isotherm

We use one and the same electrolyte for both electrodes:

Hg/solution electrode and the reference electrode
The electrocapillary curves at different electrolyte concentrations are recorded,
using the same electrolyte concentration for the reference electrode.
In order to remember that the reference electrode contains the same electrolyte
used in the cell for Hg/ electrolyte interface

we will use
the symbol E+ (when H+ ions used in the hydrogen electrode for example)
and
E- (when Cl- ions used in the calomel electrode for example).

The surface excess of an anion

0.01 N HCl

0.1 N HCl
1.0 N HCl
3.0 N HCl

E+(V vs RHE)
Consider the example of Hg/HCl interface and we want to calculate the surface
excess of Cl- ions at the Hg/HCl interface.

d q M dE

qM
d j i d i
i
n jF

d q M dE

qM
d H H d H Cl d Cl
F

At constant E+
d

qM
d H H d H Cl d Cl
F

HCl H Cl

By definition:

d HCl d H d Cl

qM
d H H d H Cl (d HCl d H )
F

d Cl d HCl (

qM
H Cl )d H
F

It can be proved that:

qM
H Cl 0
F

This is because:

qM = - qS = -(q+ + q-) = -( FH FCl )

Where

q+ = n+F + and q- = n-F n+ = 1 and n- = -1

I.e.

q+ = q H = FH and q- = q Cl = - FCl

Thus:

) E Cl
HCl

From the basis of thermodynamics:

HCl oHCl RT ln a HCl

But:

a HCl a 2 HCl
HCl oHCl 2RTn a HCl

d HCl 2RTd n a HCl

2RTn a HCl

Cl
E

The last equation is the Gibbs adsorption isotherm

The unit of R in Gibbs isotherm = 8.314107 erg mol-1 K-1.
The surface excess of a cation

2RTn a HCl

H
E

The surface excess of a neutral molecule

2RTn a i

i
E, j

Evidences of specific adsorption

qM = - qS = - (q+ + q-) = F + - F -

ve
l

ch
ar
ge
d

qS

el
ec
tr
od
ei

Charge density, mC cm-2

s+

+ve

q0.0

electrode is -vely charged

-ve

pzc
-E, V

Dependence of the charge densities on the cell voltage

for the Hg/1.0 M NaCl interface.

Point (a) is at pzc (ecm), where Hg surface is neutral:

q+ 0 and q- 0
although
qM = 0 and qS = 0
Why?
The reasonable explanation is that
one ionic form (either anion or cation) is held at Hg/S interface
by a different kind of forces rather than the electrostatic forces

(specific adsorption forces?)

The counter ions are also included
to achieve the electrical neutrality (q- = q+).
Which is the ion specifically adsorbed here?

Point (b) when Hg is positively charged:

If only the electrostatic forces would operate

qS = q- = F Cl
But, the figure shows that q+ = F Na 0
This means that some Na+ cations are involved
to partially neutralize the specifically adsorbed Cl- ions
This means accumulation of Cl- ions in the interface relative to the bulk

Point (c) when Hg is negatively charged:

qS = q+ (positive F Na ) + q- (negative F Cl )
consequently
q- is positive.
The fact that F Cl is a negative quantity
means that
there is a depletion of Cl- ions in the interface region

Contribution of electrocapillarity to the structure of M/S interface

1
1
1

C C H CG

In very dilute solutions near pzc from both sides of the curve

CG is lower than CH

C CG

Diffuse layer dominates the structure of M/S interface near pzc

Since

potential

is a significant part of EM/S

In concentrated solutions,

CG is larger than CH

C CH
Helmholtz model works better as the electrolyte concentration increases

The diffuse layer (or

potential)

vanishes at high concentration.

What is missing so far in the models of the M/S interface?

1-The orientation of water molecules at the M/S interface:
Capacitance of M/S interface 0 at pzc
even in electrocapillary inactive electrolyte
where
qM = - q S = 0
What is the origin of this capacitance?

It is not the charges anyway

Capacitance can also originate due to adsorption of dipole molecules,
such as water molecules,
It is assumed that Metal is fully covered by a monolayer of water dipole
in electrolytic solutions
In the presence of some specifically adsorbed species
some water dipoles are replaced
The center of this monolayer of oriented water molecules
form what is called inner Helmholtz plane (IHP)

2- The hydration of ions:

Practically all ions are hydrated in water
The result is that an increase in the radius of the bare ion
due to the hydration
The center of the hydrated ion is called the outer Helmholtz plane (OHP)
Capacitance at more significantly negative potentials than pzc
shows a little dependence on the nature of electrolyte

This is because the ion radius is a small fraction

of the (M OHP) distance

IHP

OHP

No specific adsorption

Diffuse Layer

Meal

Meal

Diffuse Layer

water molecules

IHP

OHP

Specific adsorption of anions

M/S interface consists of two parts;

The dense part {(MIHP) + (IHPOHP)} + diffuse part
In concentrated electrolytes (diffuse part vanishes)
M/S interface The dense part {(MIHP) + (IHPOHP)}
The M/S capacitance in concentrated electrolyte is given by:

1
1
1

C C MIHP C IHP OHP

In the presence of specific adsorption of organic molecules

CMIHP is significantly reduced and hence

C CMIHP

Why?
since decreases sharply

C CMIHP
The decrease of CMIHP increases with surface coverage with the
adsorbed organic molecules,

The Electrokinetic Phenomena

Origin of the Electrokinetic phenomena:
When one of the two phases in the electrified interface is mobile
the double layer becomes movable
we observe the electrokinetic phenomena.
The relative motion of the electrified interface
is essential to observe
the electrokinetic phenomena

Another condition to observe these phenomena in practice

is The tiny size of the mobile double layer
When large mobile double layers are involved,

the electrokinetic phenomena cannot be realized in practice

How much tiny must the mobile double layer be?
The phenomena are best observed
when
the size of the mobile charged particles
is in the range of the size of stable colloidal particles
10 -1000

Why must the particles be tiny?

The forces of gravity > Thermal collisions (large particles in suspensions)

SEDIMENTATION
The forces of gravity << Thermal collisions (very small solutes in
solutions)

STABILITY
The forces of gravity ~ Thermal collisions (colloidal particles)
Reinforced by repulsion of particles


STABILITY

How do the particles create the repulsion forces?

Colloid particles are charged particles surrounded by counter ions to
achieve the electrical neutrality
Only when the cloud of the counter ions is large in size,
the repulsion of the clouds beat the forces of attraction
that wants particles to aggregate
Large size cloud of counter ions is fulfilled
when the zeta potential predominates EM/S

zeta potential is connected with the stability of the colloid

When we add a concentrated electrolyte

or in the presence of strong specifically adsorbed species
zeta potential diminishes or vanishes
and the double layer of according to Helmholtz model predominates
The cloud of the counter ions is so small that
the aggregation forces (attraction) beat the repulsion forces
due to the dense thin double layer

repulsion force due to

the double layer

attraction forces

Potential energy

Potential energy

total potential energy > 0

no coagulation

total potential energy < 0

coagulation occurs

minimum distance between

two coagulated particles

The Four Electrokinetic Phenomena

Tiny charged solid particles are dispersed in the liquid phase
(stable colloid or suspension)

Two phenomena are observed

Electrophoresis and Sedimentation Potential

Very thin charged layers of the liquid phase move in capillaries or pores
of an immobile charged solid phase

charged inner surface

-ve electrode

+ve electrode

charged liquid layer

Pore (capillary) in the porous barrier

Two phenomena are observed

Electroosmosis and Streaming Potential

Electrophoresis
Movement of charged (colloidal or suspension) particles
under the influence of an electric field
Battery

Dispersed
particles
Dispersion
medium

Sedimentation potential
Creation of a potential difference on sedimentation (precipitation) of
charged particles (colloidal or suspension)
under the influence of the gravity

Voltmeter
Dispersed
particles
Dispersion
medium

Electroosmosis:

Movement of thin charged liquid layers through

capillaries or pores of a solid phase (porous barrier layer)
under the influence of an electric field
Battery

Porous barrier

Streaming potential
Creation of a potential difference on forcing thin liquid layers to move
through capillaries or pores of a solid phase (porous barrier layer)
by applying an external pressure
Voltmeter

Porous barrier

Applied pressure

Applications of Electrokinetic Phenomena

Separation and analysis of proteins:
Deposition of colloidal particles:
Reverse osmosis (desalination of sea water):
Pollution control

Analysis of the cell potential

V

LJ

M1

S1

c
LJ

M1
M

M'
EM1/M'

ECell
M'

EM

EM'

S1

EM'/M

EM'

EM1

ES1/M1

EM/S
ES1
ELJ

ES

a, b, c, d, and e are the interfacial regions that determining the cell potential, ECell
EM' , EM , ES , and ES1 are the internal potentilas of M', M, S and S1.
EM'/M , EM/S , ELJ, ES1/M1 , and EM1/M' are the interfacial potential differences.

ECell = EM'(a)/M'(e) = EM'/M + EM/S + ELJ + ES1/M1 + EM1/M'

Practically, EM'/M and EM1/M'

zero V

ECell = EM/S + ELJ + ES1/M1

In the absence of the liquid junction potential, ELJ

ECell = EM/S + ES1/M1

If M = M1 and S = S1

ECell = zero V

Problems
1- Outline with drawing Helmholtz model for the double layer structure.
Refer to the applicability of the model.
2- Outline with drawing Gouy-Chapman model for the double layer
structure. Refer to the applicability of the model.
3- Outline with drawing Stern model for the double layer structure.
4- Mention the factors missed in Helmholtz and Gouy-Chapman models.
5- Sketch the electrocapillary curves in the absence and presence of
capillary-active species.
6- Sketch a diagram for the variation of the charge densities with
potential in the case of Hg/NaCl interface. Show how we can extract
information about the double layer structure. Refer to potentials where
the Hg surface is positively charged, negatively charged and neutral.
7- Discuss with drawings the polarization behaviour of ideally
polarizable and ideally non-polarizable electrodes.
8- How can the electrocapillary curve be obtained? Mention the setup
and the equation used for calculation of the interfacial tension.
9- Explain the electrocapillary curve in the absence of capillary-active
species. Refer to different potential regions.
10- What are the electrokinetic phenomena? Illustrate with drawing.
11- Write on the application of the electrokinetic phenomena.
12- What is the connection between the double layer and the colloidal
system?

13- Prove diagrammatically that the zeta potential is essential for the
stability of a colloid.
14- Show how the zeta potential can be estimated from the electrokinetic
phenomena. Mention a mathematical equation that can be used, with
description of the symbols involved.
15- Describe the models of the double layer structure. Mention the
advantage and disadvantage whenever possible.
16- Derive the Gibbs adsorption isotherm for Hg/HCl interface from the
fundamental thermodynamic equation of the M/S interface.
17- Explain how the Gibbs adsorption isotherm can be studied from
electrocapillary measurements. Take HCl as the electrolyte.
18- Explain with graphical illustration the variation of the differential
capacitance of Hg/NaF interface with potential at different electrolyte
concentrations. Mention the correlation with the double layer models.
19- Use the capacity according to Helmholtz model to estimate the
thickness of the double layer in 0.2 M K2SO4. The capacity = 18.2 F cm2

, the dielectric constant of the medium in the double layer = 8.9 and the

permittivity of vacuum = 8.8510-12 C2 N-1 m-2.

19-

o
4
o
4 C

, where C (F m-2).
= 8.9 8.8510-12/ 43.14 18.210-6 104 = 0.3410-10 m

20- The capacity of Hg/0.1 NaF = 17.5 F cm-2 when EM/S = 750 mV.
Calculate the charge density in solution by assuming that the electrical
analogue of the interface is a parallel-plate condenser.

20- C = qM / EM/S
qM = C EM/S = 17.510-6 0.750 = 13.1 10-6 C cm-2
21- The electrocapillary measurements in HCl solutions with hydrogen
electrode in the same electrolyte as the reference electrode yield the
following at 25 oC and a constant potential:
/ dyne cm-1 425
aHCl
0.03

417
0.1

404
0.7

397
1.9

Find the surface excess of the Cl- ion at the studied potential.

21-

) E Cl
2RTn a HCl

Slope of curve ( versus ln a) = -6.735 dyne cm-1

Cl =

-(slope/ 2RT) = 6.735 / 2 8.314 107 298 = 1.36 10-10 mol cm-2.

For another (approximate) solution, two points may be used as follows:

(

2 1
) Cl
{ a HCl } 2 E
2RTn
{ a HCl }1

417 425
0 .1
2 8.314 10 7 298 n
0.03

1.34 10 10 mol cm 2

395
-4

-3

-2

-1
ln a