II

Processes at Electrodes
- The electrical double layer
- The rate of charge transfer
- Polarization
By Olly Norita Tetra
Much of electrochemistry depends on processes
that occur at the interface of an electrode and an
ionic solution
Kinetic problem determined is the rate at which
ion can be discharged at electrodes (current
density j, the electric current per unit area, the
charge flux)
In an electrolytic cell, an electrochemical cell in
which a non spontaneous chemical reaction is
driven by an external supply of electricity,
deposition and gas evolution occurs significantly
only when the applied potential exceeds the zero-
current cell potential to an extent called the
overpotential η
 Double Layer Models

1. Helmholtz Model

2. Gouy-Chapman Model

3. Stern Model
 Φ
ΦM xh : distance (ion radius)
+ - Φ : electric potential

+ -
electroda solution Φs
+ -

+ -

xh xh x

Considered the ordering of positive and negative chargers in a rigid

fashion on the two sides of the interfaces, giving rise to the designation
of double layer (or compact layer)
This model of the interface is comparable to the classic problem of a
parallel-plate capacitor. One plate would be on the contact surface
metal/solution. The other, formed by the ions of opposite charge from
solution rigidly linked to the electrode, would pass through the centres
of these ions
The two principal defect of this model
It neglects interactions that occur
further from the electrode than the first
layer of adsorbed species
That is does not take into account any
dependence on electrolyte concentration
 +
elektroda - +

+ solution
+
-
+ -
+

- +

The applied potential and electrolyte concentration both

influenced the value of the double layer capacity
The double layer would not be compact as in Helmholtz
description but of variable thickness, the ions being free to
move. This is diffuse double layer
 Φ

+
-
elektroda
+ ΦM
+ solution
+ Diffusi layer
-
-
+
+ Compact
layer
-
- Φs
xh x

Stern combined the Helmholtz model

for values of potential far from Ez with
the Gouy-Chapman model for values
close to Ez
Considered that the double layer was
formed by a compact layer of ions
 +
ΦM (galvani Potensial )
+
X (Surface Potensial )
Φ +
Ψ Volta Potensial )
+
elektroda
+
solution
+
X (distance)

Volta Potensial Ψ = outer potensial, the potential varies only slightly with
distance (+ 100 nm from the surfaces)
galvani Potensial ΦM = the total potential inside the electrode
Surface Potensial x = extra potential
Difference Galvani potensial (Φ) = the potential diffrence between points in
the bulk metal and the bulk solution
The most important property of the
double layer is the effect it has on the
electric potential near the electrode
This change in behavior can be traced
(using electrostatics) to the fact that the
surface charge is not poin-lake but it
spread over an area
to demonstrate the relation between ∆Ф with E we
consider the cell :
Pt | H2 (g) | H+ (aq)║ M+ (aq) | M(s)

E = ER - EL
ER (right electrode), EL (left electrode) =
difference ∆Ф to each electrode.
E = ER – EL = ∆ФR - ∆ФL

Cell reaction : M+(aq) + e- M(s)

½ H2(g) H+(g) + e-
M+(aq) + ½ H2(g) M(s) + H+(aq)
The electrical work of adding a charge z ē to a region
where the potential is Ф is :
We = ze x 
And therefore that the work per mole is :

We = zF x 
F = Faraday constant
z = ion charge

At constant T&P , the maximum electrical work can be

identified with the change in Gibbs energy, the difference in
chemical potential of an ions with and without the electrical
potential present is
− −
 −  = z F dan  =  + z F 
µ = electrochemical potential, the chemical potential of an
ion in the persence of an electric potential
µ = chemical potential
 When z = 0 (a neutral species) µ = µ
➢Ф>o z > o (ion is cation)
=+zF 
and µ > µ
➢Ф<o µ <µ
We note that the cations M+ are in the solution where the
Galvani potential is Φs and the electron are in the electrode
where the Galvani potential is Φm
GR = µ(M) – {µ(M+) + µ(e-)}
GR = µ(M) – {µ(M+) + F Фs + µ(e-) - F ФM}
= µ (M) - µ(M+) - µ (e-) + F Δ ФR
ΦR = Φm - Φs is the Galvani potential difference at the
right-hand electrode
In the hydrogen half-reaction, the electrons are in the
metal electrode at a potential ΦM and the H+ ions are in
the solution where the potential is Φs :
ΔGL = ½ µ (H2) - { µ (H+) + µ(e-) }
= ½ µ (H2) - µ (H+)- µ (e-) + F Δ ФL

ΔФL = ФPt- Фs at the left-hand electrode

pot ФPt = the electron are in the metal
electrode
pot Фs = H+ ions are in the solution
The overall change in Gibbs energy is :
ΔGR – ΔGL = µ(M) + µ(H+) - µ(M+)- 1/2µ(H2)+F(Δ ФR -ФL)
= ΔG + F (Δ ФR - ΔФL)
ΔG is the Gibbs energy of the cell reaction
When the cell is balanced against an external source of
potential the entir system is at equilibrium = 0
and : 0 = ΔG + F (ΔФR- ΔФL )

❖ Which rearranges to
ΔG= - F (ΔФR- ΔФL ) and
ΔG = - n F E dan n = 1
E = ER - EL
So when ΔG is changed :
- FE = - F(ΔФR- ΔФL )
ER - EL = ΔФR - ΔФL
 Electrode reaction is heterogen, to express

the amount of material produced /unit area

rate k = = kJ
time
[J] = the molar concentration of the relevant
species in solution
k = length / unit time (cms-1)
If the molar concentration of the oxidized and reduced
materials outside the double layer are [Ox] and [red],
respectively the rate of reduction of Ox is
Rate of reduction of Ox = kc [Ox]
And the rate of oxidation of Red is
Rate of oxidation of Red = ka [Red]
 a reaction at the electrode in which an ion is
reduced by the transfer of a single electron in the
rate-determining step
 the net current density at the electrode is the
difference of the current densities arising from the
reduction of Ox and the oxidation of Red
Cathodic current density of magnitude (j)
jc = F kc [Ox]
Anodic current density of magnitude (j)
ja = F ka [Red]
The net current density at the electrode is the difference :
j = ja – jc = Fka[Red] – Fkc[Ox]
If an ion (or neutral molecule) is to participate
in reduction or oxidation at an electrode, it
must
Discard any solvating molecules
Migrate through the electrical double layer
Adjust its hydration sphere as it receives or
discards electrons
Ion or molecule already at the inner plane
must be detached and migrate into the bulk.
Both processes are activated, we can expect to
write their rate constants in the form suggested
by activated complex theory
k = Be−ΔG/RT
ΔG‡ = the activation Gibbs energy
B = a constant with the same dimensions as k
(cms-1)
When this equation is inserted into equation j

j = FBa Rede  
−ΔG /RT −ΔG /RT
a − FBc Oks e c

When ja > jc j >0 anodic current

jc > ja j<0 chatodic current
 The net current is defined as the diffrence Ja - Jc

Anodic current
Anodic current

a. b.
Net current
Net current

Chatodic current
Chatodic current

a. When ja > jc, so that j > 0 and j = anodic current

and there is a net oxidation of the species in solution
b. When jc > ja, so that j < 0 and j = cathodic current
and the net process is reduction
Consider the reduction reaction, an electron is
transferred from the electrode where the potential
is ФM to the solution where it is Фs.
There is therefore an electric contribution to the
work of magnitude e Δ Ф
Ф(M)

potential

Ф(s)

outer Helhmoltz plane Inner Helhmoltz plane

1. If the transition state of the activated complex is
product=like (as represented by the peak of the
reaction profile being close to the electrode), the
activation Gibbs energy is changed from ΔGc‡(0) the
value it has in the absence of a potential difference
across the double layer, to ΔGc = ΔGc (0) + F 

ΔG a

ΔGc + F 
α≈1 ΔGc (0)
ΔG a (0)

OHP IHP OHP IHP

2. When the transition state resembles a species that has undergone
oxidation (and which represented here by a peak in the reaction profile
that lies very close to the outer Helmholtz plane) the chatodic current
activation Gibbs energy is almost unchanged but the anodic current
activation Gibbs energy is strongly affected then ΔGc‡ is independent of
ΔФ and the activation the Gibbs energy for reduction
ΔGc = ΔGc (0) + F 
ΔG a - F 

ΔG c ΔG c
α≈0 ΔGa

OHP IHP OHP IHP

3. When the transition state is intermediate in its resemblance to
reduced and oxidized species as represented here by a peak
located at an intermediate position as measured by α (0 < α <1) both
activation Gibbs energies are affected (α = ½) , the activation Gibbs
energy for this anodic process is
Katoda ΔGc + 1 FΔφ and Anoda ΔG a − 1 FΔ φ
2 2
Fungsi Gibbs pengaktifan secara umum adalah
ΔGc = ΔGc (0) −  F  and ΔG a = ΔG a (0) − (1 -  ) F 

ΔG a − 1 FΔ φ
2
ΔG c (0) ΔGc + 1 FΔ φ
2

ΔGa (0)

α ≈ 1/2

OHP IHP OHP IHP

The two activation Gibbs energies can now be
inserted in place of the values used in equation j
with the result that

j = FBaRede  
−ΔG  (0)/RT −ΔG  /RT
a x e (1−α)FΔφ/RT
− FBc Oks e c x e−αFΔφ/RT

When f = F
RT
So that
ja = FBaRede
−ΔG  (0)/RT
anodic current densities
a x e(1−α) f

cathodic current densities jc = FBc Oks e   −ΔG  (0)/RT

c x e −αf 

Next j = j a − jc
If the cell is balanced against an external source,
the diffrence in Galvani potential Δ Ф can be
identified as the (zero-current) electrode potential E
and we can write
ja = FBaRede
−ΔG  (0)/RT
a x e (1−α) fE
jc = FBcOkse
−ΔG  (0)/RT
c x e −αfE

there is no net current at the electrode (as the cell is

balanced), so the two current densities must be equal,jo
which is called the exchange current density
When the cell is producing current the electrode potential
changes from its zero-current value E to its working value
E‘ and the difference is the overpotential η
When η = E (kerja) – E
And ∆Ф = E + η
The two current densities become

ja = jo e( 1−α)fη
jc = jo e −αfη
So that :

 ( 1 − α)fη − αfη 
j= jo e −e 
 
 
Calculate the change in cathodic current density at an electrode when
the potential diffrence changes from 1,0 V to 2 V at 25°C
Answer :
initial cathodic current density Jc and after processed Jc’ the ratio of
chatodic current densities Jc and Jc’ when the potential diffrence are
∆Ф’ and ∆Ф is 2V – 1V = 1V
α = ½ , so that f = F/RT

1/2 x 9.65 x 10 4 C mol −1 x 1.0V

(
f  −  =
,
) −1 −1
= 19.47
8.314 JK mol x 298K

And j 'c
= e −19.47 = 6 x 10 −9
jc
  ( 1 − α)fη − αfη 
j= jo e −e
 
 

When the potential is so small that fη << 1

(η<< 0,01v)
The eksponen (e) can be expanded using
ex = 1 + x + ..…
And Butler-Volmer equation change to :
j = j o {1 + (1 −  ) f + ........ − (1 − f + .......)}
j  j o f

This equation shows that the current density j

is proportional to the overpotential η
at low overpotentials the interface behaves
like a conductor that obeys Ohm Law.
When η = (+) the current is anodic j > 0
when η > 0
When η = (-) the current is cathodic j < 0
when η < 0
when f = F/RT so
 F 
j = jo   dan
 RT 
RTj
=
Fjo
The exchange current density of a Pt / H2(g) / H+(aq)
electrode at 298 K is 0.79 mAcm-2 (jo)
What current flows through a standard electrode of total
area 5.0 cm2, when the overpotential is 5.0 mV(η)?
Answer : at 298K, f = F/RT = 1/25.69 mV
The current density is
 F  0.79 mAcm −2 x 5.0mV
j = jo   =
 RT  25.69 mV
j = 0.15 mAcm -2
The current through a standard electrode of total area
5.0 cm-2 is therefore
= 0.15 mAcm-2 x 5.0 cm2
= 0.75 mA the current is anodic
  ( 1 − α)fη − αfη 
j= jo e −e 
 Eksponen II 
 Eksponen I 

When the overpotential is large and positive (η) >>

corresponding to the electrode being the anode in
electrolysis,
The second exponential in Butler-Volmer is much smaller
than the first, and may be neglected. Then

j = jo e (1− ) f
the anode
ln j = ln jo + (1 −  ) f curve is ln j Vs η
 When the overpotential is large and negative (η) <<
cathode in electrolysis
The first exponential in Butler-Volmer equation may be
neglected. Then
−f
j = − jo e
cathodic
ln (− j ) = ln jo − f curve ln (-j) Vs η

The plot of the logarithm of the current density j against the

overpotential η is called
TAFEL PLOT
✓The slope gives the value of α and the intercept at η = 0
gives the exchange current density
 Some experimental values for the Butler-
Volmer parameters and we can see that
exchange current densities vary over a very
wide range

For example:
The N2 , N3- couple on Pt has jo = 10-76 Acm-2,
whereas the H+/H2 couple on platinum has
jo = 8 x 10-4 A cm-2 a difference of 73 orders
of magnitude.
The data below refer to the anodic current through a 2.0 cm2
platinum electrode in contact with a Fe+3, Fe+2 aqueous solution at
298K. Calculate the exchange current density and the transfer
coefficient for the electrode process
η (mV) 50 100 150 200 250
I (mA) 8.8 25.0 58.0 131 298

Answer:
The anodic process is the oxidation Fe+2 Fe+3 +e
We make a Tafel plot ln j Vs η , using anodic form
η (mV) 50 100 150 200 250
j (mAcm-2) 4.4 12.5 29.0 65.5 149
ln j 1.48 2.53 3.37 4.18 5.00
 TAFEL PLOT

4 ln j = ln jo + (1 −  ) f
ln j (mAcm-2)

3 regression is y = 0.92 + 0.0163x

2
The slope is (1 – α)f
1

0 (1 −  )F = 0.0163mV −1
0 5 10 15 20 25 30
η / mV RT
α = 0.58

At η = 0 the high overpotential region gives a straight

line of intercept 0,92 = ln jo, so jo = 2.5 mAcm-2
 EXERCISES

The transfer coefficient of acertain electrode in

contact with M3+ and M4+ in aqueous solution at
25°C is 0.39. The curent density is found to be
55.0 mAcm2 when the overvoltage is 125mV.
What is the overvoltage required for a current
density of 75 mAcm2 and Determine the
exchange current density
 EXERCISES

In an experiment on the Pt l H2 I H+ electrode in

dilute H2SO4 the following current densities were
observed at 25°C. Evaluate α and jo for the
electrode.
η (mV) 50 100 150 200 250

J(mAcm-2) 2,66 8,91 29,9 100 335

How would the current density at this electrode

depend on the overpotential of the same set of
magnitudes but of opposite sign?