Reference

Electrodes
 INTRODUCTION
• Reference electrode can be used to measure
the corrosion potential of a certain cell.

• The potential of the corroding surface can be

monitored periodically by means of a
reference electrode.
• An effective way to assess the severity of a
corrosion in a material is to measure the
corrosion potential because it is qualitatively
associated with the material corrosion rate.
 INTRODUCTION
• Reference electrode can be used to measure
the corrosion potential of a certain cell.

• The potential of the corroding surface can be

monitored periodically by means of a
reference electrode.
• An effective way to assess the severity of a
corrosion in a material is to measure the
corrosion potential because it is qualitatively
associated with the material corrosion rate.
Hydrogen Electrode
• The hydrogen electrode is used as a reference
for electrode potential measurements.
• Theoretically, it is the most important
electrode for use in aqueous solutions.
• The reversible hydrogen electrode in a
solution of hydrogen ions at unit activity
exhibits a potential, which is assumed to be
zero at all temperatures.
• Unfortunately, this electrode has some
drawbacks.
• First, the reversibility of hydrogen electrode
cannot be maintained in oxidizing media.
• Second, if a current is withdrawn from the
electrode, the electrode acts as an anode
because of the ionization of gas molecules.
• Also, the electrode is fragile and delicate to
handle.
• The electrode potential for hydrogen EH2 can
be determined as follows:

• where aH+ is activity of hydrogen ions, and

pH2 is hydrogen partial pressure. At one
atmosphere pressure (pH2 ), aH2=1, and
E◦H+/H2 =0 by definition.
• Therefore,.

• or in terms of pH,
Silver–Silver Chloride Electrode
• This electrode is composed of a silver wire
coated with silver chloride and immersed in a
solution of chloride ions .
• The chloride equilibrium is given by:

• Two other reactions involve a dynamic

equilibrium between deposition and
dissolution of silver together with solubility
equilibrium between silver chloride and its
ions.
• The metallic silver reaches equilibrium with
silver ions according to the following reaction:

• The overall electrode reaction is, therefore,

given by:

• The electrode potential, EAg/AgCl, is given by:

• The metallic silver reaches equilibrium with
silver ions according to the following reaction:

• OR

• The equation holds at 25◦C. It can also be

written in the following form:
• At low concentration log aCl− can be replaced
by pH as Cl− is provided by HCl acid, [Cl−]=[H+]
and hence −log aCl− can be replaced by −log
[H+]. Therefore,

• Hence,

• The following are the values of EAg/AgC for

different HCl concentrations:
• The following are the values of EAg/AgC for
different HCl concentrations:
The Calomel Electrode
• It is the most commonly used reference
electrode. It has a constant and reproducible
potential.
• The electrode basically consists of a platinum
wire dipped into pure mercury which rests in a
paste of mercurous chloride and mercury.
• The paste is in contact with a solution of
potassium chloride which acts as a salt bridge
to the other half of the cell
• The most commonly used concentrations of
KCl are 0.1 N, 1.0N and 3.5N and saturated
KCl.
• The saturated calomel is used when the liquid
junction potential is to be kept low. The
potential of electrode at 25◦C is 0.241V in
saturated KCl solution.
• Mercurous chloride is slightly soluble, and it is
in equilibrium with mercurous ions according
to:
• The overall equilibrium is expressed by:

• The mercurous chloride and mercury are at

unit activity. Therefore, the electrode
potential can be written as:

• Or
• The value of E◦ for the half cell reaction of
calomel electrode is 0.267 V. Thus, the
electrode potential becomes:

Electrode Potentials of Calomel Electrode

• (Standard hydrogen electrode taken as
reference)
Electrode Potentials of Calomel Electrode
• (Standard hydrogen electrode taken as
reference)
Copper–Copper Sulfate Electrode
• This is a reference electrode which is easy,
robust and stable.
• It is used mainly in cathodic protection
measurements, such as the measurement of
pipe-to-soil potential.
• It has a lower accuracy than other electrodes
used for laboratory work.
• It consists of copper metal placed in a solution
containing copper sulfate and copper sulfate
crystals placed in a non-conducting holder with
a porous plug
• The copper sulfate crystals maintain the
solution at a fixed ion concentration.
• Necessary contact with the earth is made
through the porous plug. It is easily recharged
when it becomes contaminated.
• The equation for the copper–copper sulfate
electrode potential is given by:

• The reaction of the Cu–CuSO4 half cell is

• The reaction of the Cu–CuSO4 half cell is

and the electrode potential:

Where

• A saturated solution of 1.47 M CuSO4 at 25◦C

is used.
• A saturated solution of 1.47 M CuSO4 at 25◦C
is used.

• Substituting in the above equation we obtain

• ECu2+/Cu=0.316+0.009 (T◦C) volts,

• Conversion of Cu/CuSO4 electrode potential
into Ag/AgCl and hydrogen electrode
potentials is expressed by the following
equations:
(a) emf (vs Cu/CuSO4) = emf (vs Ag/AgCl) –50mV
(b) emf (vs Cu/CuSO4) = emf (vs H2/H+) –316mV
• The following is the conversion table for
important reference electrodes
Problem 1
Convert−0.900V(on SCE, Sat.) to the SHE scale.
Solution:
−0.900V (on SCE, Sat.)=−0.900+0.242V(on SHE)

=−0.658V (on SHE)

Problem 2
Convert −0.916V (on SCE. 1.0 N) to the SHE
scale.
Solution:
−0.916V (on SCE, 1.0 N)=−0.916+0.280V(on SHE)

=−0.636V (on SHE)

Corrosion Kinetics
• Thermodynamics gives an indication of the
tendency of electrode reactions to occur,
whereas electrode kinetics addresses the rates of
such reactions.
• The reactions of concern are mainly corrosion
reactions, hence, it is more appropriate to call
the kinetics of such reactions as corrosion
kinetics.
• In order to understand the theory of aqueous
corrosion, it is important to develop a complete
understanding of the kinetics of reaction
proceeding on an electrode surface in contact
with an aqueous electrolyte.
• Methods which are used to study the rate of a
reaction involve the determination of the
amount of reactants remaining in products
after a given time.
• In aqueous corrosion, it is very important to
appreciate the nature of irreversible reactions
which take place on the electrode surface
during corrosion.
• ELECTROCHEMICAL POLARIZATION
• When a metal M, is immersed in a solution
containing its ions, M+, several reactions may
occur.
• The metal atoms may lose electrons (oxidation
reaction) to become metallic ions, or the
metal ions in solution may gain electrons
(reduction reaction) to become solid metal
atoms.
• The equilibrium conditions across the metal-
solution interface controls which reaction, if
any, will take place.
• When the metal is immersed in the
electrolyte, electrons will be transferred
across the interface until the electrochemical
potentials or chemical potentials (Gibbs free-
energies) on both sides of the interface are
balanced, that is, until thermodynamic
equilibrium is reached.
• The charge transfer rate at the electrode-
electrolyte interface depends on the electric
field across the interface and on the chemical
potential gradient.
• At equilibrium, the net current is zero and the
rates of the oxidation and reduction reactions
become equal.
• The potential when the electrode is at
equilibrium is known as the reversible half-cell
potential or equilibrium potential, .
• The net equivalent current that flows across
the interface per unit surface area when there
is no external current source is known as the
exchange current density,
• The difference between the potential, E, when
a net current flows through the
electrochemical cell and the reversible half-
cell potential, is called the electrode
polarization or simply the overpotential or
overvoltage, η.
• The overvoltage represents the extent to
which the electrode solution interface departs
from the equilibrium potential value.
1
• The overvoltage depends on the current
density.
• When there is no net current flow, the
overvoltage is equal to zero.
• Electrochemical processes are heterogeneous
reactions consisting of consecutive steps.
• The overvoltage controls the kinetics of the
charge-transfer reaction at the interface and is
associated with the slowest step, abbreviated
as the rate determining step.
• Electrochemical polarization experiments are
performed to study the kinetics of charge-
transfer reactions at the electrode-electrolyte
interface.
• When cathodic current is applied to the
electrode, the electrons accumulate in the
metal as a result of the slow charge transfer.
• This phenomenon causes the cathodic
polarization, , to be always negative.
• Conversely, when electrons are removed from
the metal as in the case of anode polarization ,
the polarization is always positive.
• A special case of concentration polarization
occurs when mass transport is an irreversible
process, corresponding to the transport
overpotential or diffusion overpotential
• When a slow chemical reaction causes
concentration polarization and all other
processes proceed reversibly, it is called
chemical or reaction overvoltage,
• When all the steps of the electrode reaction
except the charge transfer proceed reversibly,
the electrode polarization is called the charge
transfer or electrochemical overpotential,
• if the rate-determining step is the
incorporation of metallic ions in the electrode
crystal lattice, the electrode polarization is
called the phase overpotential,
• The departure of the operating electrode
potential from the equilibrium potential value
results from superposition of all types of
overpotentials,

2
• The electrochemical and the phase
overpotentials are called the activation
polarization,
• The overall overvoltage is the sum of the
concentration polarization and the activation
polarization:
3

• where is the sum of the diffusion and the

reaction overpotential.
• The rate of any electrochemical reaction, and
consequently the current, is controlled, in
part, by the rate of the charge-transfer
reaction and the rate of transport of the
electroactive species to the electrode surface.
• Let assume that the solution is homogeneous,
so that the surface concentration of the ions is
equal to the concentration in the bulk
solution.
• The rate of any electrochemical reaction, and
consequently the current, is controlled, in
part, by the rate of the charge-transfer
reaction and the rate of transport of the
electroactive species to the electrode surface.
• Let assume that the solution is homogeneous,
so that the surface concentration of the ions is
equal to the concentration in the bulk
solution.
• Under these conditions, the current is
controlled only by the rate of the electron
transfer at the electrode.
• O and R are oxidized and reduced species,
respectively. The cathodic rate is defined by ,
where is the cathodic reaction rate constant
and is the concentration of oxidized species.
• The rate of oxidation at the anode is first order
in the concentration of reduced species at the
electrode-electrolyte interface, R, and is given
by , where is the anodic reaction rate
constant and is the concentration of reduced
species.
• The net flux of ‘O’ at the electrode surface
(conversion rate of O to R) is the difference
between the cathodic and the anodic rates,
which is proportional to the net current, i, that
passes in the circuit. Thus,
4

F in Eq. (5) is Faraday’s constant, while A is the

electrode surface area.
• At equilibrium, the net current flow is equal to
zero; that is, the current flow for the forward
reaction (product formation) is equal to the
current flow for the reverse reaction (reactant
formation from the products) in an
electrochemical reaction involving oxidation
and reduction reactions.
• In most cases, the reaction rate constants ‘k’
follows the Arrhenius equation:

6
• where Z is the preexponential factor, ΔG is the
activation energy, R is the universal gas
constant, and T is the absolute temperature.
• From transition state theory, the temperature
dependence of anodic and cathodic rate
constants is given by:

7a

7b
• Under equilibrium conditions, the ratio of the
concentration of the oxidized and reduced
species is given by the Nernst equation:
8

• where and are the equilibrium and standard

half-cell potentials, respectively.
• Taking the logarithm of Eqs. (7a) and (7b) and
substituting into Eq. (6), one obtains:

9
 9
Where n is the number of electrons,

• Combining Eq. (9) with the Nernst equation,

one obtains:
10
• For the cathodic and anodic activation
energies, one can assume simple linear
relationships:
11
12
Where
is the fraction of the total energy (-nFΔE) that
decrease the enrgy barrier for the cathodic
reaction, while is the fraction that increase the
anodic potential barrier. The parameter are
called the cathodic and anodic transfer
coefficients.
• If under equilibrium conditions, the cathodic
and anodic activation free energies are
substituted into Eqs. (7a) and (7b), one
obtains:
13

14
Where
15
• Current flows through the corrosion system
(electrochemical cell) only when the redox
reaction is not at equilibrium.
• The difference between the operating
electrode potential,E, and the equilibrium
potential, is defined as the electrode
polarization, ΔE.
• The rate constants at nonequilibrium
conditions are defined as:
• The rate constants at nonequilibrium
conditions are defined as:

16
17
Thus the rate of the anodic and cathodic
reactions can be expressed as;
18a

18b
• substituting the rate constant at non-
equilibrium conditions into Eq. (3.7):

19
or
20

Where is the exchange current density while

and are the concentrations of the oxidized and
reduced species in the bulk of the solution at
equilibrium.
• At equilibrium conditions;
21
22

23

24
• Assuming fast transport, the concentrations
of the electroactive species in the bulk and at
the electrode interface are equal which
reduces Eq.(20) to the Butler-Volmer equation
(25), which is a fundamental equation in
electrode kinetics.

25
• The electrode overpotentials, η, and its effect
on current, i, are very significant in
electrochemistry and corrosion engineering.
• When η is large, one of the exponential terms
of the Butler-Volmer equation will be
negligible as compared to the other.
• For example, when the overpotential is large
and cathodic (negative), the anodic term in Eq.
(25) is negligible, and we can approximate Eq.
(25) using the form:
• For example, when the overpotential is large
and cathodic (negative), the anodic term in Eq.
(25) is negligible, and we can approximate Eq.
(25) using the form:
26
Or
27

• Equation (27) is the Tafel equation.

• named for the German scientist who
discovered the relationship between the
current equivalent to the rate of a single
reaction on a metal surface and the potential
of the metal.
• By defining the Tafel constants

28a
And
28b
• Equation (27) can be simplified to:

29
Or
30
• Similar expressions are obtained when the
overpotential is large and anodic (positive),
resulting in the cathodic term being
eliminated.
• When the anodic process takes place,
• When the anodic process takes place,
31
then
32
and
33

The Tafel relationship for the anodic process

becomes:
• The Tafel relationship for the anodic process
becomes:
34
Where
35a
And

35b
Problem 1
The potential of a platinum cathode at which
hydrogen is evolved is −0.85V relative to a
saturated calomel electrode. If the pH of the
aqueous electrolyte is 2.00, determine the
hydrogen over-potential (ηC).
Solution:
Erev(H)=−0.059×pH=−0.592×2
=−0.11840V
• It is necessary to convert the potential given,
−0.85 volt (SCE) to the hydrogen scale. The
conversion factor is
SHE = SCE + 0.242
SHE =−0.85 + 0.242 (0.242 is the potential of
standard calomel electrode)
=−0.608V (SHE)

The over-potential
ηC=E−Erev=−0.608−(−0.11840)
=−0.4896V
Problem 2
• The potential of an iron electrode when
polarized as a cathode in an aqueous medium
is -0.716 V vs. SCE. What would be the value
of the hydrogen overpotential of this
electrode in an electrolyte with a pH of 2.0?
Solution:
• The hydrogen overpotential, η, is the
difference between the potential of iron
electrode (E= -0.716 V vs. SCE) and the
potential of the hydrogen reaction.
Solution:
Problem 3
• The potential of an iron electrode when
cathodically polarized in an aqueous medium
is 0.75 V vs. SHE. Determine the hydrogen
overpotential in electrolytes with Ph between
1 and 6.
Solution:
Solution:
Problem 4
A nickel electrode is corroding in a deaerated
electrolyte which has a pH of 3.0 and a
concentration of nickel ions of 0.003 at 25◦C.
a) Determine the icorr of nickel.
b) Determine also Ecorr.
The following data is provided
Solution:
• Reaction:
Solution:

eqn (1)

eqn (2)
Equating equations (1) and (2), we get

(b) By substituting the value of icorr either in

equation (1) or (2), Ecorr can be obtained
Equating equations (1) and (2), we get

(b) By substituting the value of icorr either in

equation (1) or (2), Ecorr can be obtained
Problem 4
• An iron pipe is used for transporting of
(pH = 0.3). The rate of flow of acid in the pipe
is 0.3 m/s at 25◦C. The relationship between
the limiting current density and velocity is
given by the following additional
information is provided:
If the surface acts as the cathode, determine:
(a) The corrosion potential of iron.
(b) The corrosion rate of iron in mm/year.
(c) The corrosion rate of iron in mdd.
Solution:
From Faraday’s law:

• The rate of corrosion in mm/year can be

determine as below:
• The rate of corrosion in mm/year can be
determine as below:
• The rate of corrosion in mdd:
Example
Oxygen evolves at a platinum anode at pH 8 when a
potential of 0.515 V with respect to the saturated calomel
electrode is applied. The reaction occurs at unit pressure of
oxygen. The potential of the standard calomel electrode is
0.241 V vs. SHE.
a) Calculate the overpotential of the oxygen evolution
reaction and predict whether or not the reaction will
take place at this potential.
b) Calculate the overpotential of the reaction at pH 6, 7, 9,
and 10 and determine whether the oxygen reduction
reaction will occur if the applied potential of the
platinum remains at 0.515 V vs. SCE. Given: The standard
electrode potential for oxygen evolution reaction at pH
14 is 0.401 V vs. SHE.
.
.
EXAMPLE
Corrosion current:
EXAMPLE:
EXAMPLE: