ELECTROCHEMICAL CORROSION

INTRODUCTION
• Corrosion is a nonequilibrium electrode
process occurring under open circuit
conditions without the application of an
external current.
• During the corrosion process, metals tend to
convert to more thermodynamically stable
compounds such as oxides, hydroxides, salts,
or carbonates.
 ELECTROCHEMICAL CORROSION

• The electrochemical corrosion process consists of two

partial electrochemical reactions:
the anodic partial reaction, consisting of
oxidation/dissolution of the metal, and the
cathodic partial reaction, consisting of the reduction of
water, hydrogen, or oxygen gas.
• The energy change of the partial corrosion reactions
provides a driving force for the process and controls its
direction.
• Electrochemical corrosion reactions have different
thermodynamic and kinetic properties than chemical
reactions.
 ELECTROCHEMICAL CORROSION

• Thermodynamically, the reaction is controlled by

the ratio of the internal energy of the reactants
to their activation energy.
• The collisions of the particles are not limited in
the reaction space and may occur in any
direction.
• As a consequence, the electrons also move in
any direction in the reaction space.
• The only requirement is that the path of the
charge transfer must be very small.
 ELECTROCHEMICAL CORROSION

• With an electrochemical reaction, the

activation energy of corrosion reactions and
their kinetic properties depend not only on
activity, chemical potential, and temperature,
but also on the electrocatalytic properties of
the materials.
• The thermodynamics of corrosion processes
provides a tool to determine the theoretical
tendency of metals to corrode.
 ELECTROCHEMICAL CORROSION

• Thus, the role of corrosion thermodynamics is

to determine the conditions under which the
corrosion occurs and how to prevent corrosion
at the metal/environment interface.
• Thermodynamics, however, cannot be used to
predict the rate at which the corrosion
reaction will proceed.
• The corrosion rate must be estimated by
Faraday¯s law and is controlled by the kinetics
of the electrochemical reaction.
 ELECTROCHEMICAL CORROSION

• Corrosion occurs along the grain boundaries

of the metal, known as intercrystalline
corrosion.
• Electrochemical corrosion may occur in
aqueous electrolytes, gas atmosphere in the
presence of moisture on the metal surface
(atmospheric corrosion), or as soil corrosion.
• Corrosive failure may also occur due to
electrocorrosion, which is caused by an
external electric current.
 ELECTROCHEMICAL CORROSION

Corrosion is initiated by electrochemical reactions in:

• Technical metals that contain impurities of other
metals: Examples are technical metals such as zinc
and tin, which contain silver or iron as impurities.
• The standard electrode potentials of silver and iron
are more electropositive than those of zinc or tin,
causing zinc and tin to corrode through a form of
galvanic corrosion, while the impurities remain
intact.
• Because of their more positive electrode potentials,
silver and iron are cathodically protected by zinc or
tin.
 ELECTROCHEMICAL CORROSION

• Identical metals in contact with solutions of

different concentrations:
• The metal dissolves from the electrode
immersed in a dilute solution, and is deposited
on the electrode that is immersed in a more
concentrated solution.
• The corrosion stops when the electrolyte
concentration is homogeneous at the
interfaces of both of electrodes.
 ELECTROCHEMICAL CORROSION

• Identical metals in contact with solutions of

different concentrations:
• The metal dissolves from the electrode
immersed in a dilute solution, and is deposited
on the electrode that is immersed in a more
concentrated solution.
• The corrosion stops when the electrolyte
concentration is homogeneous at the
interfaces of both of electrodes.
 ELECTROCHEMICAL CORROSION

• differential aeration cell.

• The electrode potential difference in this case
results from different oxygen aeration of the
electrodes.
• This type of corrosion initiates crevice
corrosion in aluminum or stainless steel when
exposed to a chloride environment.
 ELECTROCHEMICAL CORROSION
• Identical metals each exposed to a different
temperature:
• The driving force for this type of corrosion results from
each electrode having a different temperature when
they are immersed in a homogeneous electrolyte.
• The metal exposed to the higher temperature acts as a
cathode.
• When this metal is in electrical contact with a metal
exposed to the lower temperature (anode), the metal
dissolves from the lower-temperature electrode
(anode) and is deposited on the higher-temperature
electrode (cathode).
 THERMODYNAMICS OF CORROSION PROCESSES
• The energy change of the partial corrosion
reactions provides the driving force for the
overall reaction and controls its spontaneous
direction.
• Corrosion thermodynamics establishes the
quantitative relationship between the
electrical energy produced or consumed
during the corrosion processes and the
chemical energy.
 THERMODYNAMICS OF CORROSION PROCESSES
• The corrosion of iron in an acid environment
occurs according to the following reaction:

1
• The dissolution of iron in an acidic solution
releases hydrogen without the formation of
any oxide barrier films on the surface.
 THERMODYNAMICS OF CORROSION PROCESSES
• The reaction shown in Eq. (1) may be
separated into two partial reactions:
2a

2b
• In Eq. (2a&b), the iron atoms are transformed
into iron ions while the electrons produced
are consumed during the reduction of
hydrogen ions to hydrogen gas.
 THERMODYNAMICS OF CORROSION PROCESSES
• In Eq. (1),”n”represents the number of elementary
charges, e = 4.803*10^-10 (1.602*10^-19
coulombs) or electrostatic units exchanged during
the anodic and cathodic charge transfer reactions.
• According to sign convention, the stoichiometric
numbers are positive for the products and negative
for the reactants.
• For the corrosion reaction presented in Eq. (1), the
changes in the number of moles of the species in
the reaction are proportional to their
stoichiometric numbers.
 THERMODYNAMICS OF CORROSION PROCESSES
• The quantity of electricity produced as a result
of the chemical reaction is equal to the product
of nFE,
• where E is the electromotive force measured in
the case of reversible reactions.
• The quantity F is the Faraday constant, which
can be estimated from the product, of F =Na * e
where Na = 6.02*10^-23 (Avogadros number)
and “e” is the elementary charge.
• The absolute value of the Faraday constant
equals 96,485 C (coulomb).
 THERMODYNAMICS OF CORROSION PROCESSES
• For any isothermal process, the reaction
described in Eq. (1), when performed at
constant pressure, decreases the Gibbs free-
energy (G).
• Assuming that the corrosion process proceeds
at constant pressure, the change of Gibbs free-
energy is the focal point for any thermodynamic
analysis of corrosion reactions.
• The change in the Gibbs free-energy represents
the maximum useful work for an isothermal
and isobaric conversion for the reaction
 THERMODYNAMICS OF CORROSION PROCESSES
• For any isothermal process, the reaction
described in Eq. (1), when performed at
constant pressure, decreases the Gibbs free-
energy (G).
• Assuming that the corrosion process proceeds
at constant pressure, the change of Gibbs free-
energy is the focal point for any thermodynamic
analysis of corrosion reactions.
• The change in the Gibbs free-energy represents
the maximum useful work for an isothermal
and isobaric conversion for the reaction
Application of Free Energy to
Corrosion Cells
• It is known that corrosion reactions produce
electrical energy.
• The amount of work done by a cell is equal to
the quantity of electrical energy which it
generates under constant pressure,
temperature and concentration of the
reaction.
• In an electrochemical reaction, electrical
energy available is equal to the product of
potential of the cell and the quantity of
electricity involved (volts × amperes × time).
That is,
• Electrical energy = E×Q.
• This is equal to the net work done by the cell.
• From Faraday’s law, Q is one Faraday (F) for
each gram equivalent of the reactants.
• For n gram equivalent of the reactants, Q is
equal to nF. Work can only be performed if
the free energy of the cell is decreased.
 Equation (1)
where
• ΔG = change in Gibbs free energy of a cell in
joules per mole
• n = number of electrons involved in the
reaction
• E = emf of the cell in volts.
• If all substances are in their standard states
(i.e.at unit activity) the expression (eqn 1)
becomes:
eqn (2)

Example 1
For the cell [Cu/Cu2+(1.0M)]//[Zn2+(1.0M)/Zn],
and the cell reaction Cu+Zn2+→Cu2++Zn:
 Nernst Equation
• The Nernst equation expresses the emf of a
cell in terms of activities of products and
reactants taking place in the cell reaction.
• Consider a general cell reaction:
Eqn (3)

• M1 and M2 represent metal electrodes, such

as Cu and Zn, in a cell, and the above reaction
(3) can be written as:
 Eqn (4)

• The free energy change (ΔG) of a reaction is

given by the difference in the molar free
energy of products and reactants as shown in .

eqn (5)

• Therefore, the free energy change for the

reaction (3) can be expressed as:
 Eqn (6)
• If the substances are in their standard states
the above expression becomes:

eqn (7)

• Free energies of any metal, such as M1 at its

standard state and any arbitrary state are
related through the following equation:
 Eqn (8)

where
• aM1 is the activity of metal M1,
• R is the universal gas constant, and equal to
8.314 joules/degree/mole, and
• T is absolute temperature in degrees Kelvin,
◦K, which is (273.16+t°C).
• Subtracting equation (7) from equation (6),
we get:

Substituting from equation (8), we obtain:

•
Eqn (9)

where
• the ‘a’ values are any arbitrary activity values,
for which ΔG is the corresponding free energy
of that reaction.
• ΔG◦ is the free energy change for the reaction
involving standard states (unit activities).
• As G=−nFE, and also G◦=−nFE◦, from
equations (1) and (2), respectively, then above
equation (9) becomes:

Eqn (10)

hence
• suppose

because aM and ae =1. hence At 25°C

• Equation (10) is a general form of the Nernst
equation.
• It expresses the emf involved in an
electrochemical reaction, such as equation (2)
in terms of R, T, F, n activities of products and
activities of reactants.
• However, the IUPAC sign convention requires
the above minus sign to be replaced by a plus
sign.
• The Nernst equation is re-written to comply
with the IUPAC sign convention, as:

• which is written regardless of which way round

the redox reaction is written, Hence, for
• which is written regardless of which way round
the redox reaction is written, Hence, for
 Application of Nernst Equation to a
Corrosion Reaction
• A corrosion reaction can be considered as
composed of two half cell reactions. One of
the half cell reactions corresponds to
‘oxidation reaction’ taking place on the
‘anode,’ and the other half cell reaction
corresponds to ‘reduction reaction’ taking
place on the ‘cathode’ of the cell.
• The contribution of each half cell reaction to
the Nernst expression can be derived as
follows:
• oxidation reaction at anode
eqn (11)

• reduction reaction at cathode

Eqn (12)

• Equation (10) can also be re-arranged into

expressions to correspond to reactions (I) and
(II):
• oxidation reaction at anode
eqn (12)

• eqn(13)
where

eqn (14)

eqn(15)
And

eqn(16)
• Equations (14) and (15) are Nernst equations
for the half cell reactions and equation (16) is
the Nernst equation for the complete cell
reaction.
• Equation (17) can be put into a mathematical
form:

eqn 17
• But, in addition to this statement ,a sign
convention is necessary as already mentioned
and this will be discussed in the next section.
Since
eqn 18

• Equation (16) is more commonly used in the

form of
• But

eqn 19

• The expression (19) can also be written with

the activities inverted, as

eqn 20
• But this equation is incomplete without a sign
convention.

• Quite separate from the above considerations,

standard Redox potentials are tabulated with
reactive metals like Zn negative instead of
positive, which accords with the experimental
fact that Zn will actually become negative
because when Zn++ ions leave it, then two
electrons will appear in the Zn metal, to
maintain a charge balance.
• Such reduction potentials are given in Table
2.1(which is given in the class) .
• By convention the cell reaction is written as if
the oxidation process is occurring at the
electrode on the left and reduction on the
right.
• This practice is in accordance with the
International Union of Pure and Applied
Chemistry (IUPAC) Convention held in 1953
and modified in 1960.
 Sign Convention
• The older American Convention has been to
use oxidation potentials rather than reduction
potentials.
• The present practice is to use reduction
potentials instead of oxidation potentials in
accordance with the recommendation of
IUPAC (International Union of Pure and
Applied Chemistry) and existing European
practice – the general convention is that the
cell emf is given by:
• The standard hydrogen electrode (SHE) is the
reference point.
• By definition, SHE has zero potential at 25°C. It
is assumed that oxidation occurs at the
hydrogen electrode so that it is placed at the
left-hand side of a cell diagram.
• If a cell is composed of SHE and some other
electrode, then the measured voltage of the
cell is the electrode potential of the second
electrode:
For example, in a galvanic cell made of a
hydrogen electrode and a zinc electrode
[Zn/Zn2+ (1.0 M)], the measured voltage is
E=−0.763 volts.
• which is opposite to that shown above. This
should clarify the confusion caused in
student’s minds by different conventions. The
simplest procedure avoids specifying ‘right’
and ‘left’ by just writing:

• which is written regardless of which way

round the chemical equation is written.
Positive and Negative EMF
• A positive emf (E >0) signifies a deficiency of
electrons on the right-hand electrode because
of the extraction of electrons from that
electrode.
• Therefore, the tendency of the right-hand
electrode is reduction (acceptance of electron;
MRE+e=MR, if E >0).
• At the same time, positive emf signifies an
excess of electrons on the left-hand electrode.
• Therefore, the electrode reaction is oxidation
(ML=M+L+e) on that electrode.
• Thus, if E >0, the cell reaction has a tendency
to proceed from left to right: that is, electrons
are produced by the left-hand electrode and
consumed by the right-hand electrode.
• It also indicates that the reaction is
spontaneous.
• Conversely, if E <0, the reaction at the right-
hand electrode is oxidation and the reaction at
the left-hand electrode reduction.
• The tendency of the reaction would,
therefore, be to proceed from right to left and
the reaction would not be spontaneous.
Example 1
Two half cell reactions are given below:

Their reduction potentials are given opposite to

each reaction. Calculate:
(a) the emf of the cell and
(b) show the spontaneous cell reaction.
solution
the left-hand electrode (Zn) is the anode and the
right-hand electrode (Cu) is the cathode
according to the convention. Therefore, zinc will
undergo oxidation and copper reduction as
shown below. Hence:
a)
b)Spontaneous cell reaction is given by:
cell reaction = cathodic reaction = anodic
reaction

• From the table of standard reduction

potentials (Table 2.1), the reduction potential
of Cu is +0.34 volts and that of Zn is −0.76
volts. The emf of the cell is positive. Hence the
reduction is spontaneous and it should
proceed from left to right.
• If the position of the electrodes are now
interchanged such that the copper electrode is
placed on the left and the zinc electrode on
the right, the sign of the cell emf will change.
• Here, zinc electrode being on the right is
treated as cathode and the copper on the left
as anode according to the IUPAC convention.
• Therefore:

• Subtracting anodic reaction from cathodic

reaction to obtain the cell reaction
• The emf obtained is now negative which
indicates that the reaction is not spontaneous
and the current flows from right to left.
• The left-hand electrode where the current
originates is, therefore, the anode, and the
right-hand electrode, the cathode. The
polarity of the cell is, therefore, clearly
established.
Example 2
Calculate the reversible potential for a zinc
electrode in contact with ZnCl2 when the
activity of inc is aZn2+ =10 Use IUPAC
convention.
Solution:
• We write the half cell reaction
Apply Nernst equation:
Example 3
Show that for the reduction reaction given
below:

Solution:
The reaction is 2H++2eH2. Using Nernst
equation we obtain for the above reaction:
Changing to 2.303 log and substituting for
R=8.314J/(mol·K), F =96490C,
T =298◦K, 2.303RT/F =0.0591V.
• The Nernst expression above can, therefore,
be written as:

• Now substituting pH=−log(H in the above

expression we get:
Example
In the cell reaction given below, what is the ratio
of the activities of ionic species required to
make the polarity reverse?

Solution:
Cell reaction:

• Ratio of activities to make the polarity reverse

at 25◦C. Standard cell potential:
Example
In the cell reaction given below, what is the ratio
of the activities of ionic species required to
make the polarity reverse?

Solution:
Cell reaction:
Solution

The reaction in this case is non-spontaneous.

That is, Fe2+/Fe electrode will act as ‘anode’ and
Sn2+/Sn electrode will act as ‘cathode,’ the
reverse case of what was assumed in the
problem.
To reverse the polarity:
Overall cell potential is given by:

Where as
Therefore,

• Assuming the reaction is taking place at t =

25◦C, n=2,T =298◦K,R=8.315 J/mol and F =
96500 C(g equiv.)−1
Then
Example
The emf of a cell made of Zn (anode) and H2
electrode (cathode) immersed in 0.7M ZnCl2 is
+0.690 volts. What is the pH of the solution?
Solution: plz change the value of activity coef
Given:
Solution:
Solution:
Example
Calculate the theoretical tendency of nickel to
corrode in deaerated water of pH=8. Assume the
corrosion products are H2 and Ni(OH)2 and the
solubility product is 1.6×10e−16.
Solution:
Solution:
Example
Calculate the pressure of H2 required to stop
corrosion of iron immersed in 0.01M FeCl2, pH=4.
Solution:
Solution:
Example
Calculate if silver would corrode when immersed
in 0.5M CuCl2 to form solid AgCl. What is the
corrosion tendency?
Solution: plz change the value of activity
Solution: