Corrosion Engineering

Introduction

Since the student has not studied electrochemistry, this course will start with the fundamentals
of electrochemical science such as galvanic cells, electrolytic cells and electrolysis, ionic
conduction, polarization, etc.
Electrochemistry (Electrochemical science)

Scope of Electrochemistry:
Electrochemistry is concerned with the relation between chemical energy and
electrical energy as shown by the following equation:

Electrolytic cell
Chemical Energy Electrical Energy
Galvanic cell
(C.E) (E.E)

Examples on conversion of chemical energy to electrical energy and vice versa:

1. In a galvanic cell such as the cell: ZnZn++ Cu++ Cu, a spontaneous reaction (ΔG= -
ve) takes place and the chemical energy change accompanying the reaction appears in
the form of electrical energy (E.E)
Zn+Cu++ Zn+++ Cu+ E.E
2. In an electrolytic cell a nonspontaneous reaction (ΔG=+ve) takes place, the energy
required to drive the reaction is provided to the cell in the form of electrical energy e.g
the production of H2 and O2 by the electrolysis of water between two platinum or
graphite electrodes.

Galvanic Cell; Electrolytic cell

Zn +Cu++  Zn+++ Cu+ EE E.E +H2O H2 + 1/2 O2

1
Galvanic Cells
A galvanic cell is composed of two electrodes between which there is a potential
difference. A galvanic cell can be considered as a chemical reactor in which a
spontaneous chemical reaction (ΔG=-ve) takes place the energy change
accompanying the reaction appears in the form of electrical energy.

Mechanism of action of galvanic cells:

To illustrate the mechanism of action of galvanic cells consider the Daniell cell
Zn Zn++ Cu++ Cu when the two electrodes are connected outside the solution
by a wire current (electrons) flow from the zinc electrode to the copper electrode
because the potential of zinc electrode is higher than the potential of copper
electrode. This potential difference originates as explained by the following
theory:-
When a zinc sheet is placed in ZnSO4 two opposing reactions take place
simultaneously: In the first reaction some Zn atoms tend to ionization Zn++ in the
solution leaving two electrons per atom on the Zn sheet
Zn Zn++ +2e (1)
In the second reaction some Zn++ from the ionization of ZnSO4 tend to deposit on the Zn sheet
which becomes positively charged while the solution becomes negatively charged
Zn++ Zn +2e i.e Zn++ +2e  Zn
Eventually an equilibrium is established between the two reactions, the equilibrium takes the
direction of the more powerful reaction which is the first reaction
Zn  Zn++ +2e (1)
As a result of this equilibrium the Zn sheet becomes negatively charged while the solution
becomes positively charged i.e a potential difference is established between the solution and
the Zn sheet. This potential difference is called the electrode potential of the zinc electrode.
Similarly at the copper electrode Cu++ Cu two opposing reactions takes place, namely:
CuCu+++2e
Cu++Cu + 2(+) i.e Cu+++2e Cu
Eventually an equilibrium is established between the two opposing reactions, the equilibrium
takes the direction of the more powerful reaction which is the second reaction in the case of
copper electrode
Cu+++2e  Cu i.e Cu++Cu + 2(+) (2)

2
As a result of the above equilibrium the copper sheet becomes positively charged while the
solution becomes negatively charged due to the presence of excess SO4-- i.e a potential
difference is established between the solution and the Cu sheet. This potential difference is
called the electrode potential of the copper electrode.
If the zinc electrode and the copper electrode are connected externally outside the solution by
a wire (fig.1) electrons accumulated on the Zn sheet flow through the wire by electrostatic
attraction to neutralize the positive charges present on the copper sheet. In the meantime Zn++
present at the surface of the Zn sheet and excess SO4-- present at the Cu sheet migrate in the
solution toward each other to attain electrical neutrality i.e electrical current flows in the
solution through ionic movement and flows outside the solution through the movement of
electrons in the metallic wire.
Reaction (1) and (2) proceed continuously in the indicated directions to produce electrical
current; the magnitude of this current depends among other things on the potential difference
between the zinc electrode and the copper electrode. The overall cell reaction can be obtained
by adding reactions (1) and (2):
Zn +Cu++ Zn++ + Cu (3)

Zn++ Cu++
Zn++ Cu++
Zn++ Cu++

Daniell cell ZnZn++ electrode Cu++ Cu electrode

ZnZn++ Cu Cu++

Factors affecting electrode potential (Nernst equation):

For the electrode MM++ where the equilibrium M M++ +2e takes place between the two
opposing reactions, Nernst found that the electrode potential e is given by:

e=eo- (ln [M++]) (1)

Where eo is the standard electrode potential which is defined as the potential developed by the
electrode when the electro active ion concentration [M++] =1.
The magnitude of eo depends on the atomic structure of the metal forming the electrode.
R=gas constant (8.3J/mol.K), T= temperature in K, Z is the number of electrons involved in
the reaction, F is Faraday’s constant (96500 Coulomb)

The value is 0.059 at 25 C, accordingly equation (1) can be written as:

3
e= eo – log[M++]

Equation (1) can be written more precisely in terms of the activity (effective concentration) of
the electroactive ion as

e= eo – log a

Activity and activity coefficient:

If for instance 1M of an electrolyte is dissolved in water its ability to react with other
substances is represented by an effective concentration lower than the dissolved concentration
(1M). The effective concentration is known as the activity a, the deciation between the activity
and the dissolved electrolyte concentration is caused by forces of interionic attraction between
the ions. Activity is related to the dissolved salt concentration by the equation
a=f±c
Where f± is the mean activity coefficient of the salt and c is the dissolved salt concentration.
The value of f can be predicted from the Debye-Huckel law which is given by the equation:
For a salt: log (f±) =-0.51 Z1Z2√
Where Z1= valency of the –ve ion, Z2= valency of thee +ve ion, I= ionic strength of the
electrolyte which is a measure of the intensity of the electrical field resulting from all ions
present in the solution. I is given by
I= ∑Ci Zi2
For a single ion the activity coefficient f can be predicted from the Debye- Huckel law which
for a single ion is given by
log (f) =-0.51Z2√
Where Z is the valency of the ion

Types of electrodes:
An electrode is composed of the oxidized from and the reduced from of a chemical system, the
equilibrium between the oxidized form and the reduced form gives rise to the establishment of
the electrode potential
reduced form oxidized form + Ze

e=eo – ln

The activity of solids and solvents e.g H2O is considered to be 1and accordingly can be
eliminated from Nernst equation.
The following systems satisfy the requirements of the electrode

4
Metal electrodes,
This type of electrodes consists of a metal dipped in its salt (MM++) as shown by the
following examples:-
AgAg+ AgAg+ +e e=eo – ln

CdCd++ Cd  Cd++ +2e e=eo – ln

AlAl+++ AlAl+++ +3e e=eo – ln

(pt) H2 H+ H22H+ +2e e=eo – ln

It is noticed that the electrode potential of this type of electrodes depends on cation
concentration i.e this type of electrodes is sensitive to cations (i.e the electrode is reversible
with respect to the cation)

Metal (insoluble salt of the metal)

A soluble salt containing an anion similar to that of the insoluble salt (MMX(s)X-)
Example: AgAgCl(s)KCl
In this type of electrodes electrode reaction takes place in two steps:
(i) Ag  Ag+ +e
(ii) Ag+ + Cl- AgCl
Overall electrode reaction: Ag+ Cl-  AgCl +e
Other examples:
AgAgBr(s)KBr Ag + Br- AgBr+e e= eo – ln

AgAgI(s) KI Ag + I-  AgI + e e= eo – ln

PbPbSO4 (s) H2SO4 Pb + SO4--  PbSO4 + e e= eo – ln

HgHg2Cl2(s) KCl 2Hg +2Cl- Hg2Cl2 + e e= eo – ln

HgHg2SO4 (s) Na2SO4 2Hg + SO4--  Hg2SO4 + e e= eo – ln

It is noticed that the electrode potential of this type of electrodes is sensitive to anion
concentration (i.e the electrode is reversible with respect to the anion)

5
Redox electrodes
In this type of electrodes both the oxidized form and reduced form are water soluble, a
platinum wire is used as electrical conductor
Example
Relation between electrode
Electrode Electrode reaction
Potential and electrolyte conc.
(pt) Fe++, Fe+++ Fe++  Fe++++e e= eo – ln

(pt) Ce+++, Ce+++ Ce+++++e e= eo – ln

++++
Ce
(pt) Sn++, Sn++++ Sn++ Sn++++ +2e e= eo – ln

(pt) I2, I- 2I-I2 +2e e= eo – ln

(pt) Br2, Br- 2Br-  Br2 +2e e= eo – ln

(pt) Cl2, Cl- 2Cl-  Cl2 +2e e= eo – ln

(pt)QH2, Q, H+ QH2  Q+2 H++ 2e e= eo – ln

(pt) OH- O2 2OH- H2O+1/2 O2 +2e

e= eo – ln

Where Q=Quinone (C6H4O2), QH2= hydroquinone (C6H4(OH)2)

The arbitrary zero of electrode potential (The H2 scale):

There is no method by which the absolute value of a single electrode potential can be
measured; only the difference in potential can be measured. To evaluate the magnitude of
different electrode potentials, H2 electrode in its standard state was taken as reference
electrode against which the potentials of other electrodes were measured. The potential of H2
electrode in its standard form was assigned (given) the value zero arbitrarily. Thus when it is
said, for example, that the standard potential of ZnZn++ electrode is 0.76 Volt, that means
that the e.m.f of the galvanic cell:
ZnZn++ (a=1) H+ (a=1)H2(P=1atm) (pt) is 0.76V.

6
Construction of galvanic cells:
In constructing galvanic cells used for scientific or analytical studies, direct contact between
solutions of different concentrations should be avoided by using a salt bridge containing
saturated KCl. Direct contact between solutions of different concentrations leads to the
establishment of a liquid junction potential (L.J.P) at the interface between the two solutions.
L.J.P arises from the unequal rates of diffusion of the cation and the anion of the diffusing
electrolyte. The advantage of KCL which is used in building the salt bridge is that the
diffusivity of K+ is equal to the diffusivity of Cl- i.e both ions diffuse at the same rate,
accordingly no L.J.P takes place at the interface between saturated KCl and other electrolytes
Example: construct the cell : ZnZnCl2 HClAgCl(s)Ag

B A
C

ZnCl2 ZnCl2
HCl

ZnCl2 HCl

AgAgCl(s)
Porous
Salt bridge composed of

3gKCl+10g H2O +0.3g agar diaphragm

(C) correct construction, L.J.P (B) correct construction (A)Incorrect

is eliminated by using a single L.J.P is aliminated by construction because of
compartment cell containing a
using a salt bridge the L.J.P at the
common electrolyte
Ecell= Etrue diaphragm
Ecell= Etrue
Ecell= Etrue+ L.J.P

7
The electromotive serice (e.m.s):
The e.m.s is a list in which different electrodes are arranged according to the value of their
standard electrode potential (eo). The e.m.s id of a great importance in the study of corrosion,
batteries, electrowinning of metals and electro-refining of metals. The following list
represents a short e.m.s with only some electrodes (for a comprehensive e.m.s see any book on
electrochem.)

8
E.M.F measurement by the compensation method:
(For details see practical part)

2 volt battery

C
B
A
Potentiometer wire of 100 cm
length made of a high
resistance alloy such as pt-Ir or
Ni-Cr

Cell of unknown e.m.f Galvanometer

The e.m.f of the cell is obtained from the equation:

Where E= e.m.f of the cell, Est= e.m.f of the standard cell, L= null point length recorded in
case of cell, Lst= null point length recorded in case of the standard cell.

Advantages of measuring the e.m.f by the compensation method

over the voltmeter method
A voltmeter measures the e.m.f of a galvanic cell while a current I is
passing through the circuit. Accordingly part of the cell voltage is lot
as IR drop where I is the current passing in the circuit, R is the
internal resistance of the cell, i.e the voltmeter reads an e.m.f. On the
other hand the compensation method measures the cell e.m.f while no
current is passing in the circuit (I=0). Accordingly there is no IR drop
and the measured e.m.f is equal to the true (real) e.m.f of the cell. In other words the
compensation method measures the e.m.f of the cell while the cell is working reversibly (I=0)
while a voltmeter measures the cell e.m.f while the cell is working irreversibly (I>0). For
precise measurements of e.m.f the compensation method should be used while the voltmeter is
used for approximate measurements.

9
The standard cell :
The standard cell is represented by: - ve Pt + ve

Cd(as 12.5% Cd amalgam)CdSO4(saturated)  Hg2SO4(S) Hg

The standard cell is used in the compensation method to Sat. CdSO4

solution
determine the e.m.f of the cell whose e.m.f is not known
because the e.m.f of the standard cell is almost constant,
this is due to:-
(i) The temperature coefficient of e.m.f of the cell dE/dT Crystals
is small i.e the e.m.f of the cell does not change with of CdSO4 Hg2SO4
temperature. Hg
12.5% Cd
(ii)The presence of saturated CdSO4 concentration will amalgam
remain constant even if small current passes through Structure of the standard
the cell cell

Reaction of the standard cell:

- ve: CdCd++ +2e
+ ve: Hg2SO4 +2e2Hg +SO4—
Overall cell reaction
Cd+ Hg2SO4  Cd+++SO4--+ 2Hg

Some rules (conventions) concerning galvanic cells:

1- To write the overall cell reaction in the correct direction individual electrode reactions
should be written in the correct direction. The left hand electrode is considered as the –
ve cell electrode (anode) where an oxidation reaction(loss of electrons) takes place; the
right hand electrode is considered as the + ve cell electrode (cathode) where a
reduction reaction (gain of electrons) takes place.
2- The e.m.f of the cell is the algebraic sum of the two electrode potentials i.e
Ecell= (e-ve)ox + (e+ve)red

10
 3- The following signs are used in writing galvanic cells
Sign Meaning
 Used to separate liquids from solids
 Means a salt bride

, Placed between two electrolytes in the same solution

Placed between two solutions in direct contact at their interface

Concentration cells:
Concentration cells are galvanic cells which are composed of two similar electrodes but of
different electrolyte concentration. Concentration cells are
useful in explaining the mechanism of corrosion of metals as
will be seen later
Example of a concentration cell: Salt

Cell: AgAgNO3 AgNO3 Ag where C2> C1 bridge

KNO3
C1 C2 + H2O
Ag Ag
Reactions: -ve: AgAg+ +e +agar

+ ve: Ag++eAg
C1 C2
Overall cell reaction: Ag+(C2)Ag+(C1)
i.e the overall process is a physical process, namely a diffusion process and not a chemical
reaction as in the case of ordinary galvanic cells
Expression for cell e.m.f:
e- ve= (eo)ox– ln(C1) Ag+

e+ ve= (eo)red + ln(C2) Ag+

E= e+ ve + e- ve = ln(C1/C2)

11
Some application of galvanic cells

Thermodynamics of galvanic cells- Determination of the thermodynamic

finctions of a reaction by e.m.f measurements
Consider the reaction: Zn+Cu++= Zn++ + Cu, this spontaneous reaction can be carried out
chemically by placing a piece of Zn in a beaker containing CuSo4—solution. In this case the
energy of the reaction will appear in the form of heat ΔH measured by a calorimeter (fig.1.a).
Alternatively, the same reaction can be carries out electrochemically in a galvanic cell (Daniell
cell) as shown in fig.1.b

W
Cu Zn
Zn

Zn Cu CuSO4

Fig.1.b Fig.1.a

The reaction is carried out The reaction is carried out, chemically in a

electrochemically in a galvanic cell beaker where all the chemical energy of the
[ZnZn++ Cu++Cu] where part of the reaction appears in the form of heat energy
chemical energy appears as electrical (ΔH)
energy (W) and the other part appears as
heat (q)

When the reaction is carried out electrochemically in a galvanic cell, part of the chemical
energy of the reaction appears in the form of heat energy q measured by the calorimeter and
the other part appears in the form of electrical energy W measured by a Wattmeter. The sum
of the electrical energy and the heat lost to the surrounding q is equal to ΔH (the heat of the
reaction) The relative amounts of W and q depends on the current withdrawn from the cell. As
the current increases W decreases while q increases owing to the conversion of a part of the
electrical energy into heat (I2R) due to the internal cell resistance R. On the other hand as the
current decreases W increases and q decrease when the current approaches zero W becomes
maximum (Wmax) and the heat lost to the surrounding (q) becomes minimum. When this
condition (I=0) is reached the cell is said to be working reversibly since the free energy of a
reaction ΔG is defined as:
12
ΔG = - maximum work done (-Wmax)
For galvanic cells, the maximum work done is the maximum electrical energy obtained from
the cell during its reversible operation Wmax
i.e ΔG= - Wmax= -ZEF Joule
To obtain ΔG from the above equation the cell e.m.f E should be measured while the cell is
working reversibly, tthis condition is realized by measuring the e.m.f of the cell (E) by the
compensation method as mentioned before.

The Gibbs- Helmholtz equation:

An energy balance on a galvanic cell working reversibly gives
ΔH= ΔG + q (1)
where ΔG is the free energy of the reaction, also is known as the useful energy or the available
work, q is the heat lost to the surrounding also known as the unavailable energy, ΔH is the
heat of the reaction or the enthalpy change of the reaction
q= T ΔS (see thermodynamic course) (2)
where ΔS is the entropy change of the reaction
ΔS= -dΔG/dT (2nd law of thermodynamics)

ΔS = -d(-ZEF)/dT = ZF (3)

Substituting for ΔS in equation (2)

q= ZEF

substituting for ΔG and q in equation (1)

ΔH = -ZEF + ZFT

ΔH = -ZF(E- T )

The above equation is known as the Gibbs- Helmholtz equation and is used to calculate ΔH

from e.m.f measurement. is called the temperature coefficient of e.m.f

Thermodynamic derivation of Nernst equation

Consider the following reaction to be taking place in a galvanic cell
aA+ bBcC+ dD
The chemical potential U which is the free energy per mole is given by
U= Uo+ RT(ln(a))
Where Uo is the standard chemical potential, a is the activity of the dissolved substance, R is
the gas constant, T is the temperature K. The free energy of the cell reaction is given by
ΔG = ∑ Gproducts -∑ Greactants
= [c (Uo+ RT (ln(ac)) + d(Uo+RT(ln(aD))] - [ a (Uo+ RT (ln(aA)) + b(Uo+RT(ln(aB))]

13
 = [cUoc+dUoD – aUoA-bUoB]+RT ln

ΔG = ΔGo + RT ln

The above equation is Known as the Vant Hoff isotherm or the reaction isotherm, it relates
the free energy of reaction to the concentrations of the products and the reactants at a constant
temperature. ΔG is the standard free energy of the reaction (ΔG0 = - ZEoF)
substituling for ΔG and ΔG0 in equation (1)

- ZEF= - ZEoF + RT ln

Dividing both sides by –ZF

E= Eo- ln

which is Nernst equation (E0 is the standard cell voltage)

Determination of the equilibrium constant of a reaction from e.m.f data:

When the cell reaction reaches the equilibrium stage ΔG becomes zero and the quotient

becomes equal to the equilibrium constant K, equation (1) (the reaction isotherm) becomes:
0= ΔGo+ RT ln(K)
since ΔGo= - ZEoF
Therefore
0 = -ZEoF+ RTln (K)
ZE0F = RTln(K)

Eo = ln(K)

The standard cell voltage Eo can be calculated from the standard electrode potential of the
cathode and the anode
Eo= (e-ve) + (e+ve)
Equation (1) can be used to calculate the equilibrium constant of the reaction taking place in
the cell.

14
pH measurement and Control :
A pH meter consists of a galvanic cell composed of two electrodes, an electrode sensitive
to H+ (reversible with respect to H+) and a reference electrode (calomel electrode). The e.m.f
of the cell is measured by an electronic potentiometer (based on the compensation method) the
dial of the potentiometer is calibrated to read the pH value directly as well as the e.m.f of the
cell in millivolts. Electrodes reversible with respect to H+ which can be used in PH
measurement include:
(i) The H2 electrode
(ii) The quinhydrone electrode and
(iii) The glass electrode

(i)The H2 electrode :
The H2 electrode is constructed by passing pure H2 gas at a pressure of 1 atmosphere inside
the solution whose pH is to be determined, a platinum wire is inserted in the solution to
conduct electricity. The following reaction takes place in the H2 electrode:
H2  2H+ + 2e
The electrode potential of the electrode is given by

e= eo-

Since eo of the hydrogen electrode = 0 and PH2= 1 atm, the above equation reduces to
eH2/H+ = -0.059 LogH+
Since pH = - Log H+
eH2/H+ = 0.059 pH (1)
To determine the potential of the H2 electrode, the electrode is coupled with a calomel
reference electrode to form the cell:
(pt) H2  H+ (test slon (pH=?))  KCl  Hg2Cl2  Hg
The e.m.f of the cell E is measured by the compensation method, the electrode potential of
H2 H+ can be calculated from the equation
E = eH2H+ + ecalomel
(ecalomel is known or it can be calculated from Nernst equation). After calculating eH2H+ from
the above equation, the pH can be calculated from equation (1)

15
 Pt

Pure H2 gas P= 1 atm H2 bubbles

Pt
KCl (0.1 M)

Hg2Cl2
Test solution pH=?
Hg
H2 Calomel
electrode electrode

Cell used for pH measurement

Limitations (drawbacks, shortcomings, disadvantages) of the H2 electrode:

(1)It is difficult to prepare because it needs pure H2 gas whose pressure should be adjusted to 1
atm.
(2)It cannot be used in solutions containing oxidizing agents which may oxidize H2 gas to H+
such as ferric salts, nitrates, permanganates, etc.
(3) Easily poisoned by compounds of Hg, S and As.

(ii)The quinhydrone electrode :

The quinhydrone electrode is prepared by dissolving a small amount of quinhydrone in the test
solution whose pH is to be measured. Quinhydrone is composed of equimolar amounts of
quinine and hydroquinone, in solution the following equilibrium takes place between
hydroquinone (QH2) and quinone (Q)

A platinum wire is inserted in the solution to conduct electricity. As a result of the above
equilibrium a potential is established whose magnitude is given by

eQH2,Q = eo –

Since Q= QH2

Therefore e = eo – 0.059 Log10 H+
Since pH = - Log10 H+
Therefore eQH2,Q = eo + 0.059 pH (1)

16
To determine the pH from the above equation the potential of the quinhydrone electrode
should be determined by coupling the quinhydrone electrode with a reference calomel
electrode and measuring the e.m.f of the resulting cell E with the compensation method
(pt) QH2, Q, H+(test soln pH=??) KClHg2Cl2 (s)  Hg
The electrode potential of the quinhydrone electrode eQH2,Q is obtained from the equation
E = eQH2,Q + ecalomel
The pH of the test solution is then calculated from equation (1) ecalomel is known or can be
calculated from Nernst equation

Pt

Pt
KCl (0.1 M)

Hg2Cl2
Test solution pH=?
Hg
Calomel
electrode

Limitations (drawbacks, shortcomings, disadvantages) of the quinhydrone electrode

(1)The quinhydrone electrode cannot be used in oxidizing or reducing solution which disturb
the ratio QH2/Q=1
(2)The quinhydrone electrode cannot be used for solutions with pH  8 owing to the oxidation
of QH2 by atmospheric oxygen in alkaline solutions.

(iii)The glass electrode

The glass electrode consists of a glass tube terminating in a thin walled bulb made of special
glass, the bulb contains a solution of constant pH (buffered solution) and an electrode of
definite potential such as Ag  AgCl(s)  Cl-. When the glass electrode is immersed in a
solution a potential is set up at the glass – solution interface, this potential depends on the H+
concentration of the solution according to the equation

eglass = e – ln H+

Where e = constant, the glass electrode differs from other electrodes in that its potential is
not caused by a chemical reaction. Although the exact mechanism of the glass electrode is not
known, it is probable that its potential arises from the diffusion of H + through the glass
membrane which is permeable only to H+.
To measure the pH of a solution, the glass electrode and a reference calomel electrode are
immersed in the solution. The e.m.f of the cell:
Ag AgCl KCl glass membrane test solution(pH=??)  calomel electrode
17
E is measured by the compensation method (electronic potentiometer). The pH of the test
solution can be calculated from E as follow:
E = eAgAgCl + eglass + ecalomel
Substituting for eglass from equation (1)

E = eAg/AgCl + e – ln H+ + ecalomel

E = constant – ln H+

E = constant – 0.059 log10 H+

Since pH = - Log H+
E = constant + 0.059 pH
The cell constant in the above equation can be determined by measuring the cell e.m.f for a
solution of known pH (buffer solution)

Pt

Pt
Ag AgCl
KCl (0.1 M)

Hg2Cl2
Test solution pH=?
Hg
Buffered Glass membrane
Calomel
HCl solution (bulb)
electrode

Glass electrode – calomel combination cell Details of the glass electrode

for pH measurement

Automatic pH measuring and control in industry

In the automatic control of pH in industry a glass electrode – calomel electrode combination is
placed in the reactor whose pH is to be controlled. The glass-calomel combination acts as a
transducer and converts the variation in the pH during the course of the reaction into an
electrical signal which is fed to a controller (computer + solenoid valve) acts according to this
signal by opening a valve which releases the amount of acid or alkali requires to restore the
pH of the reactor to the required original value

18
 pH meter
Alkali or acid pH

Computer

Solution
whose pH is
to be
controller

Chemical reactor containing glass-calomel

combination

A simplified circuit for online pH measurement & control

Advantages and disadvantages of glass electrode

1. The glass electrode can be used in all kinds of solution including oxidizing and reducing
solution.
2. The glass electrode can be used in the whole pH range from 0-14.
3. The only disadvantage of the glass electrode is that it is fragile (easily broken). In practice it
should be protected by surrounding it with perforate plastic shield or cylindrical glass
sleeve tube.

19
Potentiometric titration
Potentiometric titration is similar to ordinary titration except for the fact that the end point is
detected by e.m.f. measurement instead of using chemical indicator. Potentiometric titration is
used in case of colored or turbid solution which are difficult to analyze by the indicator
method. Potentiometric titration involves the following steps:
1. The first step in potentiometric titration is to select the suitable electrode which is
sensitive to (reversible with respect to) the ion to be determined, the electrode is
prepared using known volume (V) of the solution to be analyzed. The electrode is then
coupled with reference calomel electrode.
2. A suitable titrating agent which reacts with the ion to be analyzed is selected, the
titrating agent is added to the solution portion by portion after each addition the
solution is stirred and the e.m.f of the cell is measured by the compensation method.
The concentration of the ion to be determined decreases gradually as it reacts with the titrating
agent, accordingly the e.m.f of the cell changes according to Nernst equation
E = Eo – ln C

Where C is the concentration of the ion to be analyzed.

If the cell e.m.f E is plotted against the volume added of the titrating agent a curve as that
shown in figure is obtained. The end point is characterized by a sudden jump in the e.m.f.
Potentiometric titration can be used to analyze the following systems:
(i)Acid-base system
(ii) Precipitation system and
(iii)Oxidation-reduction system.
The following gives examples of potentiometric titration for different systems.
Ex.1 : Determination of the strength of HCl solution an electrode reversible with respect to H+
such as the quinhydrone electrode is prepared using 25 cm3 of HCl. A standard solution (e.g.
0.1 N) of NaOH is used as a titrating agent. Titration is carried out using the following cell:
Burette containing
0.1 N NaOH

Pt

Pt
KCl (0.1 M)

Hg2Cl2
Hg
25 cm3 of HCl (N=?) Calomel
containing Quinhydrone electrode

Volume of NaOH
added, cm3
20
The e.m.f of the cell changes according to the equation
e = eo -0.059 Log H+
The strength of HCl (N) can be calculated from the equation
(NV)HCl = (NV)NaOH
N×25 = 0.1×̅
V is obtained from the E vs V curve at the e.m.f jump.
EX.2 : Determination of the strength of AgNO3 solution :
An electrode reversible with respect to Ag+ is set up using 25 cm3 of AgNO3. A standard
solution of KCl (e.g 0.1 N) is used as a titrating agent where Ag+ is precipitated as AgCl
according to the reaction
AgNO3 + KCl = AgCl  + KNO3
Titration is carried out using the following cell
Ag AgNO3(N=??)  KCl  Hg2Cl2 (s)  Hg
Burette containing
0.1 N KCl

Ag wire Salt bridge made of

KNO3
Clamp

Pt
KCl (0.1 M)

KCl Hg2Cl2
Hg
25 cm3 of AgNO3 (N=?) Calomel
electrode

As a result of Ag+ removal from the solution by KCl, the e.m.f of the cell changes according
to the equation

e = eo – ln Ag+

The strength of AgNO3 is calculated from the equation:

NV = NV
25 × N = 0.1 ×V Volume of KCl
V is obtained from the E vs. volumes of KCl added curve added, cm3

EX.3 : Determination of the strength of K2Cr2O7 solution:

K2Cr2O7 is analyzed by titration against solution of FeSO4 (e.g 0.1 N) where the following
oxidation –reduction reaction takes place
Cr++++++ + 3Fe++ Cr+++ + 3 Fe+++
Titration is carried out using the following cell:
(pt) Cr6+, Cr3+  KCl  Hg2Cl2 (s)  Hg

21
 Burette containing
0.1 N FeSO4

Pt wire

Clamp

Pt
KCl (0.1 M)

KCl Hg2Cl2
Hg
Calomel Volume of FeSO4 added cm3
25 cm3 of K2Cr2O7 (N=?)
electrode

As a rest of the reduction of Cr6+ by FeSO4 to Cr3+ the potential of the redox system chsnges
according to the equation

e = eo –

The strength of K2Cr2O7 is calculated from the equation NV = NV

25 × N = 0.1 ×V

A numerical examples which proofs that a sudden jump takes place at the end point
during potentiometric titration
Consider the titration of 50 cm3 0.1 N HCl against 50 cm3 0.1 N NaOH, calculate the
normality of HCl solution after each addition of NaOH from the equation (NV)HCl =
(NV)NaOH. The following table summarizes the results of these calculations
Volume of NaOH added to 50 cm3- 0.1 N HCl NHCl Solution pH
0 0.1 1
40 0.01 2
49 0.001 3
49.9 0.0001 4
49.99 0.00001 5
49.999 0.000001 6
The above table shows that the few NaOH drops near the end point causes a sudden jump in
the pH of the solution and a corresponding sudden jump in the cell e.m.f used for
potentiometric titration.

22
Electrolytic Cells (Electrolysis)
An electrolytic cell is defined as the electrochemical reactor where thermodynamically
nonspontaneous reactions (  G=+ve) can take place where the energy required to conduct the
reaction is provided in the form of electrical energy.
An electrolytic cell consists of two electrodes placed in a container containing electrolyte, one
electrode is connected to the negative pole (Terminal) of an external direct current (d.c) power
supply, and the other electrode is connected to the positive pole of the d.c power supply. The
electrode which is connected to the –ve pole of the d.c power supply is called the cathode
while the electrode connected to the +ve pole of the d.c power supply is called the anode. At
the cathode the reaction which takes place is a reduction reaction while at the anode the
reaction is an oxidation reaction.
Electrical current is carried during electrolysis by migration of ions in solution (ionic
conduction) and is carried outside the solution by flow of electrons through the connecting
wire (electronic or metallic conduction). In solution positive ions (cations) migrate toward the
–ve electrode (cathode) while negative ions (anions) migrate toward the +ve electrode (anode)
i.e both cations and anions contribute to carrying the electrical current in the solution. The
fraction of the total current carried by the cation is called the transport number of the cation
(t+) while the fraction of the total current carried by the anion is called the transport number of
the anion (t-). The value of the transport number of the ion depends on its ionic speed (ionic
velocity or ionic mobility). The following shows the relation between the transport number
and the speed of the ion.
Let u+ and u- be the velocities of the cation and the anion respectively and let i+ and i- be the
current carried by the cations and anions respectively
i+ u+
i- u-
I = i+ + i-  u+ + u-

t+ = (1)

t- = (2)

From equations (1) and (2)

During electrolysis the following physical changes takes place in the cell as a result of the
electrode reactions and flow of current in the solution:
(i)At the beginning of electrolysis electroactive ion concentration is uniform in the cell but
during electrolysis electroactive ion concentration changes at the electrode surface owing to
electrode reaction. This gives rise to the occurrence of polarization (to be discussed later).

23
 Polarization decreases the rate of production in the cell and increases its energy
consumption.
(ii)The solution temperature increases owing to the conversion of a part of the electrical
energy provided to the cell into heat Q (Q=I2 R) because of the internal cell resistance R.
Heat generation in the solution may adversely affect the performance of the cell.
To design and operate electrolytic cells properly, the above effects should be studied first.
A note concerning the difference in polarity between galvanic cells and electrolytic cells.
electrode Galvanic cell Electrolytic cell
anode (oxidation) -ve +ve
cathode (reduction) +ve -ve

Cathode (-ve) Anode (+ve)

- +

D.C. Power supply

Electrolytic cell

Calculation of the rate of production in electrolytic cells from Faraday's law:

Faraday conducted a series of experiments on the electrodeposition of metals in electrolytic
cell.
His results can be summarized as follows:
For a given metal i.e for a given eq.wt
mQ (1)
For a constant Q
m  eq.wt (2)
Where m= amount deposited in gram, Q is the amount of electricity in coulomb, Q= It where
I = current in Ampere, t = time of electrolysis I seconds, eq.wt is the equivalent of the metal.
By combining equations (1) and (2)
24
m  eq.wt. Q
m = constant eq.wt.Q (3)
The constant in the above equation was evaluated by Faraday using his experimental data and
was found to be ( ), equation (3) becomes:

m= (4)

The number 96500 is known as Faraday's constant and is defined as the amount of electricity
in coulomb required to deposit the equivalent weight of the metal.
Equation (4) can be written in the form
m = e Q = eIt (5)
Where e is the electrochemical equivalent of the metal and is defined as the amount of metal
deposited in gram per coulomb

Current Efficiency of an electrochemical Process:

In many electrochemical reactions the actual amount of product is less than the theoretical
amount of product calculated according to Faraday's law. The % ratio between the actual
amount of product and the theoretical amount is known as the current efficiency (C.E)

C.E = × 100

The current efficiency can be also defined as the % of the current consumed in producing the
main product.

Causes of current inefficiency:

(1)The occurrence of secondary reaction along with the main reaction, for instance, H2 evolves
simultaneously during the cathodic deposition of metals such as Ni, Fe, Cd, Pb, Cr and Zn
according to the reactions
M++ + 2e  M (main reaction)
2H+ + 2e  H2 (secondary reaction)
(2)Reaction of the cathodic product with the anodic product, for example in the electrolysis of
brine (NaCl) to produce NaOH and Cl2, the cathodically produced NaOH and the
anodically produced Cl2 react together in the solution to form sodium hypochlorite
according the reaction:
2NaOH + Cl2 = NaOCl + NaCl + H2O
The occurrence of the above reaction decreases the current efficiency of chlorine and sodium
hydroxide production. To increase the current efficiency of Cl2 and NaOH production the
above reaction should be prevented by placing a porous diaphragm between the cathode and
anoda to avoid mixing of NaOH with dissolved Cl2.

25
Electrolytic (ionic) Conduction
The resistance of a cell of two parallel electrodes separated by a distance L is given by
R =  L/a (1)
Where R = cell resistance, ohm,  is the specific resistance of the solution or solution
resistivity, ohm.cm
 is defined as the resistance of 1 cm3 of the electrolyte, a is the cross sectional area of the
solution in the cell. Equation (1) can be written in the form:
(1/R) = (1/) (a/l)
̅ = K (a/l) (2)
Where ̅ is the conductance of the solution in ohm-1 ( ̅ =1/R), K is the specific conductance
of the solution in ohm-1cm-1, it is defined as the conductivity of 1 cm3 of the electrolyte. K is
the reciprocal of the specific resistance  (K= 1/)

Technical importance of the cell resistance:

(1) Knowledge of the cell resistance R is essential for calculating the voltage lost in the
cell (IR) due to the internal cell resistance, the voltage lost which is known also as the
ohmic drop constitutes a part of the total cell voltage. Hence its knowledge is essential
for calculating the total cell voltage.  I = cell current, R = cell resistance
(2)Knowledge of the cell resistance is also essential for calculating the amount of
electrical energy converted into heat because of the internal cell resistance (I2 R).

Determination of  and K :
The specific resistance  and the specific conductance K are determined experimentally by the
wheat stone bridge shown in figure according to the following steps:
(1)Place a conductivity cell made of two parallel horizontal or vertical platinum disc, each
disc is connected to an electrical wire in the solution whose  or K is to be measured.
(2)Connect the conductivity cell to one of the arms of the Wheatstone bridge (R1).
(3)Move the slider D along the wire BC until a minimum sound is heard in the earphone
(balance point).

26
 A

Conductivity cell placed

in solution of unknown Resistance box
 or k R3
Ear phone

solution of unknown
 or k
R3 R4
B C

Platinum disc

~
A. C. Source
Conductivity cell
Wheatstone Bridge

(4)Calculate the cell resistance R1 from the equation:

Since R2, R3 and R4 are known R1 can be calculated.

(5)Calculated  and K of the solution from R1
R1 =  l/a
If the cell constant (l/a) of the conductivity cell is not known it should be determined by
repeating steps 1 to 4 using a solution of known specific conductance e.g 0.01 N KCl
whose K is 0.141 ohm-1cm-1.

Factors affecting  or K:
(1)Temperature, increase of solution temperature leads to decreasing the specific resistance
and increasing the specific conductance owing to the decrease in solution viscosity with
increasing solution temperature.
(2)Nature of the ions present in the electrolyte, the higher the ionic speed (ionic mobility) the
higher the specific conductance. Electrolytes containing H+ or OH- have usually a high
specific conductance owing to the high ionic speed of H+ and OH-.
(3)Electrolyte concentration: specific conductance increase with increasing electrolyte
concentration, reaches maximum then starts to decrease with further increase in
concentration. The initial increase in k with electrolyte concentration is attributed to the
increase of the number of ions/cm3 which are able to carry the electrical current. The
decrease in k at relatively high electrolyte concentration is attributed to the decrease in the
speed of the ions as a result of the retarding force of interionic attraction (f). The
magnitude of the retarding force of interionic attraction is given by Coulomb’s law

Where q+ and q- are the charge of the cation and anion respectively, d is the distance
between the cation and the anion, is the dielectric constant of the solution. The above
27
equation shows that the retarding force increases with decreasing d i.e. with increasing
electrolyte concentration.

-ve +ve
H2SO4

Retarding force of NaOH

k ohm-1.cm-1
interionic attraction

+ - MgSO4

Accelerating force of
attraction between the
cation and the cathode
Electrolyte concentration M

28
Polarization
Concentration Polarization (concentration over potential or concentration
overvoltage)
Consider the electrode position of a metal M from its metal ions M++ of bulk concentration
C. For the metal to deposit at the cathode according to the reaction: M++ +2e = M, the cathode
potential should reach a value given by Nernst equation (eeqm)

eeqm = eo + ln C (1)

eeqm is the equilibrium (theoretical) deposition (discharge) potential of the metal M and is
defined as the minimum potential required to deposit the metal.
After the beginning of electrolysis the concentration of M++ at the cathode surface drops from
the initial value C to Ci owing to the deposition of some metal ions on the cathode surface,
according the deposition potential becomes

eactual = eo + ln Ci (2)

The difference between the actual deposition potential and the equilibrium potential is known
as concentration polarization (c)
i.e c = eact – eeqm (3)

c = ln (4)

From equation (3)

eact = eeqm + c (5)
From equation (5) concentration polarization can be defined also
as the extra voltage (extra potential) which should be added to the Ci

equilibrium deposition potential in order to deposit the metal. 

Causes of concentration polarization: Diffusion layer

Distribution of M++
Concentration polarization arises from the delay (slowness) of concentration at the
cathode surface
mass transfer of the electroactive ion from the bulk of
 c
the solution to the electrode surface. If the rate of mass
eqm potential

Actual potential
transfer of the electroactive ion were fast enough to
compensate for the amount removed by deposition at
Current

the cathode there would be no concentration

polarization since Ci would be equal to C.

eeqm
Cathode potentail
Graphical illustration of
polarization

29
Importance of concentration polarization:
Concentration polarization is objectionable (deleterious, detrimental) to electrochemical
processes as it leads to increasing the cell voltage and power consumption.
Concentration polarization should be minimized as far as possible in electrochemical.

Prediction of concentration polarization:

The formula c = ln can not be used in practice to predict the magnitude of

concentration polarization because it is difficult to know the value of Ci. In the following
concentration polarization will be expressed in terms of the operating current density (i). In
order to deduce the relation between concentration polarization and the operating current
density the mechanism of mass transfer during electrolysis should be discussed first.

Mechanism of mass transfer during electrolysis :

The electroactive ions are transferred from the solution bulk to the electrode surface by three
ways, namely.
(1)Diffusion as a result of the presence of a
-ve
concentration gradient across the diffusion layer
which is formed at the electrode after the
beginning of electrolysis. The rate of diffusion of
the electroactive ion is given by Fick's law

N diffusion = - D mole/ cm2.s

Ci
Where N is the flux (rate of diffusion), D is the

diffusion coefficient of the electroactive ion, is
Diffusion layer
-ve
the concentration gradient of the electroactive ion
across the diffusion layer.
(2)Electrical migration where the electroactive ions are attracted
V cm/s
to the electrode surface by electrostatic attraction under the
influence of electrical field, the rate of transfer by migration is Convection

given by

Nmigration = mole/cm2.s

Where i is the operating current density, t+ is the transport number of the electroactive ion,
ZF is the amount of electricity per mole
(3) Convection (natural convection or forced convection) where the electroactive ions are
transferred to the electrode surface by mechanical movement of the solution. The rate of
mass transfer by convection is given by
Nconvection = CV mole/ cm2.s

30
Where C is the concentration of the electroactive ion and V is the flow velocity of the
solution (cm/s)

Relation between conc. Polarization and current density:

After the beginning of electrolysis a steady state is reached where the rate of mass transfer of
the electroactive ion to the electrode surface is equal to the rate of electrodeposition of the
electroactive ion. A material balance on the electroactive ion at the electrode surface yields:
Rate of deposition(mole/cm2.s)=Rate of mass transfer (mole/cm2.s)

i.e = Ndiffusion + Nmigration + Nconvection

= -D + CV (1)

The above equation can be simplified by:

(i)Eliminating the convection term CV on the basis that the flow velocity is zero at the
electrode surface because of the friction between the following solution and the electrode
surface
(ii)Elimination of the migration term on the basis that the solution contains a large excess of
inert electrolyte (supporting electrode) e.g in the deposition of copper from CuSO4 in
industry a large excess of H2SO4 is added to improve the solution conductivity.
Under such conditions positive current is carried by H+ in preference to Cu++ because H+
ions are present in a large excess compared to Cu++ i.e t+ in equation (1) becomes zero and
the migration term drops from equation (1). Equation (1) reduces to

= -D

Integrating the above equation by separation of variables

∫ ∫

= D (C-Ci)

(C – Ci)

i= (C – Ci)

i = k (C – Ci)

C – Ci =

Ci = C -

If the operating current density is increased sufficiently a state is reached where the interfacial
concentration drops to zero (i.e Ci becomes zero). Under this condition the rate of mass
transfer of the electroactive ion to the electrode surface reaches a maximum value and the

31
current attains a constant value known as the limiting current density (iL) this special case
equation (2) can be written as
iL = kC
Cb= iL/k
Substituting for C in equation (3)
Ci = iL/k - i/k
Substituting for Ci and C in the equation

c = ln

c = ln

c = ln

The above equation can be used to predict c at any operating current density i provided that
the limiting current density iL is known.

The limiting current:

The limiting current (IL) is the maximum possible current at which a given electrochemical
process can be conducted. It is reached when the interfacial concentration of the electroactive
ion becomes zero i.e. when the rate of mass transfer is maximum. The limiting current is an
important industrial quantity because it corresponds to the maximum rate of production
(mmax = e IL t). If the current is forced to increase beyond the limiting value by increasing the
cell voltage, a new reaction starts e.g. in the deposition of metals from aqueous solution if the
current is increased beyond the limiting value, H2 starts to evolve simultaneously with the
metal.

H2 evolution
Current

IL Limiting current

eeqm e
Cathode potential H2

32
Methods of decreasing concentration polarization and increasing the
limiting current:
Concentration polarization is objectionable (undesirable) in industrial electrochemical
processes because it leads to increasing the cell voltage and power consumption. In the
meantime it is desirable to increase the limiting current to increase the rate of production.
Concentration polarization and the limiting current are related to the rate of mass transfer in
the cell. Increasing the rate of mass transfer leads to decreasing concentration polarization and
increasing the limiting current. An examination of the mass transfer equation:

Shows that there are three methods by which the rate of mass transfer can be increased :
(1)By increasing the diffusivity of the electroactive ion D by heating the solution. According
to the Stokes-Einstein equation : D/T = constant, increasing the solution temperature will
decrease the solution viscosity with a subsequent increase in the diffusivity D.
(2)By increasing the bulk concentration of the electroactive ion (Ci), however this method is of
limited effect because it is difficult to increase C beyond the saturation solubility of the
electroactive ion salt.
(3)The best and most economic method to increase the rate of mass transfer in electrolytic
cells is to decrease the diffusion layer thickness ( ) by stirring the solution using a
mechanical stirrer or a centrifugal pump or gas sparging. The diffusion layer thickness can
be also reduced by moving the electrode itself e.g by vibrating it or rotating it (rotating
cylinder electrode).

33
Activation (chemical) polarization (over potential or over
voltage)
Definition
Consider the deposition of a metal M from a well agitated solution of its ions (to eliminate
concentration polarization), if the concentration of the metal ions is C, the equilibrium
deposition potential is given by
M+ + e = M

eeqm = eo + ln C

In many cases the above potential is not sufficient to start the reaction, an extra potential is
known as activation or chemical polarization (over voltage or over potential) a.
eact = eeqm + a

Causes of activation polarization:

Activation polarization arises as result of the slowness in the
 a
charge transfer step which takes place at the electrode
surface
M+ + e = M (slow) Current
Activation polarization appears in the electrodeposition and
electrodissolution of metals such as Fe, Ni, Co and is more
pronounced in the discharge of gases such as H2, O2 and
eeqm
Cl2. Cathode potentail

Factors affecting activation polarization:

To discuss the factors affecting activation overpotential consider the example of H2 discharge
(2H+ +2e= H2) because of its industrial importance. The factors affecting activation
polarization are:
(1)Current density, Tafel found that activation polarization increases with increasing current
density according to the equation
a = a + b Log i (Tafel equation)
Where a and b are constants depending on electrode material and temperature, i= current
density, A/cm2.
(2)Electrode material, H2 overpotential was found to be high on soft metals such as Pb, Hg and
Zn and relatively low on metals such as Pt, Ni and Fe.
(3)Temperature, increase of temperature reduces activation polarization.
(4)Surface roughness of the electrode, activation polarization was found to decrease with
increasing electrode surface roughness probably because surface roughness increases the

34
 true electrode area with a subsequent decrease in the effective current density, according to
Tafel equation this leads to a decrease in activation polarization.

Hg 10 C
Zn
Pb 20 C

Cd


30 C
 a
Cu a

40 C

Fe
Ni

Pt

log i log i

Effect of electrode material and current Effect of temperature on

density on

Measurement of polarization:
Polarization is determined at a certain current density by measuring the electrode potential
against a reference electrode e.g calomel electrode using a potentiometer.
The value of the electrode potential is calculated from the measured e.m.f
eelectrode = Ecell - ecalomel
 is obtained from eelectrode
 = eelectrode – eeqm

eeqm = eo + ln M+

To determine activation polarization alone the cell solution should be vigoursly stirred to
eliminate concentration polarization. In unstirred solutions the sum of c and a is obtained
from measurement.
mv

Reference
electrode

potentiometer
Luggin tube

anode
cathode

+
-

D. C. power supply

35
Summary of polarization:
Electrochemical reactions like other liquid-solid heterogeneous reactions involves two steps at
least namely:
(1)Mass transfer step where the electroactive ion is transferred from the solution bulk to the
electrode surface
(M+)bulk = (M+)electrode surface
(2)Charge transfer step where the electroactive ion is discharged at the electrode surface
according to the equation
M+ + e = M
Three different cases can be distinguished as follow:
(i)If the first step is slower than the second step the reaction is termed diffusion controlled
reaction and is accompanied by concentration polarization.
(ii)If the second step is slower than the first step, the reaction is called chemically controlled
reaction and is accompanied by activation polarization.
(iii)If the two steps are slow the reaction is termed mixed control reaction and is accompanied
by both activation and concentration polarization.

How to differentiate between diffusion controlled reactions and chemically

controlled reactions:
(i)Diffusion controlled reactions are sensitive to fluid motion i.e. the rate of diffusion
controlled reaction increases with increasing the degree of stirring. On the other hand, the
rate of chemically controlled reactions are not affected by stirring.
(ii)The activation energy (E) of diffusion controlled reactions is usually small ( 5
K.Cal/mole) While the activation energy of chemically controlled reactions is relatively
high ( 10 K.Cal /mole). The activation energy E can be calculated from Arrhenius
equation
K = A e(-E/RT)
By plotting Log K vs. (1/T), the slope gives (E/R).
K=rate constant, A= frequency constant, R= gas constant (2 Cal/ mole.0K), T= absolute
temperature.

36
Cell voltage:
The voltage required to conduct electrolysis in an electrolytic cell (Ecell) is given by
Ecell = Eeqm + (c + a)cathode + (c + a)anode + IR
Where Eeqm = ecathode + eanode
ecathode and eanode are calculated by applying Nernest equation to the cathode and anode
reactions.
c and a are concentration and activation polarization resoectively, IR is the voltage lost
(ohmic drop) due to the internal cell resistance, I = cell current, R is the internal cell
resistance.

Voltage efficiency:
The voltage efficiency of electrochemical process is defined by the eqm :

Voltage efficiency = 100

Causes of voltage inefficiency:

(i)Activation polarization at the two electrodes.
(ii)Concentration polarization at the two electrodes.
(iii)IR drop due to the internal cell resistance.

How to improve the voltage efficiency :

(i)By decreasing activation polarization (see lecture on activation polarization)
(ii)By decreasing concentration polarization (see lecture on concentration polarization)
(iii)By decreasing the cell resistance R (see lecture on ionic conduction)

Energy consumption:
Energy consumption is usually expressed in K.W.h/Kg and is calculated from the formula

Energy consumption = The amount produced in Kg/h (m) can be

calculated from Faraday's law

m = e I t × current efficiency /1000
Where t = 1 ×60 ×60 second

Energy efficiency:
Energy efficiency is defined by the formula

Energy efficiency =

Energy efficiency =

Energy efficiency = voltage efficiency × current efficiency

37
Causes of energy inefficiency:
Are the same causes of (i) voltage inefficiency and (ii) current inefficiency (see lectures on
current and voltage efficiency)

How to improve the energy efficiency of an electrochemical process:

By improving (i) the current efficiency and (ii) the voltage efficiency (see lectures on current
and voltage efficiency)

Simultaneous deposition of metals (simultaneous electrochemical reactions)

For two metals M1 and M2 to deposit simultaneously the following condition should be
fulfilled (satisfied) :
(eM1)actual  (eM2)actual

i.e (eo + ln M+++)M1  (eo + ln M+++)M2

The above equation shows that there are 3 factors which affect the possibility of depositing
two metal together at the cathode surface, namely:
(i)The value of the standard electrode potential eo of the two metals.
(ii)Metal ion concentration of each metal in the solution M++.
(iii)the magnitude of polarization accompanying the deposition of each metal ().

Applications:
1. Metals lying above H2 in the e.m.s such as Pb, Ni, Cd, Fe, Zn, Cr, etc. are not Al
Cr
supposed to deposit from aqueous solutions because H2 which needs a lower Zn
Fe
equilibrium potential evolves at the cathode in preference to these metals. Cd
Thanks to the high H2 over potential on these metals it is possible to deposit Ni
Sn
these metals from aqueous solutions. Without the high H2 over potential (H2) Pb
H2
on these metals it would have been impossible to deposit these metals from Cu
Ag
aqueous solutions. Pt
Au
2. Alloy plating as shown by the following example:
e.m.s.
The standard reduction potential of Pb and Sn are -0.126 and -0.14 V
respectively, both metals deposit with negligible polarization. The small difference in the
value of eo of the two metals can be compensated for by a small adjustment of Pb++ and
Sn++ concentration in the plating bath so that simultaneous deposition of the two metal
takes place according to the equation :
-0.126 + 0.059/2 Log Pb++ = -0.14 +0.059/2 LogSn++

38
Corrosion and protection of metals
Definition of corrosion
Corrosion is the deterioration of metallic structures through chemical and/or electrochemical
reactions with the surrounding environment. Corrosion should be distinguished from erosion
which is caused by mechanical effects. Sometimes damage of the structure takes place through
corrosion and erosion.

Importance of corrosion
Corrosion of metals constitutes a big problem to industry since it causes enormous financial
losses through the following:

1. Plant shutdown due to failure of equipment by corrosion. Plant shutdown leads to loss
of profits.
2. Cost of repair and replacement of corroded equipment by new ones.
3. Cost of protecting the plant equipment against corrosion (maintenance cost).
4. Corrosion contaminates the products with objectionable and sometimes toxic ions.
This problem becomes serious in case of producing foodstuffs, drugs and dyes.
5. Corrosion decreases the efficiency of the equipment as a result of the deposition of
corrosion products on metallic surfaces. The deposited corrosion product decreases the
rate of heat transfer in heat exchangers and boilers. Also corrosion products increase
the surface roughness of pipes with a consequent increase in the power required to
pump liquids in these pipes.
6. Corrosion sometimes causes loss of human life e.g in case of boiler explosion.
7. Corrosion wastes the limited amount of metal available to mankind.

Corrosion of metals can be classified into

I. Chemical corrosion (dissolution of metals in acids)

II. Electrochemical corrosion.

39
I. Chemical corrosion (dissolution of metals in acids)
There are 3 methods by which the tendency of the metals to dissolve in acids can be predicted, namely:
(i) The position of the metal in the e.m.s, generally metals lying above H2 in the e.m.s. dissolve in
acids with H2 evolution while metals lying below H2 doesn’t dissolve with H2 evolution.
(ii) Thermodynamically for metal dissolution in acid to take place, the free energy (G) of the
reaction: M+2H+  M++ + H2 must be –ve. The higher the –ve value of G the higher the
dissolution tendency of metals.
(iii)The electrochemical theory
Methods (i) and (ii) fail to explain why pure metals such as Zn, Pb, Sn, and Sb which lie above
H2 which lie above H2 in the e.m.s do not dissolve or dissolve with difficulty in acids.
The electrochemical theory assumes that the metal dissolution in acids takes place through the
formation of galvanic cell: MM++ H+H2
For the reaction M + H+  M++ + H2 to take place in the above cell,  should be less

noble than  i.e. eo - ln [M++] should be less noble than [ ln [H+]+ ] the equation

shows that the metal dissolution in acids is favored by (a) low M++ (b) high acidity (c) low
Zn, Sb, Sn and Pb dissolve with difficulty in acids because of high H2 overpotential on
these metals

II. Mechanism of electrochemical corrosion (types of galvanic cells

responsible for corrosion)
Dissimilar metal corrosion cells:
This type of cells takes place when two different metals become in contact in the presence of
an electrolyte. The less noble metal acts as the cell anode (-ve) where metal dissolution takes
place while the more noble metal acts as the cell cathode where H2 evolution or O2 reduction
takes place.
Cell: M1 / electrolyte / M2
Reactions:
-ve(anode): M1 M1++ +2e

+ve(cathode): O2+H2O+2e 2OH- (pH 4-10)

Or: 2H+ +2e  H2 (pH <4)

40
Examples:

Electrolyte

Copper coat

Steel

Ex.1, Corrosion of steel at a break in the copper coat

Cell: Fe / electrolyte / Cu
Reactions
-ve: Fe Fe++ +2e
+ve: O2 + H2O + 2e  2OH- (pH 4-10)

Or: 2H+ +2e H2 (pH <4)

Dissimilar metal corrosion not only takes place when two different metals becomes in contact
in the presence of an electrolyte but also takes place when the metal is in contact with a more
noble phase such as an oxide or alloy as shown in the following example:
Steel is usually covered by an oxide film (magnetite, Fe3O4) formed during hot rolling of steel
to produce steel sheets from steel ingots. This oxide film which is called mill scale or
magnetite is electrically conducting and in the same time more noble than steel. If the oxide
film is broken due to differential thermal expansion or due to mechanical causes, the following
galvanic cell is setup at the break
Fe / electrolyte / Fe3O4 (magnetite)
Oxide film Fe3O4

Electrolyte

Example 2, corrosion of steel tube at a break in oxide film (magnetite)

Reactions
-ve(steel anode): Fe Fe++ +2e
+ve(Fe3O4 Cathode): O2+H2O +2e  2OH- (pH 4-10)

Or: 2H+ +2e H2 (pH <4)

As result of the above reactions tube perforation takes place eventually after sometime. In
view of this dangerous effect of magnetite, steel mills usually remove magnetite from steel
after hot rolling by acid pickling.

41
Why steel corrodes in electrolytes even without contact with more noble metals:
The presence of carbon in steel is essential to increase the mechanical strength of steel, carbon
content of steel ranges from 0.15 to 1.5% [0.15-0.25% low carbon steel; 0.25-0.5% medium
carbon steel; 0.5 to 1.5% high carbon steel].
Unfortunately C does not form a solid solution with iron; it forms a separate phase known as
cementite (Fe3C).
Cementite (Fe3C) is more noble than Fe accordingly when steel is placed in an electrolyte a
magnitude of microscopic dissimilar cells are formed between the more noble cementite and
the neighboring less noble iron(ferrite)
Fe / electrolyte / Fe3C (Cementite)
-ve(Fe): Fe Fe++ +2e
+ve(Fe3C): 1/2O2+H2O +2e  2OH- (PH 4-10)
Or: 2H+ +2e H2 (PH <4)
In practice contact between dissimilar metals should be avoided as possible in designing
industrial and civil structures the following examples shows incorrect selection of material of
construction:-
5 ‫هنا فى رسومات صفحة‬
2- Differential aeration (oxygenation) cells:
To illustrate how differential aeration cells arises consider the following experiment:
The apparatus consists of a plastic container divided in two compartments by a porous
diagram each compartment contains a sheet of iron placed in sodium chloride solution. The
two iron sheets are similar in composition and NaCl in the two compartments has the same
concentration. If the two iron sheets are connected to galvanometers, no current flows in the
galvanometer. If dissolved O2 is removed from one compartment by a stream of N2 and the
two sheets are connected again to the galvanometer, a
‫ مش موجودة‬6 ‫فى رسمة هنا وبعدين فى صفحة‬
3- Differential strain (or stress) cells:
This type of corrosion cells takes place when the metal surface is strained to different degrees.
The strained part acts as the cell anode (-ve) and the less strained part (or unstrained) acts as
the cell cathode (+ve)
Cell:
Strained part / electrolyte / unstrained part
Reactions:
Strained part (-ve): Fe Fe++ +2e
Unstrained part (+ve): 1/2O2+H2O +2e  2OH- (PH 4-10)
Or: 2H+ +2e H2 (PH <4)
This type of corrosion should be distinguished from stress corrosion cracking (SCC).
42
Stress Corrosion Cracking (SCC):
This type of corrosion takes place when the stressed metal (cold worked i.e deformed) is
subjected to a certain electrolyte as shown by the following examples:-
Stressed metal or alloy Environment which causes stress corrosion cracking to the
metal or alloy
i. Steel Hot alkalies (e.g NaOH) and nitrates
ii. Stainless steel Hot chlorides e.g sea water
iii. Copper and its alloys Ammonia solutions and organic amines
iv. Aluminum alloys Sea water, water vapor and air

The time after which failure by stress corrosion cracking takes place depends on the degree of
stress, temperature and electrolyte concentration. To avoid corrosion by differential strain cells
and occurrence of SCC, residual stresses stored in the metal during fabrication should be
removed by annealing which consists in heating the strained metal for some time at high
temperature.

Stray current corrosion:

This type of corrosion occurs when d.c (direct current) leaks from a conductor e.g the rail of a
tram to a wet salty soil which contains buried metallic structure such as a steel pipeline or
telephone cable. The stray current passes from the rail at A through the wet soil (good
conductor) to the buried pipeline at B. At location C the stray current returns again to the rail
at C when it finds a good conducting soil. During this journey the stray current causes
corrosion where it leaves i.e at location A of the rail and location C of the buried pipeline i.e
locations A & C act as anodes while locations B & D act as cathodes.
8 ‫فى رسمة هنا صفحة‬
Atmospheric corrosion:
Atmospheric corrosion differs in its severity according to the nature of the atmosphere.
Industrial atmospheres where air is polluted with gases such as SO2, H2S, Nitrogen Oxides
(NxOy), CO2 and water vapor cause severe corrosion to metallic structures. Also marine
corrosion is high in urban atmospheres and marine atmosphere where air is laden with droplets
of NaCl. In rural and desert atmospheres corrosion is almost negligible. Atmospheric
corrosion takes place by:-
i. Direct attack by the acid solution resulting from the dissolution of acidic gases
such as NxOy, CO2, SO2, SO3,etc in condensed water film or a drop of dew on the
metallic structure.
ii. The formation of a galvanic cell such as:
a. Fe / electrolyte / Fe3C and
43
 b. Fe / electrolyte / O2
For atmospheric corrosion to take place the relative humidity should exceed 50%. High
relative humidity leads to condensation of a thin film of moisture on the metal which absorbs
gases from the atmosphere and act as electrolyte which attacks the metal directly or through a
galvanic cell.
The role of dissolved oxygen in corrosion:
As seen before, O2 plays an important role in the occurrence of corrosion, namely:
i. Dissolved oxygen is responsible for cathodic reaction (electron sink) in galvanic
cells through which corrosion takes place in the PH range 4-10
(1/2O2+H2O+2e2OH-).
ii. Differential aeration cells are caused by the difference in dissolved O2
concentration at the metal surface.
iii. O2 determines the nature of corrosion products e.g in steel corrosion, the dissolved
Fe++ ions are oxidized by dissolved O2 to ferric oxide Fe2O3. H2O (brown iron
rust)
2F(OH)2+1/2O2Fe2O3.H2O+H2O
If the amount of O2 is limited, green hydrated or black unhydrated magnetite (Fe3O4) is
formed
3Fe(OH)2+1/2O2Fe3O4.H2O+2H2O

Bacterial (microbiological) corrosion:

This type of corrosion occurs to metallic structures buried in anaerobic soil (free of dissolved
O2) containing SO4—by a bacteria known as sulphate reducing bacteria. The reactions involved
in this type of corrosion are as follow. Consider a steel structure buried in anaerobic soil
containing SO4--, a multitude of microscopic cells of the type:
Fe/ electrolyte / Fe3C
Are set up on the structure, the cell reactions are:
Anode (-ve): 4Fe 4Fe++ +8e
Cathode (+ve): 8H2O+8e8H+8OH-
In the presence of sulphate reducing bacteria the cathodic reaction is accelerated through the
following reaction
8 H + SO4--  S-- + 4H2O
The following side reaction takes place
3Fe++ +6OH- 3Fe (OH)2
3F(OH)2 Fe3O4 (black magnetite) + 2H2O +H2
S-- +Fe++ FeS (black iron sulphide)
44
The overall reaction is
4Fe + 2H2O + SO4-- Fe3O4 + FeS+H2+2OH-
i.e a black rust containing FeS and Fe3O4 is formed on the steel buried structure. Type of
corrosion occurs also in polluted harbors. Come scientists are of the opinion that sulphate
reducing bacteria reduces sulphates to H2S which attack the metal chemically to form the
metal sulphide.

Methods of combating corrosion (protection of metals against corrosion)

The following methods are used to protect metals against corrosion:
I. Selection of the right material of construction
II. Surface coating.
III. Inhibitors
IV. Proper equipment design
V. Electrical protection

I. Coating
The metallic structure is isolated from the corrosive environment by coating it with
a layer of the following
1. Metallic coating
The structure is coated with a layer of other metal which may be more noble
than the structure or less noble than it e.g steel structures can be coated with
copper which is more noble than steel or zinc which is less noble. In case of
coating the structure with a more noble metal care should be taken that the coat
is free from pores or cracks to avoid the formation of dissimilar metal corrosion
cells which would lead to corrosion of the structure.
In case of coating the structure with a less noble metal in the presence of pores
and cracks in the coat is not dangerous because in this case the less noble metal
will corrode by the formation of dissimilar metal cells while the structure will
remain protected.
In practice metallic coating is carried out by different methods such:
i. Electroplating,
ii. Hot dipping of the work piece in molten metal covered with a flux,
iii. Spraying of the molten metal on the work piece.
The most famous metallic coating is coating steel with a layer of zinc, the
process is known as galvanizing of steel, the process is carried out by
electroplating, hot dipping and metal spraying.
21 ‫فى رسمة هنا صفحة‬
45
2. Inorganic coating includes the following:-
i. Oxidation: steel can be coated with an oxide film by a). heating at high
temperature, b). chemical oxidation by treating steel with hot alkaline
nitrate, or persulphated or perchlorate, c). anodic oxidation by making
the steel structure an anode in electrolytic cell.
ii. Phosphating: steel is coated with a layer of iron phosphate by dipping
in a solution containing phosphoric acid and zinc phosphate. The iron
phosphate film is not highly protective because it is porous so it usually
covered with paint. The phosphate film improves the bond between the
metal and the paint.
iii. Enamels: enamels are galssy layer applied to the metal by dipping it in
a suspension of powdered at glass, then the metal is heated in a stove
(furnace) at high temperature where the glass powder metals and coat
the metal.
iv. Cement coating: is used to coat the inner side of steel pipelines
carrying water or wastewater.
3. Organic coating such as the following:
i. Paints: Paint consists of a film forming substance such as linseed oil or
a polymer (resin), as organic solvent and a pigment (usually an
inorganic oxide or metal powder). Before applying paint to a steel
surface, the metal surface should be cleaned of oxides by sand blasting
or acid pickling. After cleaning, the metal surface is coated with a thin
layer of primer, a primer is a paint containing a pigment such as lead
oxide (Pb3O4 red lead) or zinc chromate which oxidize the steel surface
and inhibits its corrosion. Besides, the primer film increases the strength
of the bond between steel and final paint film. When the primer film
dries a thick film of the required paint is applied over the primer.
Polymers such as alkid resins, PVC, polyethylenes, polyesters, acrylics,
polyurethanes, chlorinated rubber, epoxy resins, etc. are used in paint
manufacture. For severe conditions such marine and industrial
atmosphere, a paint containing epoxy resin (water resistant) is suitable.
ii. Lacqures: a lacquer consists of a thermoplastic polymer dissolved in an
organic solvent. Lacqures can be used to line steel tanks holding
corrosive chemicals such as acids.
iii. Coal tar: is used to protect underground structures. A 50% coal tar +
50% epoxy is superior to coal tar.

46
 iv. Temporary coating: is used to protect metallic structures during
shipping and storage by coating the structure with layer of lubricating
oil which can be removed by an organic solvent when the structure is
put to service.

II. Corrosion Inhibitors:

Corrosion inhibitors are chemical compounds added in small amount (e.g 0.1%) to
the corrosive medium to inhibit corrosion. They are classified according to their
mechanism of action into:-
1. Cathodic inhibitors:
Cathodic inhibitors are chemical compounds which inhibit the cathodic
reaction of the corrosion cell examples of cathodic inhibitors:-
a. Compounds such as ZnSO4, MgSO4 and Ca(HCO3)2, these compounds
inhibit the cathodic reaction by forming insoluble Zn(OH)2 film or
Mg(OH)2 film or CaCO3 film with the cathodically formed OH- ions (in
neutral solutions) the insoluble film isolates the cathodic regions of the
corrosion cells from the corrosive medium and stops corrosion.
b. Oxygen scavengers, these are compounds which react with dissolved
oxygen and remove it from the neutral or alkaline corrosive environment
such as sodium sulphite or hydrazine (used to inhibit boiler corrosion)
Na2SO3+1/2O2  Na2SO4
N2H4+O2 N2 + 2H2O
c. Compounds such as arsenic, mercury, antimony salts which are added to
acidic H2 evolution reaction.
2. Anodic inhibitors:
Are chemical compounds which inhibit the anodic reaction of the corrosive
cells.
Examples
A compounds such as Na2SiO3, Na2CO3 and Na3PO4, these compounds form
with the andoically formed Fe++ an insoluble film of iron silicate or iron
carbonate or iron phosphate which isolates the anodic sites of the corrosion
cells from the corrosive solution.
c. Passivators: these are oxidizing agents such as Na2Cr2O7 or NaNO2 which react
with the anodically formed Fe++ to form a passive oxide film on the anodic
sites of the corrosion cells.
Na2Cr2O7+2Fe+H2OCr2O3+Fe2O3 + 2NaOH
NaNO2 + 2Fe + 2H2O  Fe2O3+ NH3 + NaOH
47
 Na2Cr2O7 (0.2%, PH =8) was used widely in industry to protect the cooling
system of the plant against corrosion. Recently chromate has been replaced by
a mixture of Zn++, polyphosphate and chromate which is less harmful to the
environment because the mixture uses a lower doze of the toxic CrO4--. More
recently zinc phosphate is being used without chromates.
3. Adsorption Inhibitors:
These are organic compounds which contain a polar group such as NH2( amino
group), these compounds (RNH2) adsorb on the metallic surface and isolate it
from the corrosive solution (usually acids). These compounds are used in acid
pickling of metals.
III. Electrical Protection :
Electrical protection can be divided into
1. Cathodic protection.
2. Anodic protection.
1. Cathodic Protection: is carried out by making the structure to be protected a
cathode in either a galvanic cell by connecting it to a less noble metal such as
Zn and Mg or
‫ مش موجودة‬26 ‫صفحة‬
2. Anodic Protection: is based on the phenomenon of passivity to understand
how the anodic protection is carried out the phenomenon of passivity should be
explained first.
Consider a metal M acting as a anode in electrolytic cell. If the anode potential
is increased gradually the metal M starts to dissolve at a potential e1 given by
MM++ +2e
E1 =e0 – RT/ZF ln[M++]
At the point A current starts to flow in the cell as a result of metal dissolution,
with increasing the anode potential the current increases till the point B is
reached, after this point any further increase in the anode potential result in a
decrease of the current from B to C owing to the formation of an oxide film on
the metal surface which prevents its dissolution. Oxide film formation takes
place at the potential e2 which is given by the equation
M + H2O  MO + 2H+ + 2e
E2 = e0 – RT/ZF ln[H+]2
With further increasing the anode potential no current flows through the cell
until the potential e3 is reached at point D where oxygen evolution starts to
evolve according to the reaction
4OH-  O2 + H2O + 4e
48
 E3=e0 – RT/ZF ln[OH]4
At point D the current increases again with increasing anode potential as
represented by the part DE.
28 ‫فى رسمة هنا صفحة‬
Anodic protect is carried out by connecting the structure to be protected to the
positive pole of an external d.c power supply, an auxiliary cathode made of
corrosion resistant material is used to complete the circuit. The anode potential
of the structure is adjusted to be in the passive region i.e the region represented
by the area BCDE on the passivity curve. Under this condition the structure
will be coated with a layer of oxide which protects it against corrosion.
28 ‫فى رسمة هنا صفحة‬
Limitation of anodic protection:
1. Anodic protection can be used only with metals which exhibit the
phenomenon of passivity such as steel, stainless steel, nickel and its alloys,
chromium and its alloys, Al and Ti and their alloys, anodic protection can
not be used with metals such as CU and Zn and their alloys.
2. Anodic protection can not be used when the electrolyte contains chloride
ions because chloride ions attack the oxide film and destroy it.

4- Selection of the proper material of construction:

There are two trends in selecting material of construction. The first trend uses expensive alloys
to eliminate the problem of corrosion, the second trend uses steel and protects against
corrosion by the different methods. Economically speaking it was found that the second trend
is more economic and steel constitute >90% of the material of construction used in industry.
Expensive alloys are used only in case of highly corrosive chemicals as shown as in the
following table.
Table 1, examples of material of constructions used in handling corrosive chemicals
Corrosive solution Material of construction
HCL Tantalum, steel lined with plastic or
graphite
H2SO4 > 70% Steel
H2SO4 < 70% Lead or steel lined with lead
Alkaline solutions e.g NaOH, KOH, Nickel and its alloys
NH4OH,etc
Oxidizing solutions such as Titanium and its alloys
Na2Cr2O7,H2O2,FeCl3,etc

49
Sea water (3.5%) Copper alloys such as brasses, bronzed
and stainless steel
Organic acids(formic, acetic, oxalic High Si steel (15% Si)
acids) phosphoric acid
HNO3 (>80%) Alumnium
HNO3 (<80%) Stainless steel

5- Minimizing corrosion by proper design

The following are examples of how proper equipment design can reduce corrosion
1. Avoid dissimilar metal contact in the presence of an electrolyte especially when the
cathode/anode ratio is high such as the following example:
12 ‫فى رسمة هنا صفحة‬
If the use of dissimilar metals is unavoidable in building the structure they should be
separated by an insulator such as plastic or rubber as shown by the following example
12 ‫فى رسمة هنا صفحة‬
Dissimilar metals are sometimes used intelligently to design structures which are
corrosion resistant and less expensive as shown by the following examples.
12 ‫فى رسمة هنا صفحة‬
Cooper tubed are used in building heat exchangers because copper has the highest
thermal exchangers because copper has the highest thermal conductivity among all
metals. Other parts of the heat exchanger such as the shell, tube sheet and head are
made of steel not copper to lower the capital costs of the heat exchanger. The use of
steel offers also the advantage of protecting copper tube against corrosion by cathodic
protection through the cell : Fe/electrolyte/Cu.
Example 2 shows a centrifugal pump made of three different materials chosen to
produce inexpensive corrosion resistant efficient pump where the steel body protects
the other parts of the pump against corrosion by cathodic protection.
2. It is better from the corrosion point of view to join different sections by welding rather
than riveting to avoid crevice corrosion. After welding the heat affected zone (H.A.Z)
should be post weld heat treated (P.W.H.T) to eliminate residual stresses which may
lead to corrosion.
[Crevice = clearance or gap between two surface in contact]
11 ‫فى رسمة هنا صفحة‬
3. Avoid erosion-corrosion (impingement corrosion) by doubling the thickness of the
parts subjected to high degree of turbulence (high shear stress) or subjected to flowing
solutions which contain suspended solids such as tube inlets, elbows, bends, impellers
of agitated vessels, etc.
50
 High turbulence may damage the protective oxide film on the metal and increase the
rate of bare metal corrosion by increasing the rate O2 transfer from the solution bulk to
the metal surface.
11 ‫فى رسمة هنا صفحة‬
4. Avoid vibration of equipment as far as possible. Vibration increases the rate of O2
transfer from the solution bulk to the corroding surface with a consequent increase in
the rate of steel corrosion.
Vibration leads also to corrosion fatigue. Metallic objects subjects to cyclic stresses
(e.g vibrations) undergoes failure at a stress below the ultimate tensile stress of the
metal especially in the presence of corrosive solutions, the stress at which failure takes
place decreases with increasing the number of cycles per second as shown in the
following figure.
12 ‫فى رسمة هنا صفحة‬
5. Dry your equipment (e.g packed columns pipelines, etc) after testing or cleaning by
passing dry N2. Leaving this equipment wet for a long time before operation leads to
serious corrosion.
6. Design tanks for easy drainage as shown below
12 ‫فى رسمة هنا صفحة‬
Resting the tank on the floor leads to crevice corrosion of the bottom (through a
differential aeration cell). Residual solution in the tank resulting from poor drainage
leads to serious corrosion of the lower part of the tank because of the high rate of O2
diffusion through the thin residual liquid layer left at the tank bottom.
7. Avoid stresses in the structure
As mentioned before residual stresses left in the structure during fabrication leads to
stress corrosion cracking of the metal if used in contact with certain electrolyte. Stress
corrosion cracking can be avoided by either removing of residual strains from the
metal and electrolytes to which it is sensitive.
Stresses may be also induced in heat exchanger tube if the thermal gradient across the
tube wall is high (dT/dx) where dT is the difference in temperature across the tube wall
and dx is the thickness of the wall.

‫ مش موجودين‬17‫و‬16 ‫ و‬15 ‫صفحة‬

Kinetics of Corrosion
I. Diffusion controlled corrosion
As mentioned before the following reactions take place during corrosion in the
PH range 4-10
Anode: Fe Fe++ +2e (fast)
51
 The cathode reaction involves two steps namely:
i. Transfer of dissolved O2 from the solution bulk to the corroding
surface.
(O2) bulk  (O2) interface (slow)
ii. O2 reduction at the cathodic sites of the corroding surface
1/2O2 + H2O + 2e  2OH- (fast)

The overall rate of corrosion is determined by the slowest step which is the transfer of
dissolved O2 from the solution bulk to the interface between the metal and the solution i.e
corrosion in the PH range 4-10 is diffusion controlled.
The rate of corrosion in the PH range 4-10 can be calculated from the rate of mass transfer
(diffusion) of dissolved O2 (N)
N = iL/ZF = kCs
Where iL = limiting current of O2 reduction, k= mass transfer coeffient, Cs is the saturation
solubility of dissolved O2 in the electrolyte, z= number of electrons involved in the reaction,
F= faraday's constant.
Since 2Fe needs 1 mole of dissolved oxygen to corrode it follows that the rate of steel
corrosion R is given by
R=2N=2kCs mole/cm2.s
R=2kCs*56 g/cm2.s
The mass transfer coefficient k can be estimated from the suitable mass transfer equation
which applies for the structure geometry e.g for turbulent flow in pipes (Re>2300) the mass
transfer coefficient k can be calculated from the equation
Sh=0.023 Sc0.33. Re0.8 (1)
While for laminar flow in tubes (Re<2300) k can be estimated from the equation
Sh=1.85 (Sc.Re.d/l)0.33
Where Sh is Sherwood number (kd/D); Sc is Schmidt number =µ/ρD and Re is Reynolds
number (ρVd/ µ); d is the tube diameter; D is the diffusivity of O2; µ and ρ are the solution
viscosity and density respectively; L is the tube length. Equation(1) can be also written in the
form
J=0.023 Re-0.2
Where J is the mass transfer J factor
J=St. Sc0.66
St= stanton number (k/V)
II. Chemically controlled corrosion
In acidic solutions (PH<4) the corrosion reactions become:
Anode: Fe Fe++ +2e (fast)
52
Cathode: 2H+ +2e  H2 (slow)
i.e the rate of corrosion in this case is determined by the slow cathodic reaction (H2 evolution).
The rate of chemically controlled corrosion can be estimated from the Stren-Geary equation
∆E/∆I = 1/2.3 icorr [ba bc/ba+bc]
Where ∆E/∆I is called the polarization resistance it can be determined experimentally by
determining the slope of the linear portion of the polarization curve or by determining the
current required to shift the initial corrosion potential by 10 mv, icorr is the corrosion current
density ; ba, bc are the Tafel slopes of the anodic and cathodic reactions respectively (E vs log
i)
The calculated icorr can be used to calculate the rate of corrosion from faraday's law.
23 ‫فى رسومات هنا صفحة‬

53