MODULE-3

CORROSION AND ELECTRODE SYSTEM

Corrosion Chemistry Introduction, electrochemical theory of corrosion, types of corrosion differential metal and
differential aeration. Corrosion control- galvanization, anodization and sacrificial anode method. Corrosion
Penetration Rate (CPR) – Introduction and numerical problem.
Electrode System: Introduction, types of electrodes. Ion selective electrode – definition, construction, working
and applications of glass electrode. Determination of pH using glass electrode. Reference electrode- Introduction,
calomel electrode– construction, working and applications of calomel electrode. Concentration cell– Definition,
construction and Numerical problems.
Analytical Techniques: Introduction, principle and instrumentation of Conductometry; its application in the
estimation of weak acid. Potentiometry; its application in the estimation of iron.
Self-learning : IR and UV-Visible spectroscopy

CORROSION CHEMISTRY
Introduction :
 Corrosion is defined as the destruction and consequent loss of metals through chemical or electrochemical
attack by the environment
 Corrosion, in general, is a process through which refined metals are converted into more stable compounds
such as metal oxides, metal sulfides, or metal hydroxides.
 Corrosion is usually an undesirable phenomenon since it negatively affects the desirable properties of the
metal. For example, iron is known to have good tensile strength and rigidity (especially alloyed with a
few other elements). However, when subjected to rusting, iron objects become brittle, flaky, and
structurally unsound.
 On the other hand, corrosion can be classified as an electrochemical process since it usually involves redox
reactions between the metal and certain atmospheric agents such as water, oxygen, sulphur dioxide, etc.
Corrosion classified as
1. Dry corrosion (Chemical corrosion)
2. Wet Corrosion (Electrochemical corrosions)
1) Dry corrosion (Chemical corrosion)
Corrosion of metal occurs by direct attack of atmospheric gases such as oxygen, hydrogen sulfide, halogens and
Sulphur dioxide in the absence of moisture to form metal oxide layer.
2) Wet corrosion (Electrochemical corrosion)
Wet corrosion occurs in presence of an aqueous solution of electrolyte and atmospheric oxygen by setting up of
tiny galvanic cells on the metal surfaces.

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Electrochemical theory of corrosion / WET Corrosion
Corrosion is an example of Oxidation. When a metal like Iron is exposed to atmosphere, the following
electrochemical changes occur gradually.
a) Formation of Galvanic cells - Anodic and cathodic areas are formed resulting in a large number of minute
galvanic cells.
b) Anodic Reaction: At the anodic area metal undergoes oxidation with the release of electrons
Fe → Fe2+ + 2 e-
c) Cathodic Reaction - The electrons flow from the anodic to cathodic area and cause reduction. There are 3
possible ways in which reduction can take place.
(i) In acidic medium and absence of oxygen: hydrogen ions are reduced to hydrogen gas.

(ii) In neutral and in the absence of oxygen: If the solution is neutral and in the absence of oxygen, water
is reduced to H2 and OH-

(iii)In neutral and aerated medium: when the solution is neutral and aerated, hydroxyl ions are formed as
follows.

(iv) Formation of corrosion product:

The hydroxyl ions migrate towards anode and react with metal ions (Mn+ ions) and forms corrosion
product. In the case of iron OH- reacts with Fe2+ ions and forms an insoluble hydrated ferric oxide
known as brown rust.

Types of corrosion
1) Differential metal corrosion
2) Differential aeration corrosion
3) Stress Corrosion
4) Grain Boundary corrosion

1) Differential metal corrosion :

 Differential metal corrosion arise when two dissimilar metals are in contact with each other.
 The metal higher in the electrochemical series is anodic to the one below it, i.e, the metal with lower
reduction potential undergoes oxidation, whereas the metal with higher reduction potential undergoes
reduction
 The rate of differential metal corrosion depends primarily on the amount of current passing from the
anode to cathode, i.e, higher the difference in potential, higher will be the rate of corrosion.
The principle of Differential metal corrosion occurring in a simple cell can be extended to a bimetallic couple.
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Let us consider a bimetallic sample of iron and copper as shown below

The standard electrode potential of Fe is – 0.44 V which is less than that of Cu whose standard electrode potential
is 0.34 V
Hence in this case iron acts as anode and undergoes corrosion whereas copper acts as cathode and remains un-
attacked.
The following are the reactions which occur during differential metal corrosion when Fe is in contact with Cu
At anode : Fe → Fe2+ + 2e-
At cathode (either hydrogen evolution or oxygen absorption)
2 H+ + 2e- → H2↑
O2+ 2 H2O + 4 e- → 4 OH-
Examples
 Steel screws in copper sheet
 Lead-tin solder around copper wire
 Buried iron pipeline connected to Zinc bar.
 Steel pipe connected to copper plumbing

2) Differential aeration corrosion :

 It occurs when a metal surface is exposed to differential air (or) oxygen concentration.
 Part of the metal exposed to lower concentration of oxygen will have lower potential and therefore acts
as anode. This part undergoes corrosion.
 The other part of the metal exposed to higher concentration of oxygen acts as cathode and remains
unaffected.
 The difference in oxygen concentration produces a
potential difference and causes corrosion current to
flow from cathode to anode.
Let us consider a strip of Zn immersed partially in a solution
of ZnCl2
Hence part of the metal below the water level acts as anode
undergoes corrosion and the part above the water level acts as

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cathode and remain unaffected. The corrosion product is formed between anodic and cathodic areas.
Waterline corrosion is a case of differential aeration corrosion.
Water line corrosion
 This takes place due to the formation of differential oxygen concentration cells.
 The part of metal exposed to lower concentration of oxygen (dissolved oxygen) acts as anodic area.
 The part of the metal above the water level is
exposed to higher concentration of oxygen
acts as cathodic area and remains unaffected.
 A distinct brown line is formed just below the
water line due to the deposition of rust.
 Water line corrosion is observed usually in
steel water tanks and ships floating in sea
water for a long time

Corrosion control
 Corrosion is a Natural process. Corrosion of metal results in huge economic loss.
 We cannot completely STOP the corrosion process of metals, but it is possible to minimize corrosion effect
by applying various methods.
Corrosion control methods are broadly classified into three types
1. Anodizing
2. Cathodic protection
3. Metal coating

1) Anodizing
Process of anodizing of Aluminum
 Anodizing is generally produced on non-ferrous metals like Al, Zn, Mg and their alloys.
 Aluminium when made cathode allows the passage of electrons but cease to conduct when it is made
anode in aqueous solution of chromic acid (or) H2SO4.This is because of the formation of a thin layer of
Al2O3 over the metal.
 Anode: Aluminum
Cathode: Cu / Steel/Lead
Electrolyte: 5-10 % chromic acid or 10 % H2SO4
Temperature: 35oC
Voltage: 40 V
Current density: 100 A /m2

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  Electrode reactions
At anode
(Oxidation): 2Al + 3 H2O → Al2O3 + 6 H++6 e-
At cathode
(Reduction): 6 H+ + 6 e- → 3 H2

Overall reaction: 2 Al + 3H2O → Al2O3 + 3H2

1.The metal after pretreatment is made to act as anode

and steel, copper or lead acts as cathode.
2.The electrolyte consists of 5-10 % chromic acid.
3.The temperature of the bath is maintained at 35 oC
4.A current density of 100 A/m2 is applied which
oxidizes the outer layer of Al to Al2O3
5.An oxide layers of Al2O3 with a thickness 2-8 µm is formed.
6.For higher thickness 10% H2SO4 is used as the electrolyte
Advantages
• Increases the corrosion resistance
• Increases in surface hardness and abrasion resistance
• Provides better adhesion for paint primers
• Electrical and thermal insulation
• Porous layer allows for the coloring and sealing of the coating
Application
Anodized articles are used as soap boxes tiffin carriers, window frames, nameplates decorative object.

2) Cathodic protection
In cathodic protection electrons are provided from an external source so that the metal or alloy remains as cathode.
It is broadly divided into two:
a) Sacrificial anodic protection: SAP method
b) Impressed current cathodic protection: ICCP method
Sacrificial Anode Protection
 In this method the metal to be protected from corrosion is converted into
cathode by connecting into a metal which is anodic to it.
 The base metal is usually iron, copper or brass.
 Metals like Mg, Al and Zn are more active and hence are used as anodes.
 These metals being more active acts as anode undergo corrosion and supply
electrons to the specimen.
 In this way the protected metals acts as cathode.
Water pipe line

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  Since anodic metals are scarified to protect the metal structure this technique is called sacrificial anode
method.

Benefits
• No power source is required
• Simple to install, operate and maintain
• Additions easily installed
Example: Mg block connected to buried oil storage tanks,
Zn wire fixed to the sides of ocean-going ships are the best examples of sacrificial anode methods.

3) Metal coating
Galvanization
The process of depositing a protective layer of zinc on steel or iron is called galvanization.
It is a method used to prevent corrosion.
 In this process the base metal is coated with Zinc.
 Zinc coatings are generally obtained by hot dipping of the base metal in a molten zinc bath and the process
is called galvanization
 Iron and steel articles are protected from corrosion usually by galvanization because of the low cost of
zinc easy application of the coating and efficient anodic protection afforded.
The primary method of galvanization is “hot dip galvanization”, which has been in use for over 150 years
Galvanization consists of hot dipping which involves the following steps.
(i) The base metal surface is washed with organic solvents to remove organic impurities such as oil and grease
present on it.
(ii) Followed by water wash to remove excess organic solvents.
(iii)Then metal surface is washed with dilute sulphuric acid (pickling) to remove rust and other inorganic
deposits.
(iv) Followed by water wash to remove excess acids.

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 (v) Then the base metal surface is subjected to steam zone process where we can dry the surface (Drying
process)
(vi) The metal is treated with mixture of aqueous solution ZnCl 2 and NH4Cl which acts as flux and dried. The
flux treatment enhances the adsorption process of base metal.
(vii) The metal is then dipped in molten zinc maintained at 450 0 C.
(viii) Excess zinc is released by passing the metal through rollers (or) by wiping, which makes uniform
coating of zn on base metal.
(ix) Finally, the base metal subjected to furnace for annealing (calcination) process at higher temperature. This
process enhances the adsorption and coating efficacy.

Advantages
Since the coating is anodic in nature the exposure of base metal will not cause corrosion.

Disadvantages
Since Zn salts are poisonous food materials cannot be stored in container.

Uses/Applications
To make galvanized articles.
Galvanized Iron objects are used as roofing sheets, buckets, wires, pipes.
To manufacture automobile parts, bolts & nuts, nails etc.

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Corrosion Penetration Rate (CPR)
The rate of material removal as a consequence of the chemical action is an important corrosion parameter, this
may be expressed as the corrosion penetration rate CPR, or the thickness loss per unit of time.
Several pieces of data must be collected to calculate the corrosion penetration rate for any given metal:
 The weight lost (the decrease in weight of the metal during the period of reference).
 The density of the metal.
 The total surface area initially present.
 The time taken for the metal to corrode.

The CPR is calculated as follows:

 CPR = (k x W) / (D x A x T) where k = a constant
W = total weight lost
T = time taken for the loss of metal
A = the surface area of the exposed metal
D = the metal density in g/cm³

 The corrosion penetration rate is best expressed in terms of thickness or weight loss where the surface of
the metal corrodes uniformly across an area.
 This method involves the exposure of a weighed piece of test metal or alloy to a specific environment for
a specific time. This is followed by a thorough cleaning to remove the corrosion products and then
determining the weight of the lost metal due to corrosion.
 Where W is weight loss after exposure time T, while D and A represent the density and exposed specimen
area respectively and k is constant, its magnitude depend on the system of units used. The CPR is
conveniently expressed in terms of either mils (1/1000 inch) per year (mpy) or millimetres per year
(mm/yr).
 k=534 to give CPR in mpy (mil per year) and W, D, A and T are specified in units milligrams, gram per
cubic centimetre ,square inches and hours respectively, in second case k=87.6 for CPR in mm/yr and unit
for the other parameters are the same for first case except that A is given in square centimetres. For most
application a corrosion penetration rate less than 20 mpy (0.5 mm/yr) is acceptable.
Numerical problem:
Q1) A piece of corroded metal alloy plate was found in a submersed ocean vessel ,it was estimated that the original
area of plate was 800 cm2 and that approximately 7.6 Kg had corroded a way during the submersion , assuming
a corrosion penetration rate of 4 mm/yr for this alloy in seawater , estimate the time of submersion in years , the
density of alloy is 4.5 g/cm3.
They have given; CPR: 4 mm/yr, K: 87.6, W: 7.6 Kg, D: 4.5 g.cm3, A: 800 cm2
We need to calculate Time ?

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Q2: A steel of area 100 inch2 is exposed to air near the seashore. After 1 year it was found that the steel sheet has
lost 485 g due to corrosion. What is the value of CPR in mils/year and in mm/year ? Can such steel sheet be
applicable for the construction purpose where the steel sheet is exposed?
Given : Area (A) =100 inch , total weight lost (W) = 485g = 485 x10 3 mg,
T = 1 year =1 x 365 x 24 hrs, D = 7.9 g/cm3 and k=534.
CPR=(K x W)/(D x A x T)
CPR=(534 x 485 x 10^3)/(7.9 x 100 x 365 x 24)
CPR = 37.42 mils/year
To calculate the result in mmpy
Area =100 inch2 = 100 x 2.54 × 2.54 cm2 (1 inch = 2.54 cm) and k =87.6
87.6 x 485 x 10
CPR =
7.9 x 100 x 2.54 x 2.54 x 365 x 24
CPR = 0.9516 mmpy
Since CPR is not less than 20 m/year or 0.5 mm/year, it is not applicable for the construction purpose.
Q3: A piece of corroded steel plate was found in a submerged ocean. It was estimated that the original area of the
plate was 12 inch2 and the approximately 2.5 kg had corroded during the submersion. Assuming a corrosion
penetration rate of 100 mpy for this alloy in seawater. Estimate the time of submersion in year. The density of
steel is 7.9 g/cm3
Answer: 16.1 year
Q4: A piece of corroded steel plate was found in a submerged ocean vessel. It was estimated that the original area
of the plate was 11 inch2 and that approximately 2.3 kg had corroded away during the submersion. Assuming a
corrosion penetration rate of 200 mpy for this alloy in seawater, estimate the time of submersion in years. The
density of steel is 7.9 g/cm3
Answer: 8.03 year

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 ELECTRODE SYSTEMS
Electrode: Electrodes can be defined as conductors that are used to make electrical contact with a non-metallic
part of the circuit.
 Types of Electrodes
Electrode is a part of an electrochemical setup where an element is in contact with its own ions at which oxidation
or reduction takes place.
i. Metal / Metal ion electrode (M / Mn+ )
When a metal is immersed in its own salt solution such type of electrode is called metal/metal ion electrode is
formed. Eg: Zn/Zn2+ , Cu/ Cu2+
In general M/ Mn+
The electrode reaction is Mn+ + ne− → M
Example : Cu(s) | Cu++(aq)
Cu(s) → Cu++(aq) + 2e– (Oxidation)
Cu++(aq) + 2e– → Cu(s) (Reduction)
ii. Gas Electrode
 A gas electrode consists of a gas (e.g. H2, Cl2, O2) in contact with a solution containing the ions derivable
from the gas e.g. H+, Cl-, OH-. The potential of the gas electrode depends upon the concentration of its
ions in the solution and the pressure of a gas.
 A gas electrode consists of gas, bubbled about inert metal wire (platinized platinum electrode) immersed
in a solution containing ions with which gas is irreversible. Platinum is used as conductor and to adsorb
the gas.
 Eg: Hydrogen electrode or SHE, chlorine electrode.

iii. Metal insoluble metal salt/ common ion electrode

The metal (M) is covered with an insoluble metal salt (MX) is in contact with a solution containing an anion of
the insoluble metal salt(X).
Eg: Calomel electrode (Hg/Hg2Cl2/Cl−), silver-silver chloride electrode (Ag/AgCl2/Cl−)
iv. Redox electrode
In this electrode, an inert metal is immersed in a solution containing ions of the same metal having two different
oxidation states. Eg: Pt/ Fe2+ /Fe3+
Reaction: Fe2+→Fe3+
v. Ion selective electrode
In this type, the sensing part of the electrode is usually made of an ion-specific membrane. The membrane can
be glass membrane, crystalline membrane and ion-exchange resin membrane. Eg: Glass electrode.

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  Ion selective electrode
Definition: “Ion selective electrode is very selective towards particular type of ions and develop a potential
proportional to the concentration of that ions. The sensitive part of electrode is its membrane which allows the
exchange of selective ions”.
Ion selective electrode (ISE) are comparatively simple membrane based potentiometric devices which are
capable of accurately measuring the concentration of ions in solution.
Ex. Glass electrode, crystalline electrodes, Ion-exchange electrodes, Enzyme electrodes, Alkali metal ISE.
Working mechanism of ion selective electrodes
External reference Solution to be Membrane Internal Internal
electrode analyzed (analyte) standard reference
solution electrode
(Mn+) = C2
(Mn+) = C1

 According to the Nernst equation, the voltage is theoretically dependent on the logarithms of the ionic
activity.
 The ion-selective electrode works based on the principle of a galvanic cell. It consists of a reference
electrode, ion-selective membranes and voltmeter.
 The transport of ions from an area of high concentration to low concentration through the selective binding
of ions with the specific sites of membrane creates a potential difference. This potential is measured with
respect to a stable reference electrode having a constant potential and net charge is determined. The
strength of the net charge thus measured is directly proportional to the concentration of the selected ion.
Application of Ion-selective electrode
 Clinical chemistry: - Analysis of electrolyte such as Na+, K+ in blood, serum etc.
 Environmental chemistry: - For the analysis of CN -, F-, NH3, NO-3, in water and wastes samples.
 Agricultural chemistry: - For the analysis of K+, NH4+, etc, in soil and plant sample
 Industry: – For the analysis CN- in electroplating bath.
 Pharmaceutical: For the analysis of F - and PH of the toothpaste.
 Research and education: For the measurement of PH and other types of ions I sample.

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Glass electrode
A glass electrode is a type of ion-selective electrode made of a doped glass membrane that is sensitive to a
specific ion. The most common application of ion-selective glass electrodes is for the measurement of pH. The
pH electrode is an example of a glass electrode that is sensitive to hydrogen ions.
Construction of Glass electrode:
 The glass electrode consists of a long glass tube with a thin walled bulb at one end as
shown in the figure
 Glass electrode is constructed by immersing Ag-AgCl internal reference electrode in a
glass bulb containing 0.1M HCl solution.
 The glass bulb is made up of a long glass tube with a thin highly conducting glass
membrane at the bottom.
 The glass membrane is selective to H+ ions in the solution, and is made up of silicate
glass having composition of 72% SiO 2, 22% Na2O and 6 % CaO.
 The electrode can be represented as
Ag / AgCl / 0.1M HCl /Glass membrane
Working of glass electrode
When a glass bulb containing 0.1M HCl is immersed in an acidic solution of different concentration, a boundary
potential (Eb) is developed across the gel layers of the glass membrane.
This boundary potential (Eb) arises due to the difference is concentration of H+ ions inside and outside of the
glass bulb.
𝐸 = 0.0591 𝑙𝑜𝑔 C1 = Concentration of H+ inside the bulb, is a constant,
C2 = concentration H+ outside the bulb.
𝐸 = 0.0591 𝑙𝑜𝑔[𝐶 ] − 0.0591 𝑙𝑜𝑔[𝐶 ]
Substitute − 0.0591 𝑙𝑜𝑔[𝐶 ] = 𝐾, a constant
Then the equation becomes
𝐸 = 𝐾 + 0.0591 𝑙𝑜𝑔[𝐶 ]
= 𝐾 + 0.0591 𝑙𝑜𝑔[𝐻 ]
+
Substitute log (H ) = - pH
The final equation for Eb is obtained as
𝐸 = 𝐾 − 0.0591 𝑝𝐻
The potential of glass electrode (EG) includes contribution from 3 factors
 Boundary Potential (Eb)
 Potential of Ag-AgCl reference electrode dipped inside the bulb E Ag/AgCl
 Asymmetric potential due to slight in homogeneity of the inner and outer surface of the glass membrane
E Asy.
𝐸 =𝐸 +𝐸 / +𝐸
𝐸 = 𝐾 − 0.0591 𝑝𝐻 + 𝐸 / +𝐸
𝐸 = 𝐿 − 0.0591 𝑝𝐻
Where constant 𝐿 = 𝐾 + 𝐸 / +𝐸

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Determination of pH using glass electrode
To measure of pH of an unknown solution a glass electrode is coupled with calomel electrode and connected to
potentiometer (or pH meter for reading pH directly)

The cell formed is represented as

Hg/Hg2Cl2/KCl solution of unknown pH/Glass electrode

The potential established at the glass electrode is higher than that of

the calomel electrode hence glass electrode is taken as cathode.
E Cell = E Cathode – E anode
E Cell = E G – E SCE
Substituting for EG
E Cell = (L- 0.0591pH) – E SCE
The above equation is arranged to obtain the expression for pH
𝐿−𝐸 −𝐸
𝑝𝐻 =
0.0591

 Reference electrode
Reference electrode are electrodes whose potentials are known and are used for the determination of other
electrodes.
Example - Standard Hydrogen Electrode (SHE), calomel electrode

Saturated Calomel Electrode (SCE)

The saturated calomel electrode (SCE) is a reference electrode based on the reaction between
elemental mercury and mercury chloride.

Construction
The calomel electrode consists of two glass tube. At the inside glass tube, there
is a paste of mercury and mercurous chloride (HgCl 2 or calomel) at the bottom
of a narrow glass tube having a porous plug at the bottom. Pure mercury is filled
above paste and connected with platinum wire for electrical connections. This
narrow tube placed inside an outer glass tube filled with a saturated KCl solution
(0.1 M or of 1 M) .The porous plug at the bottom of outer tube acts as salt bridge.

 Calomel electrodes can be represented as

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Working:

The electrode potential is decided by the concentration if chloride ions and the electrode is reversible with
chloride ions. At 298 K, the electrode potentials are as follows.
0.1 M KCl electrode (0.334 V)
1 M KCl electrode (0.281 V)
Saturated KCl electrode (0.2422 V)

Applications of calomel electrode:

 It is used as secondary reference electrode in the measurement of single electrode potentials.
 It is used in potentiometric quantitate analysis.
 The SCE is used in pH measurement,
 Measurement of electrode potential using calomel electrode

Potential of any electrode can be measured by combining with a calomel

reference electrode. For example, the following cell is constructed to measure
the potential of Zn electrode
Cell representation:
𝐙𝐧 ∣ 𝐙𝐧𝟐 ∣∣ 𝐊𝐂𝐥 ∣ 𝐇𝐠 𝟐 𝐂𝐥𝟐 ∣ 𝐇𝐠
E =E −E
E =E −E
If E = 1.0 V
E = 0.2422 V − 1.0 V
E = −0.76 V

 Electrolyte Concentration Cells

 These cells consist of identical electrodes immersed in the solutions of the same electrolytes but with
varying concentrations. Potential difference arises due to difference in electrolyte concentration.

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  The working of a concentration cell depends on the equilibrium position of concentration of the cell by
means of transfer of electrons.

Components of the Concentration Cell

 Electrode - The two electrodes are called the cathode (right side) and the anode (left side). The anode
loses electrons through oxidation reaction. The cathode gains electrons through reduction reaction.
 Salt Bridge -The salt bridge offers the perfect solution for the separation of the two half-cells while
providing a pathway for ion transfer.
 Voltmeter -The voltmeter is used to measure the cell potential of the cell.

Construction

The composition of electrode material of both electrodes is

same, but these are dipped in the electrolyte solutions of
different concentrations. For example, if we take two copper
electrodes (Cu|Cu2+) in which the concentrations of copper
ions are different (say c1 and c2 respectively; c2 > c1) and
combine them to form a galvanic cell, these will give an
electrolyte concentration cell as shown in Fig.

These cells give a small potential difference while moving

towards chemical equilibrium which can be measured using a
voltmeter. Fig. Concentration cell

The internal connection is made by salt bridge. The salt bridge offers the perfect solution for the separation of the
two half-cells while providing a pathway for ion transfer.

Ex: The anode consists of Cu/Cu2+(0.001M) whereas the cathode consists of Cu 2+(0.1M)/Cu. In this cell, the
flow of electrons from the anode to the cathode is due to the reduction of Cu 2+ ions at the cathode into metallic
copper.

Cell representation

Cell reaction

At anode :

At cathode :

Net reaction :

Nernst equation for concentration cell

Nernst equation for anodic reaction:

2.303𝑅𝑇
𝐸 =𝐸 + 𝑙𝑜𝑔 𝐶 (1)
𝑛𝐹

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Nernst equation for cathodic reaction:

2.303𝑅𝑇 (2)
𝐸 =𝐸 + 𝑙𝑜𝑔 𝐶
𝑛𝐹

Cell potential: When reduction potential of both electrodes is taken into account

𝐸 =𝐸 (𝑐𝑎𝑡ℎ𝑜𝑑𝑒) − 𝐸 (𝑎𝑛𝑜𝑑𝑒)

Substitting (1) and (2) in above equation, we get

𝐸 = (𝐸 (𝑐𝑎𝑡ℎ𝑜𝑑𝑒) − 𝐸 (𝑎𝑛𝑜𝑑𝑒)) +
.
𝑙𝑜𝑔 ………(3)

In concentration cell, both electrodes are same, hence

𝐸 (𝑐𝑎𝑡ℎ𝑜𝑑𝑒) − 𝐸 (𝑎𝑛𝑜𝑑𝑒)= 0
.
From (3) 𝐸 = 𝑙𝑜𝑔

.
(or) 𝐸 = 𝑙𝑜𝑔 𝑎𝑡 298 𝐾

Numerical problem on concentration cells

1. EMF of the cell Cu/CuSO4) // CuSO4/Cu is 0.0595V at 250C. Find X value?

It is clear that C1= 0.001M, C2 = X and n= 2

Ans:

0.0591 𝐶
𝐸 = 𝑙𝑜𝑔
𝑛 𝐶

0.0591 𝑋
𝐸 = 𝑙𝑜𝑔
2 0.001

𝑋 = 0.103 𝑀

2. A concentration cell is constructed by dipping copper rods in 0.001M and 0.1 M copper sulphate solutions.
Calculate the EMF of cell at 298K.

Ans: Cell representation

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Cell reactions

Anode (oxidation): Cu → Cu2+ + 2e-

Cathode (Reduction): Cu2+ + 2e- → Cu

Overall reaction: Cu2+ C2= 0.1 M → Cu2+ C1=0.001M

0.0591 𝐶
𝐸 = 𝑙𝑜𝑔
𝑛 𝐶

0.0591 0.1
𝐸 = 𝑙𝑜𝑔
2 0.001

E cell = 0.0591 V

3. The spontaneous galvanic cell tin/ tin ion 0.02 M// tin ion (0.06M)/Tin, develops an emf of 0.041 V at 298.
Calculate the valency of Tin.

Ans : Apply Nernst equation for concentration cells

0.0591 𝐶
𝐸 = 𝑙𝑜𝑔
𝑛 𝐶

Rearrange the equation

0.0591 𝐶
𝑛= 𝑙𝑜𝑔
𝐸 𝐶

0.0591 0.06
𝑛= 𝑙𝑜𝑔
0.0141 0.01

n=2

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 ANALYTICAL TECHNIQUES

Introduction
Analytical chemistry is the study of the separation, identification and quantification of the chemical components
of natural and artificial materials.
Analytical methods can be divided into classical and instrumental methods.
1.Classical methods (Chemical method)
Chemical method use separation such as precipitation, extraction, and distillation and analyses the samples
qualitatively by color, odor, or melting classical quantitively analysis is achieved by measurement of weight
gravimetrically or volumetrically.
2.Instrumental methods (Physical method)
Physical method or advanced instrument to measure physical quantities of the analyte by relating the
concentration with light absorption, fluorescence, conductivity or Potential.

 Conductometry
It is an electrochemical method of analysis used for the determination of the electrical conductance of the
electrolyte solution by means of a conductometer.
Conductometry is the determination of electrolytic conductivity to observe the progress of a chemical reaction
Electrical conductivity of an electrolyte solution depends on the – type of ion, concentration of ions, temperature
and mobility of ion
Principle :
 The principle is based on the conductance of the electrical current through the electrolytic solution similar to
metallic conductors.
 The electrical conductance in accordance with Ohm’s law states that the strength of current’ I ‘ flowing
through conductor is directly proportional to the applied potential, E and inversely to the resistance R of
conductor.
i.e I = E / R
 The reciprocal of resistance is called the conductance. The resistance of homogenous material of uniform
cross-section with an area of ‘ a’ sq.cm and length ‘l’ cm is given by

R= 𝜌 ∗
𝜌 → Specific resistance, l→ length, a → area cross- section.
 Specific conductance - Specific conductance of an electrolyte solution is the conductance of the solution
present between two parallel electrodes of 1cm3 area of cross-section and 1cm apart.

SI unit = Siemen m-1 (Sm-1) or ohm cm-1

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 where l/A is known as the cell constant
‘R’ is the resistance of solution
 The principle underlying conductometric titrations is the substitution of ions of one mobility by ions of other
mobility. Therefore, the conductance of a solution depends on the number & mobility of ions

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