ATRIA INSTUTUTE OF TECHNOLOGY ANAND

NAGER BANGALORE-24
Prepared by T.G.Murali M.Sc., M.Phil.B.Ed.(PhD)
(Retd. General Manager Quality pharma Ind Ltd.
And Assistant professor Chemistry)
MODULE 3: Corrosion and electrode system (8hr)
(Chemistry group)
Corrosion chemistry: Introduction, electrochemical theory of corrosion, types-
differential metal, 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: Conductometry – estimation of weak acid.
Potentiometry – estimation of iron.

Corrosion:
Introduction:
Corrosion is defined as the destruction and consequent loss of metals through
chemical or electrochemical attack by the environment is called corrosion.
Corrosion classified as
  Dry corrosion (Chemical corrosion)
 Wet Corrosion (Electrochemical corrosions)
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.
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.

Electrochemical theory of corrosion / WET Corrosion (VTU)

Corrosion is an example of Oxidation. When a metal like Iron is exposed to
atmosphere, the following electrochemical changes occur gradually.
Formation of Galvanic cells
Anodic and cathodic areas are formed resulting in a large number of minute
galvanic cells.
Anodic Reaction:
At the anodic area metal undergoes oxidation with the release of electrons
Fe → Fe2+ + 2 e-
Cathodic Reaction
At cathode area electrons are absorbed and cause reduction of constituents. The
electrons flow from the anodic to cathodic area. At the cathodic area, chemical
species present on the surface of the metal get reduced.

(a) Liberation of Hydrogen: It takes places in the absence of oxygen

(i) In acidic medium
2 H+ + 2e-→ H2↑
(ii) Neutral / alkaline medium
2 H2O → 2 H+ + 2OH-
2 H+ + 2e- → H2
2 H2O + 2e- → 2 OH- + H2↑
(b) Absorption of oxygen: It takes places in the presence of oxygen
(i) Acidic medium
O2 + 4 H++ 4e- → 2 H2O
(ii) In neutral (or) alkaline medium
O2 + 2 H2O + 4e- → 4 OH-
Fe2+ ions are smaller in size; they diffuse faster than OH- ions and they combine
near the cathodic area forming insoluble ferrous hydroxide.
2 Fe2+ + 4 OH-→ 2 Fe[OH]2
Ferrous hydroxide
Ferrous hydroxide further combines with oxygen and water resulting hydrated
ferric oxide.
4 Fe[OH]2 + O2 + 2H2O→ 2 [Fe2O3.3H2O]
Hydrated ferric oxide
In the presence of limited oxygen ferrous hydroxide is converted into magnetic
oxide and it is known as black rust.
3 Fe[OH]2 + ½ O2 → Fe3O4.3H2O
Magnetic oxide (Black rust)
 Diagram 1: Schematic representation of Rust formation

Types of corrosion
Differential metal corrosion
 The metal with lower reduction potential undergoes oxidation, whereas the
metal with higher reduction potential undergoes reduction.
 Hence the metal higher in the electrochemical series is anodic to the one
below it.
 The potential difference between the two metals is the cause for corrosion,
higher the difference faster is the rate of corrosion. The anodic metal
undergoes corrosion and the cathodic metal is un attacked.
Let us consider a bimetallic sample of iron and copper as shown below.

Fe e- → Cu
Anodic site Cathodic site
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
(i) Steel screws in copper sheet
(ii) Lead-tin solder around copper wire
(iii) Buried iron pipeline connected to Zinc bar.
(iv) Steel pipe connected to copper plumbing
Differential aeration Corrosion
1. It occurs when a metal surface is exposed to differential air (or) oxygen
concentration.
2. Part of the metal exposed to lower concentration of oxygen will have lower
potential and therefore acts as anode. This part undergoes corrosion.
3. The other part of the metal exposed to higher concentration of oxygen acts as
cathode and remains unaffected.
4. The difference in oxygen concentration produces a potential difference and
causes corosion current to flow from cathode to anode.
Let us consider a strip of Zn immersed partially in a solution of ZnCl2
 Diagram 2: Schematic representation of Differential aeration corrosion
Hence part of the metal below the water level acts as anode undergoes corrosion
and the part above the water level acts as cathode and remain unaffected. The
corrosion product is formed between anodic and cathodic areas.
Differential aeration corrosion explained by the below given examples

Water line corrosion

Diagram 3: Differential aeration corrosion – Waterline corrosion

 This take 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 are 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

Pitting corrosion
 Diagram 4: Differential aeration corrosion – Pitting corrosion

 It arises when a small portion of the metallic surface is covered by dust or

scale or oil drops.
 The metal below the dust which is exposed to lower concentration of
oxygen acts as anodic area.
 In the presence of suitable corrosive environment metal is lost at that place
a pit is formed.
 The whole remaining part of the metal which is exposed to higher
concentration of oxygen acts as cathodic area and remains unaffected.
 Once a pit is formed corrosion occurs rapidly because of small anodic
area(pit) and large cathodic area.

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
 ANODIZING
 CATHODIC PROTECTION
 METAL COATING

ANODIZING

Process of anodizing of Aluminum

1.Anodizing is generally produced on non-ferrous metals like Al, Zn, Mg
and their alloys.
2.Al 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.

Diagram 5: Anodizing of Aluminum

Anode: Aluminum
Cathode: Cu / Steel/Lead
Electrolyte: 5-10 % chromic acid or 10 % H2SO4
Temperature: 35oC
Voltage: 40 V
Current density: 100 A /m2
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 35oC
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
Application
Anodized articles are used as soap boxes tiffin carriers, window frames,
nameplates decorative object.

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:

SACRIFICIAL ANODIC PROTECTION: SAP METHOD

IMPRESSED CURRENT CATHODIC PROTECTION: ICCP METHOD

Sacrificial Anode Protection

 Diagram 6: SAP method

Diagram 7: Water pipe line Diagram 8: Ship hulk

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.
 Since anodic metals are scarified to protect the metal structure this
technique is called sacrificial anode method.
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.
Impressed Current Cathodic Protection (Impressed current / Voltage method)
It is a method of protecting the base metal by application a direct current larger
than the corrosion current, which is called impressed current.
The metal to be protected is made cathode by connecting it to the negative
terminal of a DC source.
Positive terminal is connected to an inert anode like graphite.

Diagram 9: ICCP method

 Diagram 10: Gasoline pipe line
Anode being inert remain unaffected.
Graphite is widely used as the inert anode in this method, Si, Fe can also be used
as anode.
The standard electrode potential of the metal is determined by connecting it with
a solution of its own ions of unit concentration.
METAL COATING

Galvanization
1. In this process the base metal is coated with Zinc.
2. Zinc coatings are generally obtained by hot dipping of the base metal in a
molten zinc bath and the process is called galvanization
3. 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.
Galvanization consists of hot dipping which involves the following steps.
(i) The metal surface is washed with organic solvents to remove organic
solvents to remove organic impurities such as oil and grease present
on it.
(ii) Then metal surface is washed with dilute sulphuric acid (pickling)
to remove rust and other inorganic deposits.
(iii) Then it is washed well with water and air dried.
 (iv) The metal is treated with mixture of aqueous solution ZnCl 2 and
NH4Cl which acts as flux and dried.
(v) The metal is then dipped in molten zinc maintained at 450 0 C.
(vi) Excess zinc is released by passing the metal through rollers (or) by
wiping.
Application:
Galvanized Iron objects are used as ROOFING sheets, Wires, Pipes, Bolt’s,
Tubes etc.

Diagram 11: Galvanization process

Diagram 12: Schematic representation of Galvanization process

Numerical problem on corrosion Penetration rate (CPR) and weight

loss method. VTU
Weight-loss method.
1. Weight-loss tests are mostly used for measurement of corrosion.
2. In this, clean metal coupon or a standard test piece is measured,
weighed and exposed to the corrodent for a known time.
3. The piece is then taken out, cleaned to remove the corrosion
products and reweighed.

The rate of corrosion of the metal, R is then calculated from the

equation.

CPR= KW
ATD
Where K is constant,
T- is time of exposure to the nearest 100th of an hour.
W- is the weight loss to the nearest milligram
A is the area to the nearest sq.cm, and
D- is density, g/cm3.
CPR- is corrosion penetration rate
The result are expressed in many different units such as mg/dm2/day
or oz/ft2/day or month or inches per year (IPY) or millimeters per
year (MPY). Assuming that the surface corrosion was uniform, these
units may be converted to depth of corrosion or penetration.

Note:
CPR – mpy (mil/per/year) 1mil= 0.001inch hence K=534 should be
taken.
CPR- mm/year K= 87.6 should take.
Problem 1
A piece of corroded steel plate was found in a submerged ocean
vessel. It was estimated that the original area of the plate was 10 in2
and that approximately 2.6 kg had corroded away during
submersion. Assuming a corrosion penetration rate of 20 mpy for
this alloy in sea water, estimate the time of submersion in years. The
density of steel is 7.9 g/cm3.
Formula
𝐾𝑊
𝐶𝑃𝑅 =
𝐴𝑇𝐷

Where A - (area) = 10 in2

W- (Weight loss) =2.6 Kg
CPR- (corrosion penetration rate) = 200 mpy
T- (Time taken) =? Years
K – (Constant) = 534
𝐾𝑊
𝐶𝑃𝑅 =
𝐴𝑇𝐷
534𝑋2. 6𝑋1010
200 =
7.9𝑋10𝑋𝑇
𝑇 = 534X2.6X106
7.9 X10X 200
T= 87873.41 hr
365X24
= 10.03 year
Ion selective electrode – definition, construction,
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
++
ttions”.
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 Solution to Membrane Internal Internal
reference analyzed standard reference
electrode (analyte) 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.
working and applications of glass electrode
GLASS ELECTRODE
Construction Glass electrode:
1. Glass electrode is constructed by immersing Ag-AgCl internal reference
electrode in a glass bulb containing 0.1M HCl solution.
2. The glass bulb is made up of a long glass tube with a thin highly conducting
glass membrane at the bottom.
3. The glass membrane is selective to H+ ions in the solution, and is made up of
silicate glass having composition of 72% SiO2, 22% Na2O and 6 % Cao.

Diagram 4. Glass electrode

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.
𝐶2
𝐸𝑏 = 0.0591 𝑙𝑜𝑔
𝐶1
C1 = Concentration of H+ inside the bulb, is a constant, C2 = concentration H+
outside the bulb.
𝐸𝑏 = 0.0591 𝑙𝑜𝑔[𝐶2 ] − 0.0591 𝑙𝑜𝑔[𝐶1 ]
Substitute − 0.0591 𝑙𝑜𝑔[𝐶1 ] = 𝐾, a constant
Then the equation becomes
𝐸𝑏 = 𝐾 + 0.0591 𝑙𝑜𝑔[𝐶2 ] = 𝐾 + 0.0591 𝑙𝑜𝑔[𝐻+ ]
Substitute log (H+) = - pH
The final equation for Eb is obtained as
𝐸𝑏 = 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.
𝐸𝐺 = 𝐸𝑏 + 𝐸𝐴𝑔/𝐴𝑔𝐶𝑙 + 𝐸𝐴𝑠𝑦
𝐸𝐺 = 𝐾 − 0.0591 𝑝𝐻 + 𝐸𝐴𝑔/𝐴𝑔𝐶𝑙 + 𝐸𝐴𝑠𝑦
𝐸𝐺 = 𝐿 − 0.0591 𝑝𝐻
Where constant 𝐿 = 𝐾 + 𝐸𝐴𝑔/𝐴𝑔𝐶𝑙 + 𝐸𝐴𝑠𝑦
Determination of pH using glass electrode.
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)

Diagram 5. Determination of pH
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 − 𝐸𝑆𝐶𝐸 − 𝐸𝑐𝑒𝑙𝑙
𝑝𝐻 =
0.0591
Reference electrode: Introduction, calomel electrode
– construction, working and applications of calomel
electrode.
REFERENCE ELECTRODE

An electrode having fixed potential, which can be used as a reference to

measure the potential of another electrode.

Construction
 The saturated calomel electrode (SCE) is a reference electrode based on
the reaction between elemental mercury and mercury chloride.
 The calomel electrode consists of two glass tube. At the inside glass tube,
there is a paste of mercury and mercurous chloride (calomel) (Hg 2Cl2) 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. KCI solution of 0.1 M or of 1 M can
also be used. The porous plug at the bottom of outer tube acts as salt bridge.

 Calomel electrodes can be represented as

 Diagram 2. Calomel electrode

Working:
Since the calomel electrode is reversible, two types of reactions are possible
depending upon the nature of another electrode with which it is coupled.
When it acts as anode, the electrode reaction is
2𝐻𝑔 + 2𝐶𝑙− → 2𝐻𝑔2 𝐶𝑙2 + 2𝑒 −
Thus, oxidation takes place when it is coupled with another electrode having
lower oxidation potential.
When it acts as cathode, the electrode reaction is
2𝐻𝑔2 𝐶𝑙2 + 2𝑒 − → 2𝐻𝑔 + 2𝐶𝑙−
Thus, reduction takes place when it is coupled with another electrode having
greater oxidation potential.
The net reversible electrode reaction
 2𝐻𝑔2 𝐶𝑙2 + 2𝑒 − ↔ 2𝐻𝑔 + 2𝐶𝑙 −
Electrode potential
2.303𝑅𝑇
𝐸 = 𝐸𝑜 − 𝑙𝑜𝑔[𝐶𝑙 − ] 2
2𝐹

𝐸 = 𝐸 𝑜 − 0.0591 𝑙𝑜𝑔[𝐶𝑙 − ] at 298 K

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:
1. It is used as secondary reference electrode in the measurement of single
electrode potentials.
2. It is used in potentiometric quantitate analysis.

Concentration cell – Definition, construction and

Numerical problems.
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.
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 concentration cell is a type of galvanic cell where the half-cells consist
of the same substance but at different concentrations. These cells give a small
potential difference while moving towards chemical equilibrium which can be
measured using a voltmeter.

Ex: The anode consists of Cu/Cu2+(0.001M) whereas the cathode consists of

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

Diagram 6. Concentration cell

Cell representation

Cell reaction
At anode
At cathode

Net reaction

Nernst equation for concentration cell

Nernst equation for anodic reaction:

𝑜
2.303𝑅𝑇
𝐸𝑎𝑛𝑜𝑑𝑒 = 𝐸𝑎𝑛𝑜𝑑𝑒 + 𝑙𝑜𝑔 𝐶1
𝑛𝐹
Nernst equation for anodic reaction:

𝑜
2.303𝑅𝑇
𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 + 𝑙𝑜𝑔 𝐶2
𝑛𝐹
Cell potential: When reduction potential of both electrodes is taken into account
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑟𝑒𝑑 (𝑐𝑎𝑡ℎ𝑜𝑑𝑒) − 𝐸𝑟𝑒𝑑 (𝑎𝑛𝑜𝑑𝑒)
𝑜 𝑜 2.303𝑅𝑇 𝐶2
𝐸𝑐𝑒𝑙𝑙 = (𝐸𝑟𝑒𝑑 (𝑐𝑎𝑡ℎ𝑜𝑑𝑒) − 𝐸𝑟𝑒𝑑 (𝑎𝑛𝑜𝑑𝑒)) + 𝑙𝑜𝑔
𝑛𝐹 𝐶1

In concentration cell, both electrodes are same, hence

𝑜 𝑜
𝐸𝑟𝑒𝑑 (𝑐𝑎𝑡ℎ𝑜𝑑𝑒) − 𝐸𝑟𝑒𝑑 (𝑎𝑛𝑜𝑑𝑒)= 0
2.303𝑅𝑇 𝐶2
𝐸𝑐𝑒𝑙𝑙 = 𝑙𝑜𝑔
𝑛𝐹 𝐶1
Or
0.0591 𝐶2
𝐸𝑐𝑒𝑙𝑙 = 𝑙𝑜𝑔 𝑎𝑡 298 𝐾
𝑛 𝐶1

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 𝐶2
𝐸𝑐𝑒𝑙𝑙 = 𝑙𝑜𝑔
𝑛 𝐶1
0.0591 𝑋
𝐸𝑐𝑒𝑙𝑙 = 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

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 𝐶2
𝐸𝑐𝑒𝑙𝑙 = 𝑙𝑜𝑔
𝑛 𝐶1
0.0591 0.1
𝐸𝑐𝑒𝑙𝑙 = 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.
Apply Nernst equation for concentration cells
0.0591 𝐶2
𝐸𝑐𝑒𝑙𝑙 = 𝑙𝑜𝑔
𝑛 𝐶1
Rearrange the equation
0.0591 𝐶2
𝑛= 𝑙𝑜𝑔
𝐸𝑐𝑒𝑙𝑙 𝐶1

0.0591 0.06
𝑛= 𝑙𝑜𝑔
0.0141 0.01
n=2
Analytical techniques: Introduction, principle and
instrumentation: Colorimetric sensors – estimation
of copper,
Instrumental Analysis
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 colour, odour, 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.
The instrumental methods have greatest advantage that it can investigate the
structure of complex organic molecules, reaction kinetics and even the
biochemistry of living cells.

Method Principle and Application

instrumentation
1.Colorimetry Light absorbance is To determine
proportional to concentration of ions
concentration and path and molecules in
length. Beer lambert law solutions.
based visible light source
used.
2.Flame photometry Measurement of emitted To determine
radiation. No light source concentration of
but only flame used. selective metals
(Na, K, etc.) in sample
3. Atomic Absorption Measurement of intensity To determine the
spectroscopy. of absorbed radiation. Light concentration of metal
source and flame. elements in samples.

4.Potentiometry It measures current/voltage To determine

between two electrodes concentration of ions in
where redox reaction take samples through redox
place titration.

5.Conductometry It measures only movement To measure conductivity

and concentration of ions. of sample solutions.
(no redox reaction)

Calorimetry
1. Simple technique used to determine the concentration of compounds in a
solution.
2. This method is used for solution which are themselves colored (or) which
gives colour with a suitable reagent.
3. The colour intensity of the solution is directly proportional to the
concentration of the solution.
Theory
This method is based on Beer- Lambert law
According to this law when a monochromatic light is passed through a
solution, part of light is absorbed by the solution. The extent of absorption
depends on the concentration of the solution and the path length of the light
trough the solution.
A = €.C.t
A →Absorbance
C →Concentration of solution.
t → path length
€ → Molar absorption coefficient which is dependent on the material
being studied.
Instrumentation
Photo electric calorimeter are made of the following components.
1. Tungsten lamp as light source
2. A filter which provides the desired wavelength range.
3. A sample cell.
4. A photocell detector.
 Diagram 1: Colorimeter

1. Monochromatic light of suitable wavelength can fall on the sample cell.

2. First blank solution is taken in the sample cell and placed in the path of
light beam.
3. Its absorbance is adjusted to zero.
4. Then the analyte solution is placed in the path of light and its absorbance
is measured.
5. A plot of absorbance versus standard concentration of analyte is used to
find the unknown concentration of analyte in the samples.
Application calorimetry
1. Colorimetry is used various laboratories including clinical
laboratories for biochemical estimation.
2. Colorimetry is used in clinical laboratories for the analysis of
biomolecules such as glucose, urea, etc.
3. Calorimetry is used soil testing laboratories for analysis of pesticides,
soil nutrients and plant nutrients.
Calorimetry is used in the estimation of copper in sample solutions.
Cu2+ ions are treated with NH3 to form a deep blue colored cupra-
ammonium complex ion.
1. From a burette add 2, 4, 6 and 8 Cm3 of given copper sulphate
solution into four separate 50 cm3 in volumetric flask.
 2. From another burette add 5cm3 of ammonia to each one of them, to
the unknown solution and blank solution flask.
3. To the entire six flasks add water up to the mark. Mix well wait for
10 minutes.
4. In the colorimeter set the wavelength of light to be 620 nm.
5. Using blank solution, set absorbance of colorimeter as zero
6. Record Optical density values for all the solutions including Test.
7. Plot a graph of absorbance against volume of CuSO4. Determine the
volume of CuSO4 is unknown solution from the graph.

UNKNOWN
ABSORBANCE
UNKNOWN
VOLUME
Graph 1. OD Vs Vol of NaOH

Potentiometric sensors – estimation of iron

Potentiometer
Theory
The measurement of e.m.f. (electromotive force) to determine the concentration
of ionic species in solution is referred to as potentiometry.
The relation between electrode potential and metal ion concentration is given by
Nernst equation.
E = EO + 0.591 log Fe+2
N Fe+3
Instrumentation

Diagram 4: Potentiometer

1. Potentiometer consists of a reference electrode, and indicator electrode and a

device for measuring the potential.
2. The indicator electrode respond rapidly to the changes in the potential due to
the concentration changes of the analyte.
3. A known volume of the analyte is taken in a beaker and its potential is
determined by connecting the assembly to a potentiometer.
4. The titrant is added in increments of 0.5ml and the potential is measured each
time.
5. The equivalent point there is a sharp increase in the potential against the
volume of titrant.
 Graph 3: ∆E/∆V Vs Vol of K2Cr2O7

6. Redox titration is that of ferrous ammonium sulphate (∆E/∆V) against K2Cr2O7

or KMnO4.The oxidizing agent is usually taken in the burette.
Application
1. It is used in oxidation reduction titrations to estimate the concentration of
analyte in the sample solution.
2. The potential of the electrode depends on the concentration of the substance
being oxidized or reduced.
Advantages
1. Potentiometric titrations (estimation) does not depend on color change or redox
indicator.
2. Several analyte present in the same solution can be estimated by as single
titrating solution.
Conductometric sensors – estimation of weak acid.

Conductometer
Theory
Electrolyte solution conducts current by the migration of ions under the influence
of an electric field.
E= I R
Where; I → current, R→ Resistance
Ohm’s law states that the current’ I ‘ flow through conductor is directly
proportional to the applied potential, E and inversely to the resistance R of
conductor.
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= Ᵽ. l/a
Ᵽ → 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.
K= 1/R x l/a
Where l/a is known as the cell constant
‘R’ is the resistance of solution
K = Cell constant
Resistance
Instrumentation
1.It consists of a platinum electrode each of unit area of cross-section placed unit
distance a part.
Diagram to be passed
2. The electrodes are dipped in the electrolyte solution taken in a beaker.
3. It is connected to a conductance measuring device.
4. The titrant is added from a burette and solution is stirred.
5. The conductance is measured after the addition of the titrant at intervals of 0.5
ml.

Diagram 5: Conductometer

Application of conductometry
1. Strong acid with strong base (HCl vs NaOH)
NaOH + HCl → NaCl + H2O
1. Consider the titration of strong acid HCl with a strong base NaOH.
2. You will notice that on addition of NaOH the conductance of acid solution
decreases gradually until the acid is completely neutralized.
3. A plot of conductance against the volume of NaOH is shown in the figure.
4. The point of intersection of the two lines is the neutralization point.
5. The conductance decreases, because the small and highly mobile H+ in the
acid is gradually replaced by heavier and less mobile Na+ ions. Addition of
base beyond neutralization points increase in the number of more mobile
OH- ions and conductance increases.
 Graph 4: Conductance Vs Vol of NaOH

2. Weak acid with strong base

Consider the titration of acetic acid with a strong base NaOH. (CH3COOH versus
NaOH)
NaOH + CH3COOH → CH3COONa + H2O
Consider the titration of acetic acid with a strong base NaOH, the conductance of
weak acid solution increases until the acid is completely neutralized.
A Plot of conductance against the volume of NaOH is shown in the figure. The
point of intersection of the two lines is the neutralization point.

Graph 5: Conductance Vs Vol of NaOH

Acid mixture with a strong base (HCl and CH3COOH versus NaOH)
Consider the titration of acid mixture (HCl and CH3COOH) with strong base
NaOH
1.You will notice that on addition of NaOH the conductance of the acid mixture
solution decreases steeply. The conductance decreases steeply because the small
and highly mobile H+ ions in the strong acid is gradually replaced by heavier and
less mobile Na+ ions.
HCl + NaOH → NaCl + H2O
2.Addition of base beyond the first neutralization point leads to moderate increase
in conductance. The conductance increases moderately, because the poorly
conducting weak acid (acetic acid) is gradually converted to highly conducting
salt (Sodium acetate) until the second neutralization point.
CH3COOH + NaOH → CH3COONa + H2O
Further addition of NaOH increases number of highly mobile OH- ions. Hence
conductance increases steeply.

Graph 6: Conductance acid mixture Vs NaOH