CHAPTER: Electrochemistry 1

Unit-2

Electrochemistry
CHAPTER: Electrochemistry 2

INTRODUCTION

“Electrochemistry is the branch of science that deals with the chemical applications of electricity.
It involves the inter -conversion of electrical energy to chemical energy and vice-versa”. When electric
current is passed through a conducting aqueous solution (electrolyte), the positively charged ions (cations)
move towards the negatively charged electrode known as the cathode, while the negatively charged ions
(anions) moves towards the positively charged electrode called the anode. Thus electrical energy is
converted into chemical energy. Flow of electricity through electrolytes is due to the migration of ions when
there is a potential difference applied between the two electrodes. In other words, the flow of electricity in
an electrolyte results in chemical reaction at the electrodes.

“A Material that allows the electric current to pass through is known as Conductor”. In conductors, the
electrons in the outermost orbit are very loosely bound to their nucleus which leads to the flow of electrons
in an electic field. Examples: Copper, Aluminium, fused salts, most of the bases and solutions of acids, etc.

Non-Conductors or Insulators: Materials which do not conduct electricity are called insulators or non-
conductors.

Examples: Wood, plastics, most of the non-metals.

The conductors are broadly classified into two types:

1) Metallic conductors or electronic conductors: These are the solid substances which conduct
electricity due to the movement of electrons from one end to another end.

Examples: all the metals and graphite. In all these only valence electrons carry current.

2) Electrolytic conductors: In electrolytic conductors current is carried by the ions of the electrolyte
that is present in the fused state or liquid state. In this type of conductors, increase in temperature
increases the rate of conduction due to the fast movement of ions.

Examples: Acids and bases.

Further, electrolytic conductors are classified into three types:

a) Strong electrolytes: These are the substances which ionize completely at any concentration.
Examples: HCl, aqueous solution of NaOH, NaCl and KCl

b) Weak electrolytes: Weak electrolytes are the substances which ionize partially in all solutions.

Examples: CH3COOH, NH4OH and aqueous solution of Na2CO3

c) Non-electrolytes: Substances which do not conduct electricity are called non-electrolytes,

CHAPTER: Electrochemistry 3

Examples: pure water, sugar solution, petrol.

Terminology related to Electrochemistry:

1. Current: Flow of electrons through any conducting material. It is measured in ampere.

2. Oxidation: The tendency to lose electrons. It occurs at anode

3. Reduction: The tendency to gain electrons. It occurs at cathode.

4. Electrode: When a metal rod or strip is dipped in its salt solution.

5. Anode: The electrode at which oxidation occurs.

6. Cathode: The electrode at which reduction occurs.

7. Electrolytes: Conductance takes place due to the movement of ions present in the liquid or solution.

8. Cell: Cell is an arrangement of two electrodes in electrolyte.

9. Half cell: A part of a cell containing electrode dipped in an electrolytic solution.

10. Oxidation half cell: The electrode where oxidation takes place.

11. Reduction half cell: The electrode where reduction takes place.

Types of cell:
Cell may be defined into two types:
a. Electrolytic cells
b. Electrochemical cells or galvanic cells

a. Electrolytic cells:
Electrolytic cells are cells in which electrical energy is converted into chemical energy. In these cells,
the electrical energy is supplied from an external source, which brings the dissociation of electrolytes into
ions. In these cells Cathode will be negatively charged and anode will be positively charged. It is measured
in coulometer or Ammeter.

Examples: Electrolysis and Electroplating

CHAPTER: Electrochemistry 4

Fig Electrolytic cell

b. Electrochemical cells:

A galvanic cell or electrochemical cell or Daniel cell is a device which produces electrical energy at the
expense of chemical energy .In these cells Cathode will be positively charged and anode will be negatively
charged. It is measured in It is measured by Potentiometer or Voltmeter.
Example: Daniel cell.

Daniel cell consists of copper rod dipped in 1M CuSO4 which is separated with the help of a porous
pot from 1M ZnSO4 solution in which is a dipping a rod of zinc. The porous pot prevents the diffusion of the
two solutions but allows the passage of ions when the flow of an electric current takes place, on connecting
the two rods by a metallic wire.

Process:
At anode:
At anode oxidation takes place with the liberation of electrons. The electrode is also called as negative
electrode.

Zn → Zn2+ +2e-
CHAPTER: Electrochemistry 5

At cathode
Reduction takes place at copper electrode by the acceptance of electrons. This electrode is also called as
positive electrode.

Cu2+ +2e- → Cu

Overall reaction: Zn + Cu2+ → Zn2+ + Cu

Separator:
In order to avoid mixing of different electrolytes used for electrodes a separation medium which permits
electrons only is introduced.
Example: Salt bridge , Porous pot, etc.
Salt bridge:
It consists of a U-tube containing a gel saturated with KCl or NH4NO3 in agar-agar .It connects the two half
cells of the galvanic cells by the electron movement through it.
Functions of salt bridge:
(i) It eliminates liquid intersection potential.
(ii) Complete the full circuit
(iii) Separates the two electrolytic half cell solutions.
(iv) Measure the accurate emf of the cell.

Cell Representation of Galvanic cell:

A galvanic cell consists of two electrodes-anode and cathode. According to present conventions, a galvanic
cell is represented by keeping the following points:
1) Anode is written on the left hand side while cathode is written on the right hand side.
2) The anode must be written by writing the metal first and then electrolyte. These two are separated
by a vertical line or a semicolon. The electrolyte may be written by the formula of the compound or
by ionic species with their concentrations mentioned within brackets.
Example:
Zn / Zn 2+ (or) Zn / ZnSO4 (1M) (or) Zn; Z n2+
3) The cathode must be written by writing the electrolyte first and then the metal.These two are
separated by a vertical line or a semicolon. The electrolyte may be written by the formula of the
compound or by ionic species with their concentrations mentioned within brackets.
Example:
Cu2+ / Cu (or) CuSO4 / Cu (or) Cu2+; Cu
4) A salt bridge is indicated by two vertical lines, separating the two half cells.
Using the above representation, the galvanic cell is represented as follows:
CHAPTER: Electrochemistry 6

a) Zn / ZnSO4 (1M) // CuSO4 (1M) / Cu

b) Zn / Zn 2+ (1M) // Cu2+ (1M) / Cu
c) Zn; Z n2+ (1M) // Cu2+ (1M) ; Cu

REVERSIBLE AND IRREVERSIBLE CELLS

REVERSIBLE CELLS:
Electrochemical cells which obey the following three conditions of thermodynamic reversibility are
called reversible cells. Examples: Daniel cell.
Cell reaction is represented as: Zn / ZnSO4 (1M) // CuSO4 (1M) / Cu

i) If a Daniel cell is connected to an external source of the emf equal to 1.1 Volt, no current flows
and also no chemical reaction takes place in the cell. i.e. it is in equilibrium.

Zn+CuSO4 ZnSO4+Cu

ii) If the external emf is applied slightly less than 1.1 volt,a small amount current flows from the
cell and forward chemical reaction occurs.

Zn+CuSO4 → ZnSO4+Cu

iii) If the external emf >1.1 volt, the current will flow in the opposite direction. Copper passes into
the solution as copper ions and zinc gets deposited on the zinc electrode.
ZnSO4+Cu → Zn+CuSO4

IRREVERSIBLE CELL :

Cells which do not obey the conditions of thermodynamic reversibility are called irreversible cells.
Examples: Zinc-Silver cell, Dry cell etc.,

Cell reaction is represented as: Zn / H2SO4 (aq) / Ag

The cell reactions occur at anode and cathode is:
Zn + H2SO4  ZnSO4 + H2  (at anode)
2Ag+ + 2e-  2Ag (at cathode)
CHAPTER: Electrochemistry 7

When the two electrodes are connected, zinc dissolves with the liberation of hydrogen gas.

When the external emf slightly > actual emf, the above reaction are not reversed, because one of
the product, H2 gas already escaped. Such cells, which do not obey the conditions of thermodynamic
reversibility ,are called irreversible cells.

Single electrode potential (E):

The measure of tendency of a metallic electrode to lose or gain electrons in contact with a solution
of its own salt.

EMF OF A CELL

Definition:

Electromotive force is defined as “the difference of potential which causes flow of electrons from the
electrode of higher potential to the electrode of lower potential”.

Thus, the emf of a galvanic cell can be calculated by using the following relationship,

Standard EMF= {Standard reduction potential of right hand side electrode}-

{Standard reduction potential of left hand side electrode}.

E0cell= E0right - E0left

Measurement of emf of a cell:

Emf of a cell can be measured by connecting the two electrodes to the two terminals of a voltmeter. The
voltage is read directly from the instrument. But drawbacks of using this method are:

a) The instrument draws some current from the cell, causing a change in the emf due to formation of
reaction products at the electrodes and changes in the concentration of the electrolyte around the
electrodes.

b) Secondly, with flow of current, a part of the emf is used up in overcoming the internal resistance of
the cell. Hence, the potential difference as read from the voltmeter will not be correct emf of the
cell.
CHAPTER: Electrochemistry 8

It is evident from the above discussions that emf of a cell can be measured accurately only by a
method which involves little or no flow of electricity. Such a method is based on Poggendorff’s
compensation principle. In this method, the emf to be measured is opposed by the emf of another
cell or battery until the two emf s become equal and there is no net flow of current in the circuit. The
electrical assembly used is known as potentiometer.

The potentiometer consists of a uniform wire AB .A storage battery (K) is connected to the ends A
and B of the wire through a rheostat (R) .The cell of unknown emf (x) is connected in the circuit by
connecting its positive pole to A and the negative pole is connected to a sliding contact (D) through
a galvanometer (G) .The sliding contact (D) is freely moved along the wire AB till no current flows
through the galvanometer. Then the distance AD is measured. The emf of unknown cell is directly
proportional to the distance AD.

Fig. Potentiometer for the measurement of emf

Then the unknown cell (x) is replaced by a standard cell (s) in the circuit. The sliding contact is again moved
till there is null deflection in the galvanometer. Then the distance AD’ is measured.

The emf of standard cell Es is directly proportional to the distance AD’

Es œ AD’

Then, the emf of the unknown cell can be calculated from the following equation,
CHAPTER: Electrochemistry 9

Emf of the unknown cell = Ex =

Factors affecting the emf of a cell

1. Nature of the electrolytes and electrodes

2. Concentration and composition of the electrolytes.
3. pH and temperature of the solution.

Applications of EMF Measurement

1. Determination of standard free change and equilibrium constant
2. Determination of pH
3. Solubility of sparingly soluble salts
4. Determination of valency of ion:
5. Potentiometric titration can be carried out.

NERNST EQUATION FOR SINGLE ELECTRODE POTENTIAL

Consider the following redox reaction,

Mn+ + ne– M …. (1)
For such redox reversible reaction,the free energy change (∆G) and its equilibrium constant (K) are
interrelated as:

According to Van’t Hoff’s reaction isotherm

 Product 
G = – RT ln K + RT ln  …. (2)
 Reactant 
We know that,
Gº = – RT ln K
CHAPTER: Electrochemistry 10

From the above equation

 Product 
G = Gº + RT ln  …. (3)
 Reactant 
The decrease of free energy (-∆G) in the above equation will produce electrical energy.In the cell ,if the
reaction involves the transfer of ‘n’ number of electrons,then ‘n’ faraday of electricity will flow. If E is the
emf of the cell,then the total electrical energy (Nfe0 produced in the cell is

Free energy relates with electrode potential by the following equation.

G = -nFE and Gº = -nFEº …. (4)
Comparing equations (3) & (4),

 [Product] 
 nFE  nFE 0  RT ln   …. (5)
 [Reactant] 

Divide the above equation (5) by (- nF)

RT  [Product] 
E  E0  ln   .... (6)
nF  [Reactant] 
The activity of solid metal =1,the above equation becomes,

(or)

(or)

…………..(7)

Where R=8.314 J/K/Mole; F= 96500 Coulombs;T=298 K

The above equation becomes

……(8)

The equation (8) is known as Nernst equation for single electrode potential
CHAPTER: Electrochemistry 11

Applications of Nernst Equations

➢ Nernst equation is used to calculate electrode potential of unknown metal
➢ Corrosion tendency of metals can be predicted.
➢ It is used to calculate the EMF of a cell.
➢ Concentration of the reactant can be calculated using the electrode potential.
➢ Concentration of the solution in galvanic cell can be determined.
➢ pH of a solution can be calculated by measuring the emf.
➢ To find relative ease of oxidation or reduction.
➢ To identify the displacement of one element by the other.
➢ To find the hydrogen displacement behavior.
➢ To predict the spontaneity or feasibility of redox reactions.
➢ To determine the standard free energy change (∆G) and equilibrium constant (K) for the reaction.

Problems based on Nernst Equation

1. Calculate the reduction potential of lead electrode in contact with a solution of 0.018M Pb2+
ions (standard reduction potential = - 0.13V).
GIVEN:
[Pb2+] = 0.018M E0 = -0.13V n=2
SOLUTION:
Nernst equation for reduction potential is

Oxidation potential of Pb = -0.1816 V

2. What is the potential of a nickel electrode that is in contact with a solution of 0.25 M Ni2+ ions?
CHAPTER: Electrochemistry 12

E0 for Ni → Ni2+ +2e- E0=0.24 V

Given: The oxidation reaction is given by the equation

Ni → Ni2+ +2e- -
E0=0.24 V
N=2; [Ni 2+]= 0.25 M

The Nernst equation for the above equation is

The oxidation potential of nickel electrode is 0.2578 V

Reference Electrode
The electrode potential is determined by coupling the electrode with another reference electrode, the
potential of which is known or arbitrarily fixed as zero. The best reference electrode used is the standard
hydrogen electrode. The standard electrode potential of the standard hydrogen electrode at all temperature is
taken as zero. It is very difficult to set up a hydrogen electrode. So, other reference electrode like calomel
electrodes is also used as secondary reference electrode and internal or ion selective electrodes used is glass
electrode.The reference electrodes are used to compare the potential of other electrodes. Types:
1. Primary electrode-Hyderogen electrode
2. Secondary reference electrode- Calomel electrode
3. Ion selective electrode- Glass electrode
CHAPTER: Electrochemistry 13

Ion Selective Electrode-Glass electrode

Glass electrode is a secondary reference electrode which produces a constant and reproducible
electrode potential. It is ion selective electrodes and used for the pH measurements.
Construction and Working
It is made up of a special type of glass relatively low melting point and high electrical
conductivity. Long glass tube with a thin glass bulb filled with 0.1M HCl. A Pt wire or silver wire
coated with a layer of AgCl is inserted into it to make electrical contact. Electrode representation
is, Pt/0.1MHCl,glass/Test H+ solution .The electrode potential of glass electrode is
𝐸𝐺=EG 0+ 0.0591 log[H+ ]
𝐸𝐺= EG 0 - 0.0591[pH]
EG 0 is a constant depending upon the nature of the glass and pH of the solution taken inside the
glass tube.
Determination of pH by using glass electrode Principle:
The H+ ion concentration inside the electrode is constant. When this electrode is dipped in to a
solution of unknown H+ , it becomes sensitive to the outside concentration in the solution. The
potential difference is developed across the membrane. By measuring that potential difference, we
can find out pH .
Procedure
• Unknown solution is taken in beaker
• Glass electrode is dipped in it.
• It is connected to a saturated calomel electrode.
• emf of the cell is measured.
Ecell = EC-E𝑎
Ecell = Ecalomel - Eglass
Ecell = 0.2422-[EG 0 -0.0591pH]
pH = Ecell+ EG 0 -0.2422/ 0.0591
Advantage
1. It is simple and easily be used.
2. Used in pH range 0 -12.
3. The results are accurate.
4. Can be used in presence of strong oxidizing and reducing agents.
Limitations
1. As the glass electrode has very high electrical resistance, electronic potentiometer must be used
to find EMF.
CHAPTER: Electrochemistry 14

2. Due to highly absorptive nature a lot of working is required

Fig: Glass Electrode

Electro chemical Series

The standard reduction potential values of all metals are determined with reference to standard
hydrogen electrode (SHE) and they are arranged to form a series known as emf series.
A series of elements are arranged in increasing order of their standard reduction potential is called
electrochemical series.
Electrode Electrode Reaction E0,Volts Nature

Li+ / Li Li+ +e- Li -3.01

Mg 2+ / Mg Mg2+ +2 e- Mg - 2.37
Pb 2+ / Pb Pb2+ +2 e- - 0.13
Pb
Zn 2+ / Zn Zn2+ +2 e- -0.76
Anodic
Zn
Fe 2+ / Fe Fe2+ +2 e- -0.44
Fe
2+
Sn / Sn Sn2+ +2 e- - 0.136
Sn
H+ / H2 2H+ +2e- 0.00 Reference
H2
Cu 2+ / Cu Cu2+ +2 e- + 0.34
Cu
Ag+ / Ag Ag+ +e- Ag + 0.80 Cathodic
Au+ / Au Au+ +e- Au + 1.50
½ F2 / F- 1/2 F2 +e- F- + 2.87
CHAPTER: Electrochemistry 15

Applications of electrochemical series:

1. Relative ease of oxidation or reduction

i) Higher the value of standard reduction potential (+) ve values, the greater is the tendency
to get reduced form.Eg.fluorine has highest positive value of standard reduction potential
(+2.87V),which means that F - ions are very easily reduced to F 2 .The standard reduction
potential of Li + is the least (-3.05 V),that is ,Li is very easily oxidized to Li +
2. Displacement of one species by the other

The metals with more negative reduction potential can displace those with negative or
positive potentials from their solution. Eg. Daniel cell,in which we can decide whether Cu
will displace Zn from the solution or vice -versa. We know that standard reduction potential
of Cu & Zn.

E o Cu 2 + / Cu = 0.34V and E o Zn 2 + / Zn = -0.76V

So,Cu 2 + has a greater reduction potential than Zn 2+

.Hence Zn can displace Cu from the
solution.
3. Calculation of standard emf of the cell

The standard emf of a cell (E o )can be calculated if the standard electrode potential
values are known using the following relations,

E o Cell = E o RHE – E o LHE

4. Predicting feasibility or spontaneity of the cell reaction

In a reversible cell, when the cell yields electrical energy, there is a fall in free
energy (or) -G = nFE.

(a) If G = Negative; E = Positive, then the cell reaction is feasible or spontaneous.

(b) If G = Positive; E = Negative, then the cell reaction is non spontaneous.

5. Determination of equilibrium constant

Standard electrode potential can be used to determine the equilibrium constant for the
reaction.

nFE 0
log k 
2.303 RT
CHAPTER: Electrochemistry 16

6. Hydrogen displacement behaviour

Metals with negative reduction potential (i.e., metals placed above H2 in the emf series will displace
the hydrogen from an acid solution.
Zn + H2 SO4 ZnSO4 + H2 EoZn = – 0.76 volt

Ag + H2SO4 No reaction EoAg = + 0.80 volt

Conductometric Titrations:

Many techniques re available in electrochemistry to determine the strength of a substance..A brief

account on the Conductometric titration is given in this section. The detection of the end point in the
titration of an analyte with a titrant by monitoring the change in the conductance of the solution is called
Conductometric titration. The principle involved in this titration is that electrical conductance depends upon
the number and mobility of the ions.
To obtain the accurate results, it is important to observe the following :
1. It is necessary to keep the temperature constant throughout the experiment.
2. In this type of titrations , the titrant should be 10 times stronger than the solution to be titrated
so that volume change is as little as possible.

a) Titration of Strong Acid against Strong Base (HCl vs. NaOH)

A known volume of the strong acid is placed in the conductivity cell and the
conductance is measured using a conductometer. Initially the conductance is high due to the presence of fast
moving H+ ions. When the strong base such as NaOH is added from the burette, the conductance will
decrease due to the replacement of fast moving H+ ion by the slow moving Na+ ion.Thus the conductance
will go on decreasing with increasing addition of the base until the acid has been completely neutralized.
Further addition of the base will introduce the fast moving OH- ions resulting in an increase in the
conductance. Thus after reaching a minimum value, the conductance will begin to increase with increasing
addition of NaOH.When conductance is plotted against the volume of sodium hydroxide added, two straight
lines will be obtained and the point of intersection of these lines indicates the equivalence point.

H+ + Cl- + Na+ + OH- → NaCl + H2O

CHAPTER: Electrochemistry 17

b) Titration of Mixture of acids against strong base

Electrolytic solution conducts electricity due to the presence of ions. Since specific conductance of
a solution is proportional to the concentration of each ions in the solution and conductance of the
solution can be measured during titration.

When the sodium hydroxide is added slowly from the burette to the solution in the beaker
(Mixture of acid), first the strong acid (HCl) gets neutralized. Since fast moving H+ ions are
replaced by slow moving Na+ ions, decrease in conductance take place until the end point is
reached.

HCl + NaOH NaCl + H2O

After the complete neutralization of all HCl, the neutralization of weak acid (CH3COOH )
starts.

CH3COOH + NaOH CH3COONa + H2O

Since CH3COONa is stronger electrolyte than CH3COOH, conductivity slowly increases

until all CH3COOH is completely neutralized. When the end point is reached, addition of NaOH
will cause sudden increase in the conductance. This is due to the presence of fast moving OH– ions.

The burette is filled with sodium hydroxide solution upto zero level. 20 ml of the given
mixture of acid (HCl & CH3COOH) is pipetted out into a clean 100 ml beaker and equal volume of
distilled water is added. The conductivity cell is connected to conductivity meter and immersed in
the solution in beaker. The conductance is noted. To this 1 ml portions of sodium hydroxide is
added from the burette and the conductance is noted for each addition. The titration is continued
until the first end point (A) is reached.
After the end point is reached, again NaOH is gradually added from the burette into the
solution in the beaker, which causes increase in the conductance. This increase in the conductance
is noted until the second end point (B) is reached. After the second end point, on further addition of
CHAPTER: Electrochemistry 18

NaOH, a sudden increase in conductance is observed. The reading is continuously measured for
each addition of NaOH and tabulated.
A graph is plotted between the volumes of NaOH vs conductivity. From the graph first (A)
and second (B) end points are noted. From the end point, the amount of HCl and CH3COOH
present in the whole of the mixture of acid solution can be calculated.

Fig: Mixture of acid Vs strong base

C) Titration of Sodium sulphate against Barium Chloride (Na2SO4 vs. BaCl2)

A known volume of the barium chloride is placed in the conductivity cell and
the conductance is measured using a conductometer. Initially the conductance is high due to the presence of
Ba2+ ions. When sodium sulphate is added from the burette, the conductance will decrease due to the
precipitation of Ba2+ ion by the slow moving Na+ ion.Thus the conductance will go on decreasing with
increasing addition of the base until the precipitate have been formed. Further addition of the sodium
sulphate will introduce the fast moving SO4 ions resulting in an increase in the conductance. Thus after
reaching a minimum value, the conductance will begin to increase with increasing addition of Na 2SO4
.When conductance is plotted against the volume of sodium Sulphate added, two straight lines will be
obtained and the point of intersection of these lines indicates the equivalence point.

BaCl2 + Na2SO4 → BaSO4 + 2NaCl

CHAPTER: Electrochemistry 19

Fig: Sodium sulphate Vs Barium chloride

Applications of conductometric titrations

1. Applicable to even coloured solutions without indicator.

2. Very low concentrations of solutions are enough.

3. The end point determined is accurate.

4. To estimate of a mixture of halides.

5. No special care is necessary near the end point as the end poiont is ascertained graphically.

Potentiometric Titration:
It is the Measurement of emf between reference electrode and an indicator electrode.

i) Redox titrations ( FeSO4 Vs K2Cr2O7)

A Known amount of FeSO4 solution is taken in a beaker and platinum electrode is inserted to it. It
is then connected to a calomel electrode to form a galvanic cell. The cell is then connected to the
potentiometer and its Ecell is determined. When it is titrated against the standard K2Cr2O7 solution taken in
the burette.

Cr2O7 2- + 6 Fe2+ +14 H+ 2Cr 3++6 Fe3+ +7H2O

The emf will increase first slowly, but in the equivalence point there will be a sudden increase in
potential. A more sensitive and satisfactory method of detecting the end point will be the graph of E/V
CHAPTER: Electrochemistry 20

against the volume of K2Cr2O7. The resulting curve rises to a maximum at the equivalent point, which is the
end point.

ii)Precipitation titration ( AgNO3 Vs NaCl)

A Known amount of AgNO3 solution is taken in a beaker and the indicator electrode (silver-silver ion
electrode) is placed in it. It is then connected to a reference electrode (calomel electrode) to form a galvanic
cell. The cell is connected to the potentiometer and its Ecell is determined.When the AgNO3 solution is
titrated against the standard NaCl solution, taken in the burette.The concentration of Ag+ ion goes on
decreasing and potential of indicator electrode goes on increasing continuously on the progressive addition
of NaCl.
AgNO3 + NaCl AgCl  + NaNO3
At the end point, emf suddenly decreases. After the end point there is no noticeable change in the
potential. When the emf is plotted against the volume of NaCl added, a curve is obtained. The end point is
the point where the slope of the curve is maximum. The graph E/V vs Volume of the NaCl is plotted as
above, to get the accurate end point.
Advantages of potentiometric titrations:
1) Cheap and easily available.
2) Used for coloured solution.
3) Fixing up end point is easier.
4) Very dilute solutions can be titrated with accuracy