REFERENCE ELECTRODE

The reference electrode is an electrode whose potential is arbitrarily taken as

zero or whose potential is exactly known

Types

a) Primary reference electrode

The reference electrodes whose potential is arbitrarily taken as zero are known
as Primary reference electrode

Eg: standard hydrogen electrode (SHE)

b) Secondary reference electrode

The reference electrodes whose potential is NOT zero BUT EXACTLY KNOWN,
and the electrode potential value depends on the concentration of solution in
which it is dipped

Eg: calomel electrode

STANDARD HYDROGEN ELECTRODE

CONSTRUCTION

It consisting of rectangular platinum foil, which is coated with platinum black

A platinum wire is connected to the platinum foil through mercury
This platinum wire is used for external connection and glass tube is enclosed in
the outer jacket
The outer jacket having an inlet at the top and two holes at bottom, which are
exactly at the middle of the platinum foil
The entire arrangement is dipped in the 1.0MHCl
Cell representation: Pt/H2(g)/H+(aq)

EH= - 0.0591pH

The magnitude of SHE potential is considered to be zero

CALOMEL ELECTRODE CONSTRUCTION

The electrode vessel consists of a glass tube having a side tube on both the
sides
A layer of mercury is placed at the bottom of the tube
A platinum wire sealed into glass tube dips in mercury and serves to make
electrical contact of the electrode with the circuit
Above the mercury layer, a paste prepared by grinding calomel (solid
mercurous chloride) with a few drops of mercury and some KCl solution is
placed
The whole vessel is then filled with KCl solution
The concentration of the solution is either 0.1M, 1M or fully saturated
The KCl solution also fills the side tube

Cell representation : Pt; Hg/Hg2Cl2(s)/KCl(satd)

QUINHYDRONE ELECTRODE

This is an oxidation reduction electrode

It is prepared by dissolving quinhydrone in an aqueous solution containing
Hydrogen ions
On dissolving , it decomposes into an equimolar mixture of quinone and
hydroquinone which are oxidised and reduced forms
The potential developed in solution is picked up by dipping a platinum wire
into it

EQ= EQ0-0.0591pH

Electrode potential of this depends on the pH of the solution

The electrode is represented as : Pt/Q, QH2, H+ (aq)

ADVANTAGES OF QUINHYDRONE ELECTRODE

• Very easy and convenient to setup

• Presence of impurities and oxidising agents will not affect the electrode
reaction
So it can be used for the solutions containing impurities
• The indicated pH values are accurate
• a good substitute for hydrogen electrode

LIMITATIONS OF QUINHYDRONE ELECTRODE

 The electrode is suitable for the solution of pH less than 8 because

higher pH value
affect the electrode reaction
 It cannot be used for solutions of proteins or higher concentrations of
salts
 cannot be used with solutions that contain a strong oxidising or reducing
agent
 Cannot be used with MnO2, aniline, Fe2+ etc which reacts with quinone
or hydroquinone

DETERMINATION OF pH OF A SOLUTION USING QUINHYDRONE ELECTRODE

GLASS ELECTRODE

Potential difference develops across a glass membrane when it separates two

solutions of different pH

The magnitude of this potential difference for a given variety of glass varies
with the concentration of hydrogen ions

CONSTRUCTION
Glass electrode has bulb made up of thin glass membrane
Bulb is filled with HCl solution
Ag/AgCl wire or Pt wire is dipped in HCl solution
the glass electrode is dipped in a solution containing H+ ions
Working:

• the glass electrode is dipped in a solution containing H+ ions

• The electrode potential depends potential at glass junction
• Since the solution inside the bulb remains the same, Ag/AgCl electrode
potential remains constant and potential at the junction depends only
on the pH of the solution outside
• The potential of the electrode is given by the formula

EG = EG0 - 0.0591pH

EG0 is constant for the given glass electrode

ADVANTAGES OF GLASS ELECTRODE

o The electrode will not be affected by the presence of impurities ie

oxidising or reducing agents in the solution
o Can be used even in the presence of catalytic poisons
o Easy to set up and simple to operate
o Small quantities of solutions are sufficient

LIMITATIONS OF GLASS ELECTRODE

1. With ordinary glass electrode, pH only upto 9 can be measured,

with special kind of glass electrode pH only upto 12 can be measured
2. It cannot be used for solutions containing F- ions because F- ions attack
glass
 DETERMINATION OF pH OF A SOLUTION USING GLASS ELECTRODE

CONCENTRATION CELL

In CONCENTRATION CELL EMF arises due to transfer of matter from one half
cell to the other because of a difference of concentration between the two .
Such cells are called concentration cells

DEFINITION: a concentration cell is a electrochemical device where both

anode and cathode are made up of same metal and are in contact with same
electrolyte but of different concentration

Two types
1. Electrode concentration cell
2. Electrolyte concentration cell
 1.Electrode concentration cell

2.Electrolyte concentration cell

Concentration cell is function of concentration ratio . So as the concentration

difference is higher, higher the cell potential
What is Solubility?

Solubility is the property of a substance to dissolve in a solvent.

What is Solubility Product?

Solubility product is the mathematical derivation that shows the equilibrium

between dissolved and undissolved species of a substance in a solvent.
Therefore, it represents the level at which a solute dissolves in a solution.

Significance: smaller the solubility product of a substance, lower is its solubility

DETERMINATION OF SOLUBILITY PRODUCT OF A SPARINGLY SOLUBLE SALT

(E.g AgCl)
But the concentration of a saturated solution is equal to the solubility (s)

C2 is the concentration of Ag+ ions in AgNO3 solution = 0.001 N

E.M.F of the cell is measured and it is found to be 0.1182 V
Eqn (2) can be written as
POTENTIOMETRIC TITRATION

Types of potentiometric titration

• Acid base titration
 Redox titration
• Complexometric titration
• Precipitation titration

OXIDATION-REDUCTION TITRATION
POTENTIOMETRIC TITRATION INVOLVING ONLY REDOX SYSTEMS. Example:
Fe2+/Fe3+.

Apparatus:

Principle:

o the oxidation –reduction electrode , Pt/ Fe2+/Fe3+ is set up by dipping a

platinum electrode into a known volume of the given ferrous sulphate
solution
o This electrode is combined with a calomel electrode to obtain the
experimental cell represented as follows:
Saturated calomel electrode // Fe3+, Fe2+ / Pt

The E.M.F of the cell is given by the expression (Nernst equation)

PROCEDURE

• A known volume of ferrous sulphate solution is pipetted out into a

beaker
• Equal volume of dilute sulphuric acid is added
• A platinum wire is dipped into the solution to pick up the potential
• This is the experimental redox elctrode . This is combined with a
saturated calomel electrode
• The resulting cell is the experimental cell .The E.M.F of this cell is noted
 • Dichromate solution is added to ferrous sulphate solution from a burette
and after each addition the E.M.F noted. As the end point is approached
the E.M.F changes faster
• Hence dichromate is added in smaller quantities towards the end point
• After the equivalence point, two more readings are taken, in each case,
the ratio
of ΔE/ ΔV is calculated
• A graph of ΔE/ ΔV versus volume of dichromate added is drawn
• The peak in the graph corresponds to the endpoint.
• From the titre value, strength of the given ferrous salt solution can be
calculated