ARMY PUBLIC SCHOOL GOPALPUR

SESSION( 2021-22)
CLASS- XII (SCIENCE)
SUB-Chemistry
CHAPTER-Electrochemistry
NOTES, ACTIVITIES and ASSIGNMENTS (2021)

1. Electrochemistry
Electrochemistry deals with the study of electrical properties of solutions
of electrolytes and with the interrelation of chemical phenomenon and ele
ctrical energies. Electrical energy is carried through matter in the
form of electric current with the help of suitable source and charge
carriers (ions or electrons).
2. Electrochemical Cell
A device that generates a potential difference between electrodes by chemical
reactions is called an electrochemical cell. It comprises two electron conductors
which are separated by an ionic conductor and are linked by an electron conductor.
The two metallic electrodes are dipped in the electrolytic solution.

Types Of Electrochemical Cell

Electrochemical cells are of two types. They are Galvanic cell and Electrolytic cell.
These are two fundamental types of electrochemical cell.

 Galvanic cell – In a galvanic cell, spontaneous redox reaction, the chemical

energy is converted into electrical energy. It is also called voltaic cell or
Daniel cell.
 Electrolytic cell – In an electrolytic cell, the nonspontaneous redox reaction is
carried out by electrical energy.

3. ELECTRO CHEMICAL CELL/GALVANAIC CELL/ VOLTAIC CELL :

Example – Daniel Cell

A cell in which the chemical energy is transformed into electrical energy.
The chemical reaction occuring in a galvanic cell is always a redox reaction.
During the chemical process, the reduction in free energy will obtain as a re
sult in the form of electrical energy.
  Principle of Galvanic (Voltaic) Cell
Electric work done by a galvanic cell is mainly due to the Gibbs energy of
spontaneous redox reaction in the voltaic cell. It generally consists of two half cells
and a salt bridge. Each half cell further consists of a metallic electrode dipped into
an electrolyte. These two half-cells are connected to a voltmeter and a switch
externally with the help of metallic wires. In some cases, when both
the electrodes are dipped in the same electrolyte, a salt bridge is not required.

 Parts of Galvanic Cell

 Anode – Oxidation occurs at this electrode.

 Cathode – Reduction occurs at this electrode.
 Salt bridge – Contains electrolytes which are required to complete the circuit
in a galvanic cell.
 Half-cells – reduction and oxidation reactions are separated into
compartments.
 External circuit – Conducts the flow of electrons between electrodes
 Load – A part of the circuit utilizes the electron to flow to perform its
function.

 Working of Galvanic Cell

 In a galvanic cell, when an electrode is exposed to the electrolyte at the

electrode-electrolyte interface, the atoms of the metal electrode have a
 tendency to generate ions in the electrolyte solution leaving behind the
electrons at the electrode. Thus, making the metal electrode negatively
charged.
 While at the same time metal ions in the electrolyte solution too, have a
tendency to deposit on a metal electrode. Thus, making the electrode
positively charged.
 Under equilibrium condition, charge separation is observed and depending on
the tendencies of two opposing reactions, the electrode can be positively or
negatively charged. Hence, a potential difference is developed between the
electrode and electrolyte.This potential difference is known as electrode
potential.
 Out of two electrodes, the electrode at which oxidation takes place is called
anode while the electrode at which reduction takes place is called cathode.
 The anode has a negative potential with respect to the solution while the
cathode has a positive potential with respect to the solution.
 Thus, a potential difference develops between two electrodes of the galvanic
cell. This potential difference is known as cell potential.
 When no current is drawn from the galvanic cell, cell potential is known as
the electromotive force of the galvanic cell.
 When the switch is set on, due to the potential difference, electrons flow from
the negative electrode to the positive electrode.

 Example of Galvanic Cell

Electrochemical or galvanic cells were introduced as a tool for studying the
thermodynamic properties of fused salts more than a century ago. Daniel’s cell is an
example of a galvanic cell that converts chemical energy into electrical energy. In
Daniel’s cell, copper ions are reduced at the cathode while zinc is oxidized at the
anode.
Reactions of Daniel cell at cathode and anode are:
At cathode: Cu 2+ + 2e– → Cu
At anode: Zn → Zn2+ + 2e–
4. ELECTROLY TIC CELL :
This cell converts electric energy into chemical energy. The entire assembly except
that of the external battery is known as the electrolytic cell.
 5. REPRESENTATION OF ELECTROCHEMICAL CELL :
Ex :
(i) Zn (s) | Zn2+ (aq) || Cu2+ (aq.) / Cu (s)
(ii) Pt/H2 (g) (1 atm)|H+ (aq) || Cu2+ (aq.) | Cu (s).
( Salt Bridge taken i.e Inert electrolyte KCl, KNO3 , NH4 Cl etc. with
Gelatin or Agar-Agar powder)
1. First of all, the anode is written.
2. After anode, the electrolyte of the anode should be written with its
concentration in the bracket..
3. A slash ( / ) is put between anode and electrolyte to denote the surface
barrier between the two as they exists in different phases.
4. Then we denote salt bridge by two vertical parallel lines. (II).
5. Then, we write the electrolyte of cathode (negative electrode) followed By
its concentration in bracket.
6. Finally, after a slash, we write the cathode.
7. In case of gas, the gas is to be indicated after the electrode in case of anode
and before the electrode in case of cathode.

8. ELECTRODE POTENTIAL :
When a strip of metal is brought in contact with the solution containing its own ions
then the strip of metal gets positively charged or negatively charged and results into
a potential being developed between the metallic strip and its solution which is
known as electrode potential.
At anode
M  M+n + ne— (Oxidation Potential)
At cathode
M+n + ne—  M (Reduction Potential)
  The value of electrode potential depends upon :
(1) the nature of electrode
(2) the concentration of solution
(3) the temperature
 Oxidation potential
The tendency to lose electrons in the above case is known as oxidation potential.
Oxidation potential of a half-cell is inversely proportional to the concentration of
ions in the solution.

 Reduction potential
The tendency to gain electrons in the above case is known as reduction potential.
According to IUPAC convention, the reduction potential alone be called as the
electrode potential unless it is specifically mentioned.
E°red = – E°oxidalion
It is not possible to determine the absolute value of electrode potential. For this a
reference electrode [NHE or SHE] is required. The electrode potential is only the
difference of potentials between two electrodes that we can measure by combining
them to give a complete cell.

 Standard electrode potent ial (E0) :

If the concentration of ions is unity, temperature is 25°C and pressure is 1 atm
(standard conditions), the potential of the electrode is called standard electrode
potential.
 The given value of electrode potential be regarded as reduction potential
unless it is specifically mentioned that it is an oxidation potential.

9. Electro motive force of cell or cell voltage or cell potential :

The difference in the electrode potentials of the two electrodes of the cell is termed
as electro motive force [EMF] or cell voltage.

Ecell = Ered (cathode) – Ered (anode)

Or Ecell = Eoxi.(anode) – Eoxi.(Cathode)
Or Ecell = Eoxi.(anode) + Ered(cathode)
10.Reference Electrode:
The electrode of known potential is called reference electrode. It may be primary
reference electrode like hydrogen electrode or secondary reference electrode like
calomel electrode.
 a) Standard hydrogen electrode (SHE)

Standard hydrogen electrode (SHE) also known as normal hydrogen electrode

(NHE), consists of platinum wire, carrying platinum foil coated with finely divided
platinum black. The wire is sealed into a glass tube. placed in beaker containing 1 M
HCl. The hydrogen gas at 1 atm pressure is bubbled through the solution at 298K.
Half-cell is pt H2 (1 atm) H+ (1 M)

In SHE. at the surface of plantinum, either of (he following reaction can take place

2H+(ag) + 2e– → H2G Reduction

H2(g) → 2H+(ag) + 2e– Oxidation
The electrode potential of SHE has been fixed as zero at all temperatures.

Its main drawbacks are:

1. It is difficult to maintain 1 atm pressure of H2 gas.

2. It is difficult to maintain H+ ion concentration 1 M.
3. The platinum electrode is easily poisoned by traces of impurities.

11.Nernst Equation:
With the help of Nernst equation, we can calculate the electrode potential of
electrode or EMF of cell.
The relationship between the concentration of ions and electrode potential is given
by Nernst equation.
Where,
E= Electrode potential at any temperature and concentration
E0 = Standard electrode potential
R = gas constant
T = temperature (in K)
F = Faraday (96500 coulomb mol–1)
n = no. of e– gained or loosed in balanced equation.

For a electrochemical cell,

NOTE:Concentration of pure solids and liquids is taken as unity.