Class XII
Chemistry
Unit-2
Electrochemistry
Electrochemistry is the study of production of electricity from energy released during
spontaneous chemical reactions and the use of electrical energy to bring about
non-spontaneous chemical transformations.
Electrochemical Cell
The device or cell that converts the chemical energy
liberated during the redox reaction to electrical energy or
use electrical energy to carry out non-spontaneous
chemical reactions
GALVANIC CELL ELECTROLYTIC CELL
cell converts the chemical energy device for using electrical energy to
liberated during the redox reaction carry non-spontaneous chemical
to electrical energy reactions.
Galvanic Cells
Daniell cell
Anode- Oxidation takes place and negatively charged or –ve terminal
Cathode-reduction takes place & positively charged or +ve terminal
Direction of flow of electron- from –ve to +ve
terminal
Direction of current- from +ve to –ve terminal
• ELECTRODE POTENTIAL- When there is an equilibrium between metal atoms and its ions , a charge
separation takes place, this results in a potential difference. And depending on the tendencies of the two
opposing reactions, the electrode may be positively or negatively charged with respect to the solution
• A potential difference between the electrode and the electrolyte is called electrode potential.
• When the concentrations of all the species involved in a half-cell is unity then the electrode potential is known as
STANDARD ELECTRODE POTENTIAL.
• According to IUPAC convention, standard reduction potentials are now called standard electrode potentials.
• In a galvanic cell, the half-cell in which oxidation takes place is called anode and it has a negative potential
with respect to the solution.
• The other half-cell in which reduction takes place is called cathode and it has a positive potential with respect
to the solution.
• Thus, there exists a potential difference between the two electrodes and as soon as the switch is in the on
position the electrons flow from negative electrode to positive electrode.
Standard Hydrogen Electrode
Measurement of Electrode Potential
• The potential of individual half-cell (Electrode) cannot be measured because neither the oxidation nor
the reduction reaction can occur by itself.
• We can measure only the difference between the two half-cell potentials that gives the emf of the cell.
• If we arbitrarily choose the potential of one electrode (half-cell) then that of the other can be
determined with respect to this.
• The electrode whose electrode potential is known is referred as Reference Electrode.
• SHE is used as Reference Electrode as its standard electrode potential is taken as Zero.
• To measure the electrode potential of an unknown electrode, construct a Galvanic cell using unknown
electrode and SHE, and determine its cell potential or emf.
• From emf of the cell, the reduction potential (Standard electrode potential) of the other half-cell
(unknown) can be determined.
Measurement of Electrode Potential
Electrochemical series
The standard electrode
potential decreases from
top to bottom and with
this, decreases the
oxidizing power of the
species on the left and
increases the reducing
power of the species on
the right hand side of
the reaction
• Lithium has the lowest electrode potential indicating
that lithium ion is the weakest oxidising agent while
lithium metal is the most powerful reducing agent in an
aqueous solution
• If the standard electrode potential of an electrode is
greater than zero then its reduced form is more stable
compared to hydrogen gas.
• Similarly, if the standard electrode potential is negative
then hydrogen gas is more stable than the reduced
form of the species.
• Electrochemical cells are extensively used for
determining the pH of solutions, solubility product,
equilibrium constant and other thermodynamic
properties and for potentiometric titrations.
Nernst Equation:-
By converting the natural logarithm to the base 10 and
substituting the values of R, F and T = 298 K
By converting the natural logarithm to the base 10 and substituting the values of R, F and T = 298 K, n=2
for the following cell
The Nernst equation can be written as
and for a general electrochemical reaction of the type:
Nernst equation can be written as:
Equilibrium Constant from Nernst Equation
Electrochemical Cell and Gibbs Energy of the Reaction
Intensive
property:-not
depend on the
amount of matter
Gibbs Energy
and Equilibrium
constant
ELECTROCHEMISTRY- NUMERICAL PROBLEMS BASED ON NERNST EQUATION
For memorising:-
Example
Solution
Example:-
Example:-
Anti-log table
Example
Solution
Example:-
Solution:-
Conductance of Electrolytic Solutions
• Electrical conductance through metals is called metallic or electronic conductance and is due to
the movement of electrons.
• The electronic conductance depends on
(i) the nature and structure of the metal
(ii) the number of valence electrons per atom
(iii) temperature (it decreases with increase of temperature).
• The conductance of electricity by ions present in the solutions is called electrolytic or ionic conductance.
• The conductivity of electrolytic (ionic) solutions depends on:
(i) the nature of the electrolyte added
(ii) size of the ions produced and their solvation
(iii) the nature of the solvent and its viscosity
(iv) concentration of the electrolyte
(v) temperature (it increases with the increase of temperature).
Differences between Electronic and Electrolytic conduction
S.No Electronic conduction Electrolytic conduction
.
1. It is due to the flow electrons It is due to the flow of ions
2. It involves no chemical It involves chemical changes
change
3. There is no transfer of matter It involves transfer of matter
4. It decreases with increase in It increases with increase in
temperature temperature
Measurement of the Conductivity of Ionic Solutions
• Measurement of an unknown resistance can be performed on a Wheatstone bridge.
• However, for measuring the resistance of an ionic solution we face two problems.
• Firstly, passing direct current (DC) changes the composition of the solution.
• Secondly, a solution cannot be connected to the bridge like a metallic wire or
other solid conductor.
• The first difficulty is resolved by using an alternating current (AC) source of power.
• The second problem is solved by using a specially designed vessel called
conductivity cell.
conductivity cell:-
Two different types of conductivity cells
Measurement of cell constant:-
Wheatstone bridge:-
Example:-
• Resistance of a conductivity cell filled with 0.1 mol / L KCl solution is 100 Ω . If the resistance of the same
cell when filled with 0.02 mol /L KCl solution is 520 Ω , calculate the conductivity and molar conductivity of
0.02 mol /L KCl solution. The conductivity of 0.1 mol /L KCl solution is 1.29 S/m.
Class XII Chemistry
Unit-3
Electrochemistry
Variation of Conductivity and Molar Conductivity with Concentration &
Kohlrausch law of independent migration of ions
Variation of Conductivity and Molar Conductivity with Concentration:-
Class XII Chemistry
Unit-3
Electrochemistry
Electrolytic Cells and Electrolysis
Faraday’s Laws of Electrolysis
Electrolytic Cells and Electrolysis:-
Faraday’s Laws of Electrolysis:-
Faraday’s Laws of Electrolysis:-
Class XII Chemistry
Unit-3
Electrochemistry
Products of Electrolysis
Differences between Galvanic cell and Electrolytic cell
Products of Electrolysis:-
Products of electrolysis depend on
• The nature of material being electrolyzed,
• The type of electrodes being used. If the electrode is inert (e.g., platinum or gold), it does not
participate in the chemical reaction and acts only as source or sink for electrons. On the other hand, if
the electrode is reactive, it participates in the electrode reaction. Thus, the products of electrolysis
may be different for reactive and inert electrodes.
• The different oxidizing and reducing species present in the electrolytic cell and their standard electrode
potentials.
• Some processes are electrochemically and thermodynamically feasible, but kinetically very slow .At lower
voltages these do not seem to take place and extra potential (called over potential) has to be applied, which
makes such process more difficult to occur.
• The concentration of electrolytes.
Differences between Galvanic Cell and Electrolytic Cell
Galvanic Cell Electrolytic Cell
1. Electrical energy is produced 1. Electrical energy is consumed
2. Reaction taking place is spontaneous 2. Reaction taking place is
non-spontaneous
3. The two half cells are set up in 3. Both the electrodes are placed in the
different containers and are connected solution or molten electrolyte in the
through salt bridge or porous partition same container
4. Anode is negative and cathode is 4. Anode is positive and cathode is
positive negative
5. The electrons move from anode to 5. The electrons are supplied by the
cathode in external circuit external source. They enter through
cathode and come out through anode.
When Eext > 1.1 V
When Eext = 1.1 V (i) Electrons flow from Cu
(i) No flow of electrons to Zn and current flows
or current. from Zn to Cu.
(ii) No chemical (ii) Zinc is deposited at
reaction. the zinc electrode and
copper dissolves at
copper electrode.
Batteries
• Any battery (actually it may have one or more than one cell connected in series) or cell that we use as a
source of electrical energy is basically a galvanic cell where the chemical energy of the redox reaction
is converted into electrical energy.
• However, for a battery to be of practical use it should be reasonably light, compact and its voltage
should not vary appreciably during its use.
• There are mainly two types of batteries.
• Primary Batteries:-In the primary batteries, the reaction occurs only once and after use over a period of
time battery becomes dead and cannot be reused again. E.g. dry cell (known as Leclanche cell), mercury cell
• Secondary Batteries:-A secondary cell or battery after use can be recharged by passing current through it in
the opposite direction so that it can be used again. E.g. lead storage battery, nickel-cadmium cell
Lead storage battery :-
• It is an example of secondary battery.
• commonly used in automobiles and invertors.
• It consists of a lead anode and a grid of lead packed
with lead dioxide (PbO2 ) as cathode.
• A 38% solution of sulphuric acid is used as an
electrolyte.
Nickel-cadmium cell:-
• It is also a secondary cell
• It has longer life than the lead storage cell but more
expensive to manufacture.
• The overall reaction during discharge is:
Cd (s) + 2Ni(OH)3 (s) → CdO (s) + 2Ni(OH)2 (s) + H2O (l )
Fuel Cells:-
• Galvanic cells that are designed to convert the energy of combustion of fuels like hydrogen,
methane, methanol, etc. directly into electrical energy are called fuel cells.
• Example Hydrogen-oxygen fuel cell.
• The cell was used for providing electrical power in the Apollo space programme.
• The water vapours produced during the reaction were condensed and added to the drinking water supply
for the astronauts.
• Hydrogen-oxygen fuel cell.
Electrode- porous carbon
Anode: Hydrogen gas is bubbled
Cathode:-Oxygen gas is bubbled
Electrolyte: concentrated aqueous sodium hydroxide
Catalyst :- finely divided platinum or palladium metal
Advantages :-
• The cell runs continuously as long as the reactants are supplied.
• Fuel cells produce electricity with an efficiency of about 70 % compared to thermal plants whose
efficiency is about 40%.
• Fuel cells are pollution free
Corrosion:-
• Electrochemical theory of Rusting
Prevention of corrosion :-
• One of the simplest methods of preventing corrosion is to prevent the surface of the metallic object
to come in contact with atmosphere.
• This can be done by covering the surface with paint or by some chemicals (e.g. bisphenol).
• Another simple method is to cover the surface by other metals (Sn, Zn, etc.) that are inert or react to
save the object.
• Galvanization:- Coating of Zn over Iron.
• An electrochemical method is to provide a sacrificial electrode of another metal (like Mg, Zn, etc.)
which corrodes itself but saves the object.
