Chemistry XII Theory
Unit III: Electrochemistry 12
Redox reactions, EMF of a cell, standard electrode potential, Nernst equation and its application to
Periods
chemical cells, Relation between Gibbs energy change and EMF of a cell, conductance in electrolytic
solutions, specific and molar conductivity, variations of conductivity with concentration,
Kohlrausch's Law, electrolysis and law of electrolysis (elementary idea), dry cell-electrolytic cells and
Galvanic cells, lead accumulator, fuel cells, corrosion.
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.
Importance of Electrochemistry
Metals Production
Electroplating
Purification of metals
Batteries and cells
Creating new technologies that are eco-friendly
Medical and communication
Important Terms:
Electrochemical Cells
An electrochemical cell is a device used for the
interconversion of electrical and chemical energy.
An electrochemical cell contains two electrodes
(cathode and anode) and an electrolyte.
Galvanic cell (voltaic cell)
Types of Electrochemical cell.
Convert chemical energy into electrical energy.
Electrolytic cell (Faradaic cell)
Types of Electrochemical cell.
Convert electrical energy into chemical energy
Salt Bridge
It is an electrolyte material that is used to connect
the two sides of an electrochemical cell to
maintain electrical neutrality by allowing the flow
of ions between the two half-cells.
Salt bridge prevents charge build up and sustains
the cell's operation.
Electrode potential
A potential difference develops between the
electrode and the electrolyte.
Standard 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.
Anode
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.
Cathode
In a galvanic cell, the half-cell in which reduction
takes place is called cathode and it has a positive
potential with respect to the solution.
Cell potential
Difference between the electrode potentials
(reduction potentials) of the cathode and anode.
Cell electromotive force (emf)
Emf of a cell is the potential difference between its
two electrodes when no current flow.
Nernst Equation for a general
electrochemical reaction
Relationship between temperature and
reactant/product concentrations.
Nernst Equation for Electrode
Potential
Nernst Equation for Cell emf
Equilibrium Constant (Kc)
log Kc= nFE0(cell)/ 2.303 RT
ΔG0 = Wmax =–nFE0 Gibb’s Free Energy (Gibbs Energy)
ΔG= ΔH-TΔS The maximum amount of work that a cell in its
standard state can perform.
Conductance of Electrolytic The phenomenon of conduction of current
through a solution is called electrolytic conduction.
Solutions
Electrolytes The chemical substances whose aqueous solutions
conduct electricity are called electrolytes.
Non Electrolytes The chemical substances whose aqueous solutions
do not conduct current are called as non
electrolytes.
Conductance (G)
Conductance is the property of material by virtue of
which it favours flow of current.
[unit of G is mho or ohm–1 or Siemens (S)]
Resistance (R)
Resistance is the property of material by virtue of
which it oppose the flow of current.
Molar conductivity
Conducting power of all the ions furnished by one
mole of an electrolyte in a solution of specified
concentration.
Wheatstone bridge
A Wheatstone bridge is an electrical circuit used to
measure an unknown electrical resistance.
Electrolytic/Ionic conductance The conductance of electricity by ions present in the
solutions.
Conductivity cell
Used to measure the conductance of electrolyte.
Limiting molar conductivity (ʌ°m )
The concentration decreases upon dilution.
Upon dilution when the concentration approaches
zero, the molar conductivity of the solution is
known as limiting molar conductivity.
Kohlrausch law of independent
migration of ions Limiting molar conductivity
ʌ° m(NaCl) = λo Na+ + λo Cl- of an electrolyte can be represented as the sum of
the individual contributions of the anion and cation
of the electrolyte.
w∞Q Faraday’s First Laws of Electrolysis
Q=It Mass of a substance liberated during electrolysis is
directly proportional to the quantity of electricity
w=zIt passed through the electrolyte taken as a solution
or as melt.
Faraday’s Second Laws of Electrolysis
The amount of substances liberated or deposited
at electrode (anode or cathode) when the same
quantity of electricity passing through the
electrolytic solution are proportional to their
chemical equivalent weights.
Discharge potential or Decomposition
potential
Minimum potential required for any
electrochemical processes to occur.
Batteries
Combination of two or more cells.
Primary Batteries (Leclanche cell)
The reaction occurs only once and after use battery
becomes dead and cannot be reused again.
Commonly used in transistors and clocks.
Secondary Batteries
After use they can be recharged by passing current
through it and can be used again.
Commonly used in automobiles and invertors.
Fuel cells (Galvanic cells)
Convert the energy of combustion of fuels like
hydrogen, methane, methanol, etc. directly into
electrical energy.
Corrosion
In corrosion a metal gets oxidised by loss of
electrons to oxygen and formation of oxides.
Hydrogen Economy
Hydrogen is another proposed alternative source
of energy.
