ELECTROCHEMISTRY

Electrochemistry Branch of chemistry which deals with inter conversion of chemical energy into electrical enery

Non - conductor Substances which do not allow electric current to pass through them Example:-pure water, ice,
glass, rubber etc
Conductors Substances which allow electric current to flow through them Example:- Metals, Aqueous solution
of acids, bases and salts, fused salts and impure water etc.
Types of conductor Metallic Conductor And Electrolytic Conductor

Metallic conductor The conductors which conduct electric current by movement of electrons without undergoing any
chemicalchange are known as metallic conductors.
Metals (Cu,Ag,Fe,Al etc),
Electrolytic Substance which conduct electric current through its ions in aqueous solution or in its molten state
conductors :
Strong electrolyte Electrolytes which are completely ionized in aqueous solution or in their molten state, are called
strong electrolytes. Example – all salts, strong acid and strong base
Weak electrolyte : Electrolytes which are not completely ionized in aqueous solution or in their molten state, are
called weak electrolytes. Examples :- All carbonic acids (except sulphonic acid), CH3 COOH, HCN,
NH3 , amine, etc
Diffrance between
Metallic and
Electrolytic
Conductor

Resistance (R) : Metallic and electrolytic conductors obey ohm's law according to which the resistance of a
conductor is the ratio of the applied potential difference (V) to the current following(I).

Specific resistance The resistance (R) of a conductor of uniform cross section is directly proportional to its length()
() : and inversely proportional to its area of cross section (A)

Conductance (C) : It is the property by virtue of it favour the flow of electric current. The conductance of a conductor is
equal to reciprocal of resistance

Specific conductance It is defined as the reciprocal of specific resistance

() :
 ELECTROCHEMISTRY

Specific conductivity of a solution is defined as the conductance of one centimeter cube of the
solution of the electrolyte
Molar conductance It is defined as the conductance of all the ion produced by one mole of electrolyte present in given volume
of solution

Equivalent It is defined as the conductance of all the ion produced by one gram equivalent of the electrolyte
Conductance present in given volume of solution

Relation

Numerical Which of the following have maximum molar conductivity.

(i)0.08M solution and its specific conductivity is 2 × 10–2  cm–1.
(ii) 0.1M solution and its resistivity is 50  cm.
FACTORS INFLUENCING THE CONDUCTIVITY OF ELECTROLYTES
(a)Inter ionic If inter ionic attraction between solute is more, then the conductivity will be less.
attraction
( b ) Polarity of If the solvent is greater polarized then the ionization and conductivity will be more.
solvent
( c ) Viscosity of By increasing the viscosity of medium, the conductivity decreases
medium
(d ) Temperature As the temperature of electrolyte solution is increased, the conductivity increases because K.E. of
ions increases and all type of attraction forces decreases and the viscosity of medium decreases
( e ) Dilution : The degree of ionisation increases with the increase of dilution of the solution the conductivity is
increases due to increasing the number of ions
Effect of dilution on specific conductance : Specific conductance decreases with the increase of
dilution of the solution due to the presence of no. of ions in 1cm3 solution decreases
Effect of dilution on equivalent/molar conductivity : The equivalent/molar conductivity increases
with dilution. This is due to the fact that degree of ionisation increases with dilution.
Infinite dilution When the whole of the electrolyte has ionised, further addition of the water bring a small change
in the value of equivalent/molar conductance`
Degree of The ratio of equivalent conductivity at any dilution to equivalent conductivity at infinite dilution is
dissociation called conductivity ratio or degree of dissociation of solute
Determination of molar conductivity at infinite dilution

KOHLR AUSCH The equivalent /molar conductivity of any electrolyte at infinite dilution is the sum of ionic
LAW conductances of the cation and anion given by the electrolytes at infinite dilution

Application : Determine the equivalent conductivities of weak electrolytes at infinite dilution.

Calculate degree of dissociation

Calculate dissociation constant of weak electrolyte

Molar conductivity of weak electrolyte:-Calculate m for acetic acid.

 ELECTROCHEMISTRY
Given that 0m (HCl) = 426 S cm2 mol-1 0
m (NaCl) = 126 S cm2 mol-1
0 2 -1
m (CH3COONa) = 91 S cm mol

Solubility S and Ksp of sparingly soluble salt:-

ELECTROLYSIS :

FAR ADAY'S Faraday's first law of elecrolysis :

LAWS OF "The amount of a substance deposited or dissolved at an electrode is directly proportional to the
ELECTROLYSIS : charge passing through the electrolytes.

Faraday's second law : This law states that the amounts of different substances deposited at electrodes by
passage of the same quantity of electricity are proportional to their chemical equivalent(E).
W  E
W  It E
If W1 and W2 be the amounts of two different substances deposited at electrodes and E1 and E2
be the equivalent weights then - W1/ W2 = E1/ E2
ELECTRO Zn road dipped in 1M ZnSO4 solution act as anode(Oxidation takesplace) and Cu rod dipped in 1M CuSO4
CHEMICAL act as catode (Reduction takes place)both are connected with salt bridge. Current carrier inside cell are ion
CELL/GALVANAIC while in electric circuit are free electron
CELL/ VOLTAIC Zn/Zn+2 // Cu+2/ Cu
CELL Overall Reaction:- Zn + Cu+2  Zn+2 + Cu

Diagram and function

Electrode Potential The potential develop between Metal and its ion.
Standard Electrode The potential develop between metal electrode and the solution of its ion at 1M concentration at 1 bar
Potential (E0) pressure and 298 k is known as standred electrode potential.
Oxidation The electrode potential for oxidation half reaction M(s)-M+(aq) + ne-
 ELECTROCHEMISTRY
Potential(OP) Greater the O.P. greater will be the tendency to get oxidised

Reduction Potential The electrode potential for reduction half reaction M +(aq) + ne-  M(s)
Greater the R.P. greater will be the tendency to get reduced

Factor affecting Concentration of the solution Nature of the metal Pressure and temperature condition
electrode potential
Reference Electrode Primary Reference electrode(Standard hydrogen electrode)

Secondary reference
electrode:-

Cell Potential(E0Cell) E0Cell = E0Cathode-E0 Anode

Nernst Equation

Application of Nernst Calculation of electrode potential:-

Equation Mn+(aq) + ne-  M(s)

Calculation of PH of hydrogen electrode

2H+ + 2e- H2(g)
ERP = -0.0591 log[H+] ERP = -0.0591 PH EOP = +0.0591 PH
Calculation of EMF of cell or cell Voltage
Zn + Cu+2 Zn+2 + Cu

Prediction and feasibility of a cell reaction(ΔG is negative Or E cell =+ve then reaction would be
feasibile)
ΔG = -nE0cellF
Calculation of equilibrium constant
KC = R/P Ecell =0

Battery Primary Battery:-Elcetrochemical cell or Baterry which can not be charged

Secondary Battery:- Elcetrochemical cell or Baterry which can be charged
Cell Electrolyte Used Anode Reaction Cathode Reaction Remark
Dry Cell A moist paste of zinc container acts as anode carbon (graphite) rod Ammonia produced in
ammonium Zn(s) → Zn2+ + 2e– surrounded Powdered the reaction forms a
chloride (NH4 Cl) manganese dioxide and complex with Zn2+ to
and zinc chloride carbon give [Zn (NH3 )4 ]2+.
 ELECTROCHEMISTRY
(ZnCl2 ) MnO2 + NH4 + + e– →
MnO(OH) + NH3
Ni/Cd Battery KOH solution Cd rod act as anode Nickel oxide act as cathode Cd + 2NiO(OH)
Cd+2OH-Cd(OH)2 + 2e- NiO(OH) +H2O + 1e- +2H2O Cd(OH)2 +
2Ni(OH)2
Mercury Cell A paste of KOH zinc – mercury amalgam as A paste of HgO and carbon
and ZnO anode HgO + H2O + 2e– → Hg(l ) ZnO(s) + Hg(l)
Zn(Hg) + 2OH– → ZnO(s) + + 2OH– The overall reaction
H2O + 2e– does not involve any
ion in solution so Cell
potential is constant
through its life
Lead Storage A 38% solution of Pb grid packed with Lead Lead grid Packed with PbO Pb(s) + PbO2 (s) +
Cell sulphuric acid Pb(s) + SO42–(aq) → PbSO4 PbO2 (s) + SO42–(aq) + 4H+ 2H2SO4 (aq) →
(s) + 2e– (aq) + 2e– → PbSO4(s) + 2PbSO4 (s) + 2H2O(l)
2H2O (l )
Fuell Cell KOH solution Hydrogen are bubbled through Oxygen are bubbled through Overall Reaction
Fuel cells produce porous carbon electrodes porous carbon electrodes 2H2 (g) + O2 (g) → 2
electricity with an O2 (g) + 2H2O(l) + 4e–→ 2H2 (g) + 4OH– (aq) → H2O(l )
efficiency of 4OH– (aq) 4H2O(l) + 4e– Finely divided
about 70 % platinum or palladium
metal are incorporated
into the electrodes for
increasing the rate of
electrode reactions
Use Apollo space
programme
Corrosion Fe (s)→ Fe2+ (aq) +2e– O2 (g) + 4H+ (aq) +4e– → Atmospheric oxidation:
2H2O(l) 2Fe2+(aq) + 2H2O(l) +
½O2 (g) → Fe2O3 (s) +
4H+ (aq)

Question For Practice

ELECTROCHEMISTRY
ELECTROCHEMISTRY

Nernst Equation
ELECTROCHEMISTRY
 ELECTROCHEMISTRY

Faraday Laws:- Numerical

1. The time required to coat a metal surface of 80 cm2 with 0.005mm thick layer of silver (density = 10.5 g cm–3) with the passage
of 3A current through silver nitrate solution is –

2.The same current if passed through solution of silver nitrate and cupric salt connected in series. If the weight of silver
deposited is 1.08 g. Calculate the weight of copper deposited

Sol : According to faradays second law

ELECTROCHEMISTRY
ELECTROCHEMISTRY
ELECTROCHEMISTRY

DO YOURSELF
ELECTROCHEMISTRY