ELECTROCHEMISTRY

* An electrochemical cell or a galvanic cell or voltaic cell is a device used to convert chemical energy
produced in a redox reaction into electrical energy.

* A redox reaction consists of two half reactions called oxidation half reaction and reduction half
reaction.

Zn+CuSO4 ZnSO4+Cu is made up of two half reactions.

Zn Zn2++2e- :-Oxidation half reaction

Cu2++2e- Cu: - Reduction half reaction

* Salt Bridge is a U-Shaped tube containing concentrated solution of an electrolyte like KCl, KNO3,
K2SO4, etc or solidified solution of such an electrolyte in agar-agar.

* Function of salt bridge is to complete the inner circuit by flow of ions and to maintain electrical
neutrality in the solution of half cells.

* In electrochemical cell the electrode on which oxidation takes place is called anode (or negative pole)
and electrode on which reduction takes place is called cathode (or positive pole).

*The cell based on the redox reaction

Zn+CuSO4 ZnSO4+Cu is called Daniel cell.

ELECTROCHEMICAL CELL: -- Convert chemical energy produced in redox reaction to electrical

energy.

NOTE: - KCl, NaCl, NH4Cl in salt bridge of a electrode.

ELECTROLYTIC CELL: - Electrical energy is passed to bring about redox reaction.

REPRESENTATION OF CELL

Metal/ Metal ion (conc)// Metal ion(conc)/ Metal

Anode:-Oxidation occurs (left).

Cathode: - Reduction occurs (right).

Zn+Cu2 +
Zn2++Cu

Zn/ Zn2+(c1) // Cu2+(c2)/ Cu

Electrode Potential: - The tendency of an

electrode to lose or gain electrons when it is in contact with solution of its own ions.

Tendency to lose electrons - Oxidation Potential

Tendency to gain electrons- Reduction Potential.

STANDARD ELECTRODE POTENTIAL

If standard condition are used ie, temp=298K, concentration =1M, pressure=1atm, the electrode Potential
is called standard electrode Potential.
Need of a reference electrode:- Absolute value of electrode potential cannot be determined because
Oxidation or Reduction half life reaction cannot occur alone. Therefore a reference electrode is required.

NORMAL HYDROGEN ELECTRODE [NHE]. (REFERENCE ELECTRODE)

The standard electrode Potential is taken as zero. It is

represented as

Pt, H2 (1atm)/H+ (1M)

EMF or cell Potential is difference between electrode

Potentials of half cells.

Ecell= Eright - Eleft OR Ecell= Ereduction - Eoxidation

ELECTROCHEMICAL SERIES:-

It is the arrangement of electrodes in the order of increasing

reduction Potentials (standard electrode Potentials).

Variation of Conductivity and molar conductivity with concentration

Conductivity decreases with dilution (decrease in concentration)-for both Strong and Weak electrolyte.

Reason – Number of ions per unit volume that carry the current in a solution decreases on dilution.

Molar Conductivity:-increases with dilution (decrease in concentration).

Reason-Volume of solution containing one mole of electrolyte also increases.

λ =K V.

K decreases with volume increases.

Decrease in K is more than compensated by increase in volume.

Variation of λ is different for Strong and Weak electrolytes.

For strong electrolyte Λ increases slowly with dilution because inter ionic
attraction decreases with dilution.

If λ is plotted against c1/2 a straight line is retained with intercept λ0 and

slope=-A

λ = λ0-Ac1/2. λ0 is called molar conductivity at infinite dilution.

Weak electrolyte:- λ increases steeply on dilution.

Reason- for weak electrolytes change in Λ with dilution is due to increase in the
number of ions, in total volume of solution that contains 1 mole of electrolytes.

λ0 for weak electrolyte is obtained by Kohlrausch’s law of independent

migration of ions.

Kohlrausch’s law states that molar conductivity of an electrolyte at infinite

dilution is the sum of ionic conductivities of cation and anions each multiplied
by number of ions in one formula unit of electrolyte.
Eg.:- for Ax, By

λom = x λoA +y λoB

Applications of Kohlrausch’s law:-

1) To calculate Λ0 of weak electrolytes.

Eg :- Λ0 CH3COOH= Λ0CH3COONa + Λ0HCl - Λ0NaCl.

2) To calculate degree of dissociation, α

α= Λc/ Λ0 =molar conductivity at conc C/molar conductivity at infinite dilution.

Batteries

Primary cells:- These are the cells which can be recharged.

Eg :- dry cell, Mercury cell.

Secondary cells:- the cells which can be recharged.

Eg :- Lead storage battery & Ni-Cd cell.

Dry cell - Potential=1.5 V

Anode = Zinc container

Cathode = graphite rod surrounded by MnO2 and C.

Electrolyte = NH4Cl + ZnCl2 .

Result – Anode = Zn0 Zn2+ + 2e-.

Cathode = MnO2 + NH4+ + e- MnO(OH) + NH3

NH3 gas forms complex with Zn2+ to form [Zn(NH3)4]2+.

Mercury cell - Potential = 1.35 V (Potential remains

constant)

Anode = Zn-Hg amalgam

Cathode = HgO + C paste.

Electrolyte = KOH + ZnO

Result – Anode= Zn(Hg) + 2OH- ZnO(s) + H2O + 2e-.

Cathode = HgO + H2O + 2e- Hg + 2OH-

Overall Reaction = Zn(Hg) + HgO(s) ZnO(s) + Hg. (Concentration of ion does not change. )
Secondary Batteries

Lead storage battery

Discharging

Anode = Lead

Cathode = grid of Lead packed with PbO2

Electrolyte = 38% H2SO4 .solution.

At Anode = Pb(s) + SO42-(aq) PbSO4(s) + 2e-

At Cathode = PbO2(s) + SO42-(aq) + 4H+(aq) + 2e-

PbSO4(s) + 2H2O

Overall reacn = Pb(s) + PbO2(s) + 4H+(aq) + 2 SO42-(aq) 2 PbSO4(s) + 2H2O.

During the reaction of cell concn of H2So4 decreases as sulphate and hydrogen ions are consumed to form
PbSO4 + H2O.

Recharging

Recharging reverses the flow of current resulting in the formation of Pb on anode and PbO 2 on cathode.

At Anode = PbSO4 + 2e- Pb + SO42-

At Cathode = PbSO4(s) + 2H2O PbO2(s) + SO42- + 4H+ + 2e-

Overall reaction = 2 PbSO4(s) + 2H2O Pb + PbO2+ 4H++ 2 SO42-.

Nickel – Cadmium cell

Anode = Cadmium

Cathode = metal grid containing Nickel(IV)oxide

Electrolytes = KOH

At anode = Cd + 2OH- Cd(OH)2 + 2e-

At cathode = NiO2 + 2H2O + 2e- Ni(OH)2 +

2OH-

Fuel cells

These cells are those in which energy produced from

Combustion of fuels can be converted to electrical energy.

Eg :- H2-O2 fuel cell.

In the cell hydrogen and oxygen are bubbled through porous Carbon electrodes into concentrated
aqueous NaOH solution.

At cathode = O2 + H2O + 4e- 4OH-

At anode = 2h2 + 3OH- 4H2O + 4e-

Overall reaction = 2H2 + O2 2H2O

Corrosion

The process of change of metal surface into salts like

oxides, sulphides, carbonates etc.

Due to attack of atmospheric gases.

Rust is hydrated ferric oxide (Fe2O3.xH2O)

Rusting of iron occurs in the presence of air and water.

Chemistry of corrosion

H2O + CO2 H2CO3

H2CO3 2H+ + CO32-

At cathodic site = H+ + e- H

4H + O2 2H2O

At anodic site = Fe 2Fe2+ + 2e-

4Fe2+ + O2 + 4H2O 2 Fe2O3 + 8H+

Electrolysis

Electrolysis is the process of decomposition of an electrolyte by passage of electricity through its aqueous
solution or molten state.

Electrode connected to +ve pole of battery is anode and electrode connected to –ve is cathode.

Faradays Laws
1st law :- weight of any substance deposited at any electrode is proportional to quantity of electricity
passed.

W = ZQ

Q=It

W= weight of substance deposited / liberated , Q = electricity, I = current , t =seconds, Z =

electrochemical equivalent.

2nd law :- When same quantity of electricity is passed through solution of different electrolytes the
weights of substance deposited are directly proportional to their chemical equivalents weights.

One Faraday is the quantity of charge carried by one male of electron.

... 1F = 6.02 1.6023 10-19 Coulombs

= 96500 Coulombs.

i.e, Mn+ + ne- M

‘ n’ Faradays of electricity will deposit 1mol of M.

Resistance R= l/A ( = resistivity)

1/R = G (conductance)

... G = A/ l

K = 1/ (kappa) = conductivity.

Cell constant (G*) = l/A

K = G*/R

PREDICTING PRODUCTS OF ELLECTROLYSIS

*When aq. Solution of electrolyte is electrolysed.

*If cations have higher reduction potential than water cation is liberated at cathode, otherwise H 2 is
liberated by reduction of water.

*If anion has higher oxidation potential than water anion is liberated at anode otherwise O 2 due to
oxidation of water.

1. ELECTROLYSIS OF MOLTEN NaCl

Cathode Na++e- Na

Anode Cl- Cl +e-

Cl + Cl Cl 2

Overall 2 NaCl 2Na+ Cl 2

2. ELECTROLYSIS OF aq. NaCl

Cathode 2H2O+2e- 2OH- + H2

Anode 2Cl- Cl2 +2e-

Overall 2Cl-+2H2O 2OH-+ H2+ Cl2

OR

2Na++2Cl-+2H2O 2Na+ + 2OH- + H2+ Cl2

3. ELECTROLYSIS OF aq. CuSO4 solution- Pt Electrode

Cathode Cu2+ +2e - Cu(s)

Anode 2H2O 4H+ + O2 + 4e-

Overall 2Cu2++2H2O 2Cu+ 4H+ + O2

OR

2Cu2++2SO42- + 2H2O 2Cu+ 4H+ +2SO42- + O2

4. ELECTROLYSIS OF CuSO4 Using Cu Electrode

Cathode Cu2+ +2e- Cu

Anode Cu Cu2+ +2e-

NET RESULT:- Copper deposited at cathode from solution Eqt. Amount of Cu from anode dissolve into
solution.

To predict whether metal can liberate hydrogen from Acids

* Metals with- Eo values (negative reduction potential) can liberate hydrogen from Acids.

Since hydrogen will have greater tendency to get reduced (accept electron) metals lose electrons.

Example: - Zn, Mg, Ni can liberate hydrogen from HCl, H 2SO4 etc. but Cu & Ag etc can not.

PREDICTING FEASIBILITY OF THE REACTION

A redox reaction is feasible only if species with lower reduction potential is oxidised ie, loses electrons.

Example: - Cu + ZnSO4 CuSO4+ Zn

Cu/ Cu2+// Zn2+/ Zn

Zn2+/ Zn= -0.76V

Cu/ Cu2+=0.34V

Eo cell = Eright -Eleft

= -0.76-(+0.34)
 = -1.1 V Reaction not feasible.

Nernest Equation:
Equilibrium Constant From Nernst Equation

Electro-Chemical Cell and Gibbs Energy of Reaction