Module - 1

ELECTROCHEMISTRY
&
CORROSION
Electrochemistry

Electrochemical
cell

Electrolytic
cell
 Electrolytic cell Electrical energy

Electrolysis- Process of decomposition of an electrolyte by

the passage of electricity
Chemical energy
Electrolysis of molten NaCl using inert Pt electrodes

NaCl → Na + + Cl -

Anode - Oxidation
Cl - → Cl + e
Cl + Cl → Cl2

Cathode - Reduction
Na + + e → Na

Chlorine is liberated at anode

Sodium is deposited at cathode
 Electrochemical cell Chemical energy
Galvanic cell / Voltaic cell
Daniel cell Electrical energy

Anode

Zn → Zn 2+ + 2e

Cathode

Cu 2+ + 2e → Cu

Net reaction

Zn + Cu 2+ → Zn 2+ + Cu
Single electrode potential
▪ Double layer formed is known as Helmholtz electrical double layer
▪ A difference in potential is set up between the metal and the solution – Single
electrode potential
▪ The tendency of the electrode to lose electrons – Oxidation potential
▪ The tendency of the electrode to gain electrons – Reduction potential
▪ This potential difference is constant at equilibrium
▪ The potential difference developed when a metal is in contact with its own salt
solution of concentration 1M at 25oC – Standard electrode potential
▪ In general reduction potential is taken as the electrode potential
Electrochemical Series / Activity Series

Arrangement of metals in the increasing order of their standard electrode potential

Applications of electrochemical series

❖Reactivity of metals-
From top to bottom reactivity decreases

❖Determination of emf of the cell-

Emf = Ecathode- Eanode
lower E 0 value- tendency towards oxidation- anode
Higher E 0 value- tendency towards reduction - cathode

❖Displacement reaction- metals above in the series(low E0) can displace a metal below
it from its salt solution.
Eg- Zn can displace Cu from CuSO4 solution
Zn + CuSO4 → ZnSO4 + Cu
❖Reaction with H2 - metals having negative E0 value can
liberate from dil.acids

❖Spontaneity of redox reaction-

❖Analysis of products of electrolysis-

Relation between free energy and emf of the cell

Decrease in free energy = electrical energy generated in a reversible cell

electrical energy generated per mole = nFE

Decrease in free energy = -nFE

Calculate the amount of electric energy available from a dry cell of
emf 1.5 V which consumes 10g of Zn (At wt of Zn=65.5)
Nernst equation for the electrode potential
It is the relation between electrolyte concentration and electrode potential
Consider a general reduction reaction . The decrease in free energy accompanying in this process is given
by Vant Hoff’s equation
Nernst equation for single electrode

Nernst equation for a complete cell

Variation of EMF with temperature
Zn(S) + Cu 2+(aq) → Zn 2+(aq) + Cu (S)

Case1 [Zn 2+ ] = [Cu 2+ ] , Q=1 logarithmic term-zero Ecell = E0 cell EMF is independent on temperature

Case2 [Zn 2+ ] > [Cu 2+ ] Q >1 logarithmic term-negative Ecell < E0 cell EMF decreases with rise of temperature

Case3 [Zn 2+ ] < [Cu 2+ ] Q <1 logarithmic term-positive Ecell > E0 cell EMF increases with rise of temperature
Variation of EMF of hydrogen electrode with pH of solution
For hydrogen electrode at 250C H+ + e → ½ H2

E = E 0 - .0591 log 1
[H+ ]
E = E 0 - .0591 pH

E = 0 - .0591 pH = -.0591pH

Case 1 When pH=0 ie 1M HCl ie SHE E= 0V

Case 2 When pH=7 Neutral solution E = -0.591 X 7 = -.414V

Case3 When pH=14 Alkaline solution E = -0.591 x 14 = -.828 V

Variation of EMF of oxygen electrode with pH of solution

For oxygen electrode at 250C O2 + 4H+ + 4e → 2 H2O E0= 1.23V

E = E 0 - .0591 log 4
4
E = E 0 - .0591 pH = 1.23 - .0591 pH

Case 1 When pH=0 ie 1M HCl ie SHE E= 1.23 - 0.591 x 0 = 1.23 V

Case 2 When pH=7 Neutral solution E = 1.23 - 0.591 X 7 = -.81V

Case3 When pH=14 Alkaline solution E = 1.23 - 0.591 x 14 = -.40 V

Applications of Nernst equation

▪ Study the effect of electrolyte concentration on electrode potential

▪ Calculation of potential of a cell under non standard conditions

▪ The unknown concentration of one ionic species can be determined

▪ pH of a solution can be calculated

▪ Finding the valency of an ion or the number of electrons involved in a electrode reaction

▪ Solubility of sparingly soluble salt can be determined

 Types of electrodes
i. Metal / Metal ion electrode – Zn in ZnSO4

ii. Gas electrode- Hydrogen electrode

iii. Metal/insoluble metal salt/common ion electrode – Calomel electrode

iv. Redox electrode- Pt dipped in a solution containing mixture of FeCl2 and FeCl 3

v. Ion selective electrode – Glass electrode

 Standard hydrogen electrode (SHE) / Normal hydrogen electrode (NHE)
• Gas electrode
• Primary reference electrode
• E 0 =0
• Pt/H2(g)1atm/H+(1M)
• Act as anode and cathode

Reduction Oxidation

H+ + e → ½ H 2 ½ H2 → H+ + e
Limitations
▪ Very cumbersome to set up
▪ Requires considerable volume of solution
▪ Hydrogen electrode will be poisoned by compounds like Hg ,As ,S etc
▪ Difficult to maintain pressure of H2 gas at 1 atm and conc 1M HCl
 Calomel electrode • Secondary reference electrode
• Metal/insoluble metal salt/common ion electrode
• Hg/Hg2Cl2(s)/KCl

Reduction
Hg2Cl 2(s) + 2e → 2Hg(l) + 2Cl-(aq)

Ecal = E0 cal – 0.0591 log [Cl-]2

2
Ecal = E0 cal – 0.0591 log [Cl-]

KCl 0.1N (DNCE) 1N( NCE) Saturated (SCE)

concentration
Oxidation Electrode 0.3335 0.2810 0.2422
potential
2Hg(l) + 2Cl-(aq)→ Hg2Cl 2(s) + 2e
Measurement of electrode potential using calomel electrode
Zn electrode Cathode
Anode
Zn → Zn 2+ + 2e Hg2Cl 2(s) + 2e → 2Hg(l) + 2Cl-(aq)

Zn/ Zn 2+//Cl-/ Hg2Cl 2 /Hg

Ecell = E cathode –E anode
= Esce - E Zn 2+/Zn
=0.2422 - E Zn 2+/Zn
Cu electrode
Anode Cathode
2Hg(l) + 2Cl-(aq)→ Hg2Cl 2(s) + 2e Cu 2+(aq) + 2 e → Cu (S)
Ecell = E cathode –E anode

Hg/ Hg2Cl 2 / Cl- // Cu 2+ /Cu = E Cu 2+/Cu – Esce

= E Cu 2+/Cu – .2422
Glass electrode
• Ion selective electrode
• Used for pH measurement
• Ag/AgCl/.1MH+/glass/H+ (c= )

• If two different [H+] ion concentrations are separated by a very thin

glass membrane , there develops a difference in potential between
two surfaces of glass membrane.

• By keeping the pH of one of the solution inside electrode as

constant, the pH of the other solution can be determined.

• The glass membrane functions as an ion selective membrane and an

equilibrium is set up between Na + ions of glass and H+ ions in the
solution

E G = E0G - .0591 log

E G = E0G - .0591 pH
Measurement of pH

• For measuring the pH of a test solution the glass electrode is immersed in the test
solution and coupled with saturated calomel electrode

E cell = E cathode – E anode E G = E0G - .0591 pH

E cell = E G – E sce
E cell = E0G - .0591 pH - Esce