Class XII

Chapter 3: Electrochemistry

Electrochemistry is that branch of chemistry which deals with 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
(1) Production of metals like Na, Mg, Ca and Al. (2) Electroplating. (3) Purification of metals, (4) Batteries
and cells used in various instruments. (5) Explanation of natural phenomenon like corrosion etc.
Conductors : Substances that allow electric current to pass through them are known as conductors.
(i) Metallic Conductors or Electronic Conductors: Substances which allow the electric current to pass
through them by the movement of electrons are called metallic conductors, e.g.. metals.
It depends on (i) the nature & structure of the metal (ii) the no. of valence electrons per atom (iii) the
density of metal & (iv) temperature (it decreases with the increase in temperature)
(ii) Electrolytic Conductors or Electrolytes: Substances which allow the passage of electricity through their
fused state or aqueous solution and undergo chemical decomposition are called electrolytes or electrolytic
conductors, e.g., aqueous solution of acids. bases and salts.
Metallic Conduction Electrolytic conduction
1) Metallic conduction is carried by the movement 1) Electrolytic conduction is carried by the
of electrons movement of ions.
2) It involves no change in the chemical properties 2) It involves the decomposition of the electrolyte
of the conductor as a result of the chemical reaction.
3) It does not involve the transfer of matter or ions. 3) It involves the transfer of matter or ions.
4) Metallic conduction decreases with the increase 4) Electrolytic conduction increases with the
in temperature. increase in temperature.
Electrolytes are of two types:
1. Strong electrolytes: The electrolytes that completely dissociate or ionise into ions are called strong
electrolytes. e.g., HCl, NaOH, K2SO4 etc
2. Weak electrolytes
The electrolytes that dissociate partially ( degree of dissociation < 1) are called weak electrolytes, e.g.,
CH3COOH, H2CO3, NH4OH, H2S, etc.
 Electrochemical Cell and Electrolytic Cell

A spontaneous chemical process is the one which can take place on its own and in such a process the
Gibb’s energy of the system decreases. It is this energy that gets converted to electrical energy. The reverse
process is also possible in which we can make non-spontaneous processes occur by supplying external
energy in the form of electrical energy. These inter conversions are carried out in equipment called
Electrochemical Cells. The reactions carried out electrochemically can be energy efficient and less polluting.
An electrochemical cell of almost constant emf is called standard cell. The most common is Weston
standard cell. Galvanic cell is also called voltaic cell.
General Representation of an Electrochemical Cell : M1(s) / M1n+ (aq) || M2n+(aq)/M2(s)
Anode→𝑂𝑥𝑑𝑛. Redn. ← Cathode
Other features of the electrochemical cell are
(1) There is no evolution of heat.
(2) The solution remains neutral on both sides.
(3) The reaction and flow of electrons stops after sometime.

(a) When Ecell <1.1 V (b) When Ecell = 1.1 V (c) When Ecell > 1.1 V
(i) Electron flow from Zn rod to (i) No flow of electrons or current (i) Electrons flow & current flows
Cu rod hence current flows from from Zn to copper.
Cu to Zn.
(ii) Zn dissolves at anode and Cu (ii) No chemical reaction. (ii) Zn is deposited at the Zn
deposits at cathode. Cell reaction electrode & Cu is dissolved at Cu
is takes place. electrode. Cell reaction is
reversed.

Galvanic Cell (Daniell Cell)

Cell energy is extracted from a spontaneous chemical process or reaction and it is converted to electric
current.
For example, Daniell Cell is a Galvanic Cell in which Zinc and Copper are used for the redox reaction to take
place.
Zn is the reducing agent and Cu2+ is the oxidising agent. The half cells are also known as Electrodes.
The oxidation half is known as Anode and the reduction half is called Cathode.
Electrons flow from anode to cathode in the external circuit. Anode is assigned negative polarity and
cathode is assigned positive polarity.
In Daniell Cell, Zn acts as the anode and Cu acts as the cathode.
An electrochemical cell of zinc and copper metals is known as Daniell cell. It is represented as

Remember for a Daniell cell when external potential is applied:

Standard cell potential Ecell = 1.10 V
 By convention an anode on the LHS and cathode is represented on the RHS. [REMEMBER: L O A N ]

Electrochemical Anode Cathode

cell
Position (L) Left electrode Right electrode
Reaction (O) Oxidation Reduction
Name of electrode (A) Anode Cathode
Charge of electrode (N) Negative Positive electrode
electrode
Movement of Out of cell from Into the cell from
electrons anode cathode

Salt bridge: A salt bridge connects the two electrolytic solutions of an electrochemical cell.
Functions of a salt bridge:
1) It completes the circuit and allows the flow of current.
2) It maintains the electrical neutrality on both sides. Salt-bridge generally contains solution of strong
electrolyte such as KNO3, KCl etc in agar-agar or gelatine gel etc. (Jelly does not allow the salt of salt bridge
to mix with the electrolytic solution).
KCI is preferred because the transport numbers of K+ and Cl-are almost same. (Ionic mobility of K+(aq) &
Cl-(aq) is nearly same so it reduces the internal resistance of a cell.
Preferential Discharge of ions :
Where there are more than one cation or anion the process of discharge becomes competitive in nature.
Discharge of any ion requires energy and in case of several ions being present the discharge of that ion will
take place first which requires the energy.

Electrode Potential (𝐸𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑑𝑒)

When an electrode is in contact with the solution of its ions in a half-cell, it has a tendency to lose or gain
electrons which is known as electrode potential. It is expressed in volts. It is an intensive property, i.e.,
independent of the amount of species in the reaction. So, the potential difference between an electrode
and its ion in solution is called its electrode potential (𝐸𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑑𝑒)
The electrode potential will be named as oxidation or reduction potential depending upon whether
oxidation or reduction has taken place.
Oxidation potential (Eoxdn or 𝐸 𝑛+)
𝑀(𝑠)/𝑀
The tendency to lose electrons when an electrode is in contact with its ions is known as oxidation potential.
Oxidation potential of a half-cell is inversely proportional to the concentration of ions in the solution. It is
denoted by 𝐸 𝑛+
𝑀/𝑀
The half reaction is M ⇌ Mn+ + ne (Oxidation)
Reduction potential (Eredn or 𝐸 𝑛+ )
𝑀 /𝑀(𝑠)
The tendency to gain electrons when an electrode is in contact with its ions in the solution is known as
reduction potential.
It is denoted by 𝐸 𝑛+ . The half reaction is Mn+ + ne ⇌ M (reduction)
𝑀 /𝑀
According to IUPAC convention, the reduction potential alone be called as the electrode potential unless it
is specifically mentioned.

Remember: (a) Both oxidation and reduction potentials are equal in magnitude but opposite in sign.
(b) It is not a thermodynamic property, so values of Eredn are not additive.
Ereduction = – Eoxidation
 It is not possible to determine the absolute value of electrode potential, as oxidation & reduction takes
place simultaneously & not individually. So, a reference electrode [NHE or SHE] is required to determine
its value.
The electrode potential is only the difference of potentials between two electrodes that we can
measure by combining them to form a complete cell.

𝑜 θ
Standard Electrode Potential (𝐸 𝑜𝑟 𝐸 )
The potential difference developed between metal electrode and solution of its ions of unit molarity (1M)
𝑜
at 1 atm pressure and 25°C (298 K) is called standard electrode potential. It is denotes as 𝐸𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑑𝑒.
It can be standard reduction potential or standard oxidation potential.
θ θ
(Standard states: 1 atm. pressure, 298 K & 1M solution) So, 𝐸𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛 = − 𝐸𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛
θ θ
Example: 𝐸 2+ = +0.34V so, 𝐸 2+ = - 0.34V
𝐶𝑢 /𝐶𝑢 𝐶𝑢/𝐶𝑢
Reference Electrode
The electrode of known potential is called reference electrode. It may be primary reference electrode like
standard hydrogen electrode (SHE) or secondary reference electrode like calomel electrode etc.
Standard hydrogen electrode (SHE): - also known as normal hydrogen electrode (NHE), consists of
platinum wire, carrying platinum foil coated with finely divided platinum black. The wire is sealed into a
glass tube. placed in beaker containing 1 M HCl. The hydrogen gas at 1 atm pressure is bubbled through the
solution at 298K. Half-cell is Pt, H2 (1 atm) /H+ (1 M)

Electromotive Force (e.m.f) of a Cell:

It is the difference between the electrode potentials of two half-cells and cause flow of current from
electrode at higher potential to electrode at lower potential. It is also the measure of free energy change.
𝑜
Standard emf of a cell is denoted as 𝐸𝑐𝑒𝑙𝑙

θ θ θ θ θ θ
It is calculated as 𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒 = 𝐸𝑟𝑖𝑔ℎ𝑡 − 𝐸𝑙𝑒𝑓𝑡 where 𝐸𝑐𝑒𝑙𝑙 = Standard e.m.f or

Standard cell potential.

 θ θ
(Remember: For numerical purpose always take 𝐸𝑟𝑖𝑔ℎ𝑡& 𝐸𝑙𝑒𝑓𝑡 values as standard reduction potentials.)

Sl. E.m.f. Cell potential

No.
1 Potential difference between two The potential difference of the two half cells
electrodes when no current flows in the when electric current flows through the cells is
circuit. called cell potential
2 Emf is the maximum voltage which can be It is always less than the maximum voltage
obtained from a cell. It gives maximum work obtained from the cell.
obtained from a cell. The work obtained is less than the maximum
work from a cell.
3 It is measured by a potentiometer It is measured by a voltmeter

For a Daniell Cell: Zn(s) / Zn2+(aq) // Cu2+(aq) / Cu(s)

Cell reaction: Zn(s) + Cu2+(aq) 🡪 Zn2+(aq) + Cu(s)
[Zn acts as anode & Cu acts as cathode]

θ θ θ θ θ
Standard cell potential : 𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒 = 𝐸 2+ − 𝐸 2+
𝐶𝑢 /𝐶𝑢 𝑍𝑛 /𝑍𝑛
θ
𝐸𝑐𝑒𝑙𝑙 = + 0.34 – (- 0.76) = 1.10 V

Electrochemical Series:
It is the arrangement of electrodes in the increasing order of their standard reduction potentials at 298K.

Electrochemical series or Standard Electrode Potential values at 298 K

Applications of Electrochemical Series (ECS)

(1) The lower the value of E°, the greater the tendency to form cation. & the metal undergoes oxidation &
is a reducing agent. M → Mn+ + ne- (Metal, M 🡪 oxdn.) 🡪 reducing agent,so, Li is the best reducing
agent having least std. reduction value = -3.05 V)

(2) Metals placed below hydrogen in ECS replace hydrogen from dilute acids but metals placed above
hydrogen cannot replace hydrogen from dilute acids. Example: Zn + dil. H2SO4 🡪 ZnSO4 + H2(g)
or Fe + 2H+ 🡪 Fe2+ + H2(g). These reactions are feasible as Zn or Fe lie below H2 in ECS.
But, Cu + (dil.) H2SO4 🡪 No reaction or Ag + H+ 🡪 No reaction. These reaction are not feasible as Cu or Ag lie
above H2 in ECS.

(3) Oxides of metals placed below hydrogen are not reduced by H2 but oxides of iron and metals placed
above iron are reduced by H2·
•SnO, PbO, CuO etc are reduced by H2
•CaO, K2O, Na2O etc are not reduced by H2·
(4) Reducing character increases down the series & oxidising character decreasing down the series. The
best oxidising agent is F2.

(5) Reactivity increases down the series (metallic character)

(6) Determination of emf; emf is the difference of reduction potentials of two half-cells. Eemf = ERHS – ELHS
(a) If Ecell is positive. Then the cell reaction take place spontaneously, otherwise not.(the cell works)
(b) If Ecell < 0, the cell reaction is non spontaneous & the cell does not work.
(c) If Ecell = the cell reaction is in equilibrium.
(7) Greater the reduction potential of a substance, greater is the oxidising power. (e.g.. F2 > Cl2 > Br2 > I2)
(8) Oxides of metals having E°red ≥ 0.79 V will be decomposed by heating to form O2 and metal.
HgO(s) → Hg(l) + (½)O2(g) Here, (E°Hg 2+/Hg = 0.79 V)
(9) Electrochemical cells are extensively used for determining the pH of solutions, solubility product (Ksp),
equilibrium constant (Kc) and other thermodynamic properties & for potentiometric titrations.

Think: (1) Can we store nickel sulphate solution in a zinc vessel?

(2) Can we stir ferrous sulphate solution with silver spoon? Take standard reduction values from the table)

Nernst Equation
It relates mathematically the electrode potential of an electrode or cell potential of an electrochemical cell
with their standard states at different concentrations & temperature.
The electrode potential of an electrode at any concentration is measured with respect to the SHE.

For a electrochemical cell,

aA + bB 🡪 cC + dD
where no. of electrons exchanged = n.

Nernst equation can be written as

𝑜 2.303 𝑅 𝑇
Ecell = 𝐸𝑐𝑒𝑙𝑙 − 𝑛𝐹
log 𝑙𝑜𝑔 𝑄𝑐 or,
𝑐 𝑑 𝑐 𝑑
𝑜 2.303 𝑅 𝑇 [𝐶] [𝐷] 𝑜 0.059 [𝐶] [𝐷]
Ecell = 𝐸𝑐𝑒𝑙𝑙 − 𝑛𝐹
𝑙𝑜𝑔 𝑎 𝑏 or Ecel l = 𝐸𝑐𝑒𝑙𝑙 − 𝑛
𝑙𝑜𝑔 𝑎 𝑏
[𝐴] [𝐵] [𝐴] [𝐵]
 𝑐 𝑑
𝑜 0.059 [𝐶] [𝐷]
In general, Ecell = 𝐸𝑐𝑒𝑙𝑙 − 𝑛
log 𝑙𝑜𝑔 𝑄𝑐 (where Qc is the reaction quotient and Qc = 𝑎 𝑏 )
[𝐴] [𝐵]

Example: Write the Nernst equation at 298K for a cell: Al(s)/Al3+(C1) // Zn2+ (C2) /Zn(s).
Solution: The cell reaction: Anode (Oxidation: Al 🡪 Al3+ + 3e [x 2
Cathode (Reduction: Zn2+ + 2e 🡪 Zn [ x 3
Cell reaction: 2Al + 3Zn2+ (C2) 🡪 2Al3+(C1) + 3Zn [Here n = 2 x 3 = 6]
2 2 3
3+ 3 𝐶1(1)
𝑙𝑜𝑔 [ 2 ] 2+ 3 = 𝐸𝑐𝑒𝑙𝑙 −
𝑜 0.059 𝐴𝑙 [𝑍𝑛] 𝑜 0.059
The Nernst Equation: Ecell = 𝐸𝑐𝑒𝑙𝑙 − 𝑛 6
log 2 3
[𝐴𝑙] [𝑍𝑛 ] (1) 𝐶2
2
𝑜 0.059 𝐶1
= 𝐸𝑐𝑒𝑙𝑙 − 6
log 3 (Ans)
𝐶2

Nernst equation and Equilibrium constant, Kc

At equilibrium : No net electrons flow in an electrochemical cell, so Qc = Kc. & Ecell = 0
𝑜 2.303 𝑅 𝑇 𝑜 2.303 𝑅 𝑇
We know, Ecell = 𝐸𝑐𝑒𝑙𝑙 − 𝑛𝐹
log 𝑙𝑜𝑔 𝑄𝑐 , At Equilibrium, 0 = 𝐸𝑐𝑒𝑙𝑙 − 𝑛𝐹
log 𝑙𝑜𝑔 𝐾𝑐
𝑜 2.303 𝑅 𝑇
or, 𝐸𝑐𝑒𝑙𝑙 = 𝑛𝐹
log 𝑙𝑜𝑔 𝐾𝑐

𝑜 0.059
Hence, 𝐸𝑐𝑒𝑙𝑙 = 𝑛
log 𝑙𝑜𝑔 𝐾𝑐
.
Relationship between free energy change (ΔG°) and equilibrium constant (Kc)
ΔG° is the standard Gibbs free energy change
𝑜 2.303 𝑅 𝑇
We know, 𝐸𝑐𝑒𝑙𝑙 = 𝑛𝐹
log 𝑙𝑜𝑔 𝐾𝑐

𝑜 𝑜
or, 𝑛𝐹𝐸𝑐𝑒𝑙𝑙 = 2. 303𝑅𝑇 log 𝑙𝑜𝑔 𝐾𝑐 or, ΔG° = – 2.303 RT log Kc [ΔG° = - nF𝐸𝑐𝑒𝑙𝑙]

Type of ΔG° 𝑜
𝐸𝑐𝑒𝑙𝑙 Type of cell
reaction
Spontaneous -ve +ve Galvanic cell
Non +ve -ve Electrolytic cell
spontaneous
Equilibrium 0 0 Dead cell

[Concentration Cell is an electrochemical cell in which two electrodes their ions are same, but they differ in
𝑜
ionic concentrations of electrolytes. Its 𝐸𝑐𝑒𝑙𝑙 = 0

For a concentration cell: M(s) / Mn+(C1) // Mn+(C2)/M(s)

Here the cell reaction is Mn+ (C2) 🡪 Mn+(C1) where no. of electrons = n and C2 > C1
2.303 𝑅 𝑇 𝐶1 2.303 𝑅 𝑇 𝐶2
Nernst equation can be written as Ecell = - 𝑛𝐹
𝑙𝑜𝑔 𝐶2
or, Ecell = 𝑛𝐹
𝑙𝑜𝑔 𝐶1

0.059 𝐶2
or, Ecell = 𝑛
𝑙𝑜𝑔 𝐶1

Case 1: Electrode concentration cell: two hydrogen electrodes or different pressures are dipped In the
𝑜
same solution of electrolyte, e.g. Pt, H2 (p1) /H+/H2(p2), Pt at 25°C, where p1> p2 and 𝐸𝑐𝑒𝑙𝑙 = 0

2.303 𝑅 𝑇 𝑝2 0.059 𝑝2
Nernst Equation can be written as Ecell = 𝑛𝐹
𝑙𝑜𝑔 𝑝1
or, Ecell = 𝑛
𝑙𝑜𝑔 𝑝1

Case 2: Electrolyte concentration cells: Electrodes (say Zn) are the same but electrolyte solutions have
different concentrations, e.g. Zn(s) / Zn2+(C1) // Zn2+(C2)/Zn(s),
2.303 𝑅 𝑇 𝐶2 0.059 𝐶2
Here, C2 > C1 Hence, Nernst Eqn. is written as Ecell = 2𝐹
𝑙𝑜𝑔 𝐶1
or, Ecell = 2
𝑙𝑜𝑔 𝐶1
]

** Out of CBSE syllabus

Numerical problem:
(1) Calculate the potential of hydrogen electrode in contact with a solution whose pH is 10.
Solution: We have, H+ (pH = 10) + 1e 🡪 ½ H2 , SHE = 0.00V and pH = - log [H+]
0.059 1
Nernst equation: 𝐸 + = − 1 𝑙𝑜𝑔 + = 0.059 (- log [H+]) = 0.059 pH = 0.059 x 10 = 0.59 V (Ans)
𝐻 /𝐻2 [𝐻 ]

Numerical problems for practice:

(1) Write the Nernst equation & calculate the emf of the following cell at 298K Cu(s)/Cu2+(0.13M)//Ag+(10-4
M)/Ag(s)(Given Standard reduction potential of Cu & Ag are 0.34V & 0.80V ) [Ans. 0.25V]
(2) A cell contains two hydrogen electrodes. The negative electrode is in contact with a solution of 10-6M
hydrogen ions. The emf of the cell is 0.118 V at 298K. Calculate the concentration of hydrogen ions at the
positive electrode. Find its pH. [Ans; 10-4M, 4]
𝑜
(3) Calculate the e.m.f. of the following cell at 298K. 2Cr(s) + 3Fe2+(0.1M) 🡪 2Cr3+(0.01M) + Fe(s) (𝐸 2+ =
𝐶𝑢 /𝐶𝑢
𝑜
+0.34V & 𝐸 2+ = -0.44 V) [Ans: 0.31V]
𝐹𝑒 /𝐹𝑒
𝑜
(4) Consider the following cell reaction: 2Fe(s) + O2 + 4H+(aq) 🡪 2 Fe2+(aq) + 2H2O(l) ; 𝐸𝑐𝑒𝑙𝑙 = 1.67V, [Fe2+]
=10-3M, 𝑝𝑂 = 0.1 atm, The e.m.f. of the cell is 1.57 V. Calculate the pH of the solution. [Ans; pH = 2.95]
2

(5) Calculate the equilibrium constant (Kc) for the reaction: 4Br- + O2 + 4H+ ⇌ 2Br2 + H2O(l) , Given that
θ
𝐸𝐶𝑒𝑙𝑙 = 0.16 V. Comment on the reaction.
[Ans. 7.03 x 1010, large, the reaction proceeds towards the production of product.]
𝑜
(6) For a cell reaction at 298 K: A(s) + 2B-(aq) ⇌ A2+ + 2B(s) the equilibrium constant is 104. Calculate 𝐸𝑐𝑒𝑙𝑙.
[Ans. 0.118V]
(7) The zinc/silver oxide cell is used is used in hearing aids and electric watches.
Zn 🡪 Zn2+ + 2e (Eo = 0.76V) & Ag2O + H2O + 2e 🡪 2Ag + 2OH- (Eo = 0.344 V) (a) Which is oxidised &
𝑜 θ
which is reduced? (b) Find 𝐸𝑐𝑒𝑙𝑙 𝑎𝑛𝑑 ∆𝑟𝐺 . [Ans. 1.104 V, - 2.13 x 102 kJ]
(8) Calculate the e.m.f. of a cell & its standard Gibbs energy at 298K :
Al(s)/Al3+(0.01M)//Fe2+(0.022M)/Fe(s). Standard electrode potential of Al & Fe are -1.66V & -0.44V
respectively. [Ans. 1.209 V, - 706.38kJ]
Conductance (G) (or electrolytic conductance)
It is the ease of flow of electric current through the conductor. It is reciprocal of resistance (R).
1 −1
G= 𝑅
Unit of G is ohm-1, mho, S, Ω . (S denotes seimens)

Conductivity (k) is defined as the conductance of a

Solution if 1 cm length and having 1 sq. cm as the
area of cross section. (k 🡪 kappa)
Conductivity is the conductance of 1cm3 of a solution of
an electrolyte.

Conductivity of a solution is the reciprocal of resistivity

of a solution of an electrolyte.
1 1 1 𝑙
K = ρ or k = 𝑅 𝑎 k = G.G* where cell constant G* = 𝑎
. Unit of cell constant is cm-1 or m-1 (SI unit)
𝑙

Molar Conductivity (Λm)

The conductivity of all the ions produced when 1 mole of an electrolyte is dissolved in V mL of solution is
known as molar conductivity. It is the conductance of 1 mole of an electrolyte in solution placed between
two electrodes 1 cm apart having V cm2 area of cross section.
It is the conduction of 1mole of an electrolyte in V cm3 of solution.
1000 𝑘
It is related to conductance as Λm = 𝑀 where M is the molarity of solution of electrolyte.
It units are Ω-1 cm2 mol-1 or S m2 mol-1 (in SI unit) Also, 1 S m2 mol-1 = 102 S cm2 mol-1

Examples: (1) The resistance of a conductivity cell containing 0.001 M KCl solution at 298 K is 1500 Ω.
What is the cell constant f conductivity of 0.001 M KCl solution at 298 K is 0.146 x 10-3 S cm-1?
*
𝐺
Solution: Given k = 0.146 x 10-3 S cm-1 & R = 1500 Ω We know, G = 1/R & k = GG* = 𝑅
or, G* = k.R =
0.146 x 10-3 x 1500
Hence G* = 0.219 cm-1 (Ans)

(2) A 0.05 M NaOH solution : a resistance of 31.6 ohm in a conductivity cell at 298 K. If area of plates of
conductivity cell is 3.8 cm2 & distance between them is 1.4 cm, calculate the molar conductivity of NaOH
solution.
1.4 𝑐𝑚 -1
Solution: Cell constant G* = l/a = 2 = 0.368 cm . Given concentration = 0.05M, R = 31.6 ohm,
3.8 𝑐𝑚
 *
𝐺 0.368 1000 𝑘 1000 𝑥 0.0116
So, conductivity k = GG* = 𝑅
= 31.6
– 0.0116 S cm-1. Hence, Λ𝑚 = 𝑀
= 0.05
= 232 S cm2 mol-1
(Ans)

(3) A conductivity cell when filled with 0.01 M KCl has a resistance of 747.5 ohm at 298K. When the same
cell was filled with an aqueous solution of 0.005 M CaCl2 solution, the resistance was 876 ohm. Calculate
(i) conductivity and (ii) molar conductivity of CaCl2 solution.
( conductivity of 0.01 M KCl solution is 0.14114 S/m.
Solution: (a) For KCl solution: R = 747.5 ohm k = 0.14114 S/m Hence Cell constant G* = R. k = 747.5 x
0.14114 = 105.5 m-1.
(b) For CaCl2 solution, conductivity cell is same. So cell constant (G*) is same. Hence, conductivity k =
𝑐𝑒𝑙𝑙 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 105.5
𝑅
= 876 = 0.1204 S/m
1000 𝑘 1000 𝑥 0.1204
(c) For CaCl2 solution, molar concentration = 0.005 mol dm-3. Λ𝑚 = 𝑀
= 0.005
= 0.0241 S m2 mol-1 (Ans)

Numerical problems for practice:

(1) The molar conductivity of a 1.5 M solution of an electrolyte is found to be 138.9 S cm2mol-1. Calculate the
conductivity of this solution. [Ans: 0.2083 S/cm]
(2) The conductivity of a solution containing 1.0 g of anhydrous BaCl2 in 200 mL of the solution has found to 0.0058
Scm-1. Calculate the molar conductivity of the solution. (At. No. Ba = 137, Cl = 35.5) [
Ans241.67 Scm2mol-1]
(3) The resistance of a conductivity cell with 0.1 M KCl solution is found to be 200 ohm at 298 K. When the same cell
was filled with 0.02 M NaCl solution, the resistance at the at the same temperature is found to be 1100 ohm.
Calculate (i) cell constant of the cell in m-1.. (ii) the molar conductivity of 0.02 M NaCl solution in S m2 mol-1. (k for 0.1
M KCl solution at 298 K = 1.29 S/m) [Ans: 258 m-1, 1.175 x 10-2 S m2 mol-1]
(4) The molar conductance of 0.05 M solution of MgCl2 is 194.5 S cm2 mol-1 at 298 K. A cell with electrodes having
1.50 cm2 surface area and 0.50 cm apart is filled with 0.05 M solution of MgCl2. How much current will flow when the
potential difference between the electrodes is 5 V?
[Ans. 0.146 A]

Variation of molar conductivity with concentration for strong electrolytes.

In case of a strong electrolyte, molar conductivity increases slowly on dilution. On further dilution till
infinite dilution when concentration tends to zero , molar conductivity value becomes a constant value for a
particular electrolyte.
The molar conductivity when the concentration approaches zero is called molar conductivity at infinite
𝑜
dilution (Λ𝑚)
𝑜
We can say, Λ𝑚 = Λ𝑚 when molar concentration C tends to zero.

Debye-Huckel Onsager equation :

It gives a relation between molar conductivity, Λm at a particular concentration and molar conductivity at
𝑜
infinite dilution Λ𝑚.
Λm = Λ0 m – A√C where, A is a constant. It depends upon the nature of solvent and
temperature.
Variation of molar conductivity with concentration for weak electrolytes.

Variation of molar conductivity with Temperature: The increase of temperature decreases inter-ionic
attractions and
increases kinetic energy of ions and their speed. Thus, Λm increase with temperature.

Applications of Kohlrausch law of independent migration of ions:

(i) We can determine the molar conductivities of weak electrolytes at infinite dilution, e.g.,
𝑜 𝑜 𝑜 𝑜
( ) (
Λ𝑚 𝐶𝐻3𝐶𝑂𝑂𝐻 = Λ𝑚 𝐶𝐻3𝐶𝑂𝑁𝑎 + Λ𝐻𝐶𝑙 − Λ𝑁𝑎𝐶𝑙 )
𝑜 𝑜 𝑜 𝑜
( )
Λ𝑚(𝑁𝐻4𝑂𝐻) = Λ𝑚 𝑁𝐻4𝐶𝑙 + Λ𝑁𝑎𝑂𝐻 − Λ𝑁𝑎𝐶𝑙

(ii) Determination of degree of dissociation (α) of an electrolyte at a given dilution.

𝑚𝑜𝑙𝑎𝑟 𝑐𝑜𝑛𝑑𝑢𝑐𝑡𝑖𝑣𝑖𝑡𝑦 𝑎𝑡 𝑎 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝐶 Λ𝑚
𝝰= 𝑚𝑜𝑙𝑎𝑟 𝑐𝑜𝑛𝑑𝑢𝑐𝑡𝑖𝑣𝑖𝑡𝑦 𝑎𝑡 𝑖𝑛𝑓𝑖𝑛𝑖𝑡𝑒 𝑑𝑖𝑙𝑢𝑡𝑖𝑜𝑛 (𝑙𝑖𝑚𝑖𝑡𝑖𝑛𝑔 𝑚𝑜𝑙𝑎𝑟 𝑐𝑜𝑛𝑑𝑢𝑐𝑡𝑖𝑣𝑖𝑡𝑦)
or 𝝰= 𝑜
Λ𝑚

The dissociation constant (Kc) of the weak electrolyte (of type AB) at concentration C of the solution can be
2
𝐶α
calculated by using the formula Kc = 1− α
where, α is the degree of dissociation of the electrolyte.
(iii) Salts like BaSO4, PbSO4, AgCl, AgBr, AgI etc which do not dissolve to a large extent in water are called
sparingly soluble salts.
𝑜 1000 𝑘
The solubility of a sparingly soluble salt can be calculated as Λ𝑚 = 𝑆
where S is the solubility of a
salt in mol/L.

Example: (1) The limiting molar conductivities of NaCl, NaAc & HCl are 126.4, 425.9 and 91.0 S cm2 mol-1
respectively. Calculate the limiting molar conductivity of AcH.
𝑜 𝑜 𝑜 𝑜 𝑜 𝑜 𝑜 𝑜 𝑜
Solution: Λ 𝐴𝑐𝐻 = λ − + λ + = λ − + λ + + λ + + λ − − λ + −λ −
𝐴𝑐 𝐻 𝐴𝑐 𝑁𝑎 𝐻 𝐶𝑙 𝑁𝑎 𝐶𝑙
0 0 0
= Λ𝑁𝑎𝐴𝑐 + Λ𝐻𝐶𝑙 − Λ𝑁𝑎𝐶𝑙
= 425.9 + 91.0 – 126.4 = 226.0 S cm2 mol-1 (Ans)

Example (2) The conductivity (k) of 0.001028 M acetic acid is 4.95 x 10-5 S cm-1. Calculate its dissociation
constant if limiting molar conductivity is acetic acid is 390.5 S cm2 mol-1.
Solution:
−5
1000 𝑘 1000 𝑥 4.95 𝑥 10
We know, Λm = 𝑀
= 0.001028
= 48.15 S cm2mol-1.
Λ𝑚 48.15
Degree of dissociation 𝝰 = 𝑜 = 390.5
= 0.1233
Λ𝑚
2 2
𝐶α 0.001028 𝑥 (0.1233)
And dissociation constant Kc = 1− α 1−0.1233
= 1.78 x 10-5 mol L-1 (Ans)

Numerical problems for practice:

(1) Suggest a way to determine limiting molar conductivity of water.
0 0 0 0
[Ans: Λ𝐻 𝑂 = Λ𝑁𝑎𝑂𝐻 + Λ𝐻𝐶𝑙 − Λ𝑁𝑎𝐶𝑙 ]
2

(2) The molar conductivity of of 0.025 M HCOOH is 46.1 S cm2 mol-1. Calculate its degree of dissociation &
𝑜 𝑜
dissociation constant. (Given: λ + = 349. 6 S cm2 mol-1 & λ − = 54.6 S cm2 mol-1.
𝐻 𝐻𝐶𝑂𝑂
[Ans: 0.114, 3.67 x 10-4]
(3) The molar conductivity at infinity dilution of aluminium sulphate is 858 S cm2 mol-1. Calculate the
0
limiting molar ionic conductivity of Al3+ ion. (Given λ 2− = 160 S cm2 mol-1.
𝑆𝑂4
[Ans. 189 Scm2 mol-1]
(4) The limiting molar conductivity of NaOH, NaCl and BaCl2 at 298K are 2.481 x 10-2, 1.265 x 10-2 and 2.80 x
𝑜
10-2 S cm2 mol-1 respectively. Calculate Λ𝑚 for Ba(OH)2. [Ans 5.23 x 10-2 S cm2 mol-1]

Electrolytic cells & Electrolysis

In an electrolytic cell external source of voltage is used to bring about a non-spontaneous chemical
reaction.
Electrolysis is the process of decomposition of an electrolyte when electric current is passed through
either its aqueous solution or molten state.

1. In electrolytic cell both oxidation and reduction takes place in the same cell.
2. Anode is positively charged where oxidation takes place and cathode is negatively charged where
reduction takes place in electrolytic cell.[Anode (oxidation) 🡪 + ve and Cathode (reduction) 🡪 - ve]
3. During electrolysis of molten electrolyte, cations are liberated at cathode (negatively charged). while
anions at the anode (positively charged).
4. When two or more ions compete at the electrodes, the ion with higher reduction potential gets liberated
at the cathode while the ion with lower reduction potential at the anode.
 For metals to be deposited on the cathode during electrolysis, the voltage required is almost the
same as the standard electrode potential. However for liberation of gases, some extra voltage is required
than the theoretical value of the standard electrode potential. The extra voltage thus required is called over
voltage or bubble voltage or over potential.
Discharge potential is defined as the minimum potential that must be applied across the electrodes to
bring about the electrolysis and subsequent discharge of the ion on the electrode.

How to Predict the Products of Electrolysis?

When an aqueous solution of an electrolyte is electrolysed, if the cation has higher reduction potential
than water (standard reduction potential H2O/ H2,OH- = -0.83 V), cation is liberated at the cathode (e.g.. in
the electrolysis of copper and silver salts , standard reduction potential of Cu2+/Cu & Ag+/Ag are +0.34 &
0.80V respectively) otherwise H2 gas is liberated due to reduction of water (e.g., in the electrolysis of K, Na,
Ca salts, etc, standard reduction potential of Na+/Na, K+/K, Ca2+/Ca are -2.71, -2.93 and -2.87V respectively).
Similarly if anion has higher oxidation potential than water
(Standard oxidation potential: H2O/ O2, H+ = - 1.23 V), anion is liberated (e.g., Br2/Br- = -1.09V), otherwise
O2 gas is liberated due to oxidation of water (e.g., in case of F- /F2 = -2.87V, aqueous solution of Na2SO4 as
oxidation potential of SO42- is – 0.2 V).

(1) Electrolysis of molten NaCl using graphite electrodes

NaCl (Molten) ∆→ Na+ + Cl- (molten state)
At Cathode (reduction, -ve electrode): Na+ + 1e 🡪 Na and
at Anode (oxidation, +ve electrode): Cl- 🡪 ½Cl2(g) +1e
[ 2NaCl (molten) 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑙𝑦𝑠𝑖𝑠 (𝑔𝑟𝑎𝑝ℎ𝑖𝑡𝑒 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑑𝑒𝑠)→ 2Na (at cathode) + Cl2 (at anode) ]

(2) Electrolysis of aqueous NaCl solution using graphite electrodes

NaCl + aq 🡪 Na+(aq) + Cl-(aq) and water dissociates very slightly as H2O ⇌ H+ + OH-
At cathode (reduction) H+ + 1e 🡪 ½H2 [Std reduction potential of H+/H2 (=0.00V) > Na+/Na (= -2.71V)]
At anode (oxidation) Cl- 🡪 ½Cl2(g) + 1e
[ Std reduction potential Cl2 / Cl- (= 1.36V < H2O/O2,H+ (= 1.23V), so O2 should be liberated at anode but
dissociation of H2O into O2 is kinetically slow. To enhance the rate , extra potential is applied called over
voltage or over potential, the oxidation potential of Cl-/Cl2 is achieved thus Cl2 is preferentially produces at
anode in place of O2]
& Na+ + OH- 🡪 NaOH ; thus, pH of the solution increases after the electrolysis.
[NaCl (aq) + H2O(l) 𝐸𝑙𝑒𝑐𝑡𝑟𝑜𝑙𝑦𝑠𝑖𝑠→ [Na+(aq) + OH-(aq) ] + ½H2 (at cathode) + ½Cl2(g) (at anode)

(3) Electrolysis of molten PbBr2 using Pt electrodes.

PbBr2 ∆→ Pb2+ + 2Br-(molten)
At Cathode(reduction): Pb2+ + 2e 🡪 Pb
anode (oxidation) 2Br- 🡪 Br2 + 2e

(4) Electrolysis of acidified water using Pt electrodes: (generally acidified by a few drops of dilute sulphuric
acid)
H2O ⇌ H+ + OH-
At cathode (reduction) H+ + 1e 🡪 ½H2(g) & at anode (oxidation) OH- 🡪 OH + 1e & 4OH 🡪 2H2O + O2(g)
( 2H2O 𝐸𝑙𝑒𝑐𝑡𝑟𝑜𝑙𝑦𝑠𝑖𝑠→ 2H2 (at cathode) + O2 (at anode)]

(5) Electrolysis of H2SO4 using Pt electrodes:

H2SO4 + aq 🡪 2H+(aq) + SO42-(aq)
At cathode (reduction) H+ + 1e 🡪 ½H2 [ or 2H2O + 2e 🡪 H2 + 2OH-]
θ
At anode (oxidation) There are two possible reactions (i) 2H2O 🡪 O2 + 4H+ +4e ( 𝐸𝐻 𝑂/𝑂 = +1.23 V]
2 2
 θ
(ii) 2SO42-(aq) 🡪 S2O82-(aq) + 2e (𝐸 2− 2− = 1.96V)
𝑆𝑂4 / 𝑆2𝑂8
(a) for dilute H2SO4 solution: reaction (i) is preferred & O2 is liberated at anode.
(b) for higher concentration of H2SO4, reaction (ii) is followed & peroxodisulphuric acid H2S2O8 is formed.

(6) Electrolysis of CuSO4 solution using Pt electrodes:

CuSO4 + aq 🡪 Cu2+(aq) + SO42- (aq)
θ θ
At cathode (reduction) Cu2+ + 2e 🡪 Cu(s) [ Here 𝐸 2+ (=0.34V) > 𝐸 + (= 0.00V) ]
𝐶𝑢 /𝐶𝑢 𝐻 /𝐻2
At anode (oxidation): 2H2O 🡪 O2 + 4H+ +4e
(SO42- ion will not oxidise as maximum oxidation state of S is +6)
[ 2H + SO4 🡪 H2SO4, solution becomes more acidic pH of the solution decreases.)
+ 2-

(7) Electrolysis of CuSO4 solution using Cu electrodes:

CuSO4 + aq 🡪 Cu2+(aq) + SO42- (aq)
θ θ
At cathode (reduction) : Cu2+ + 2e 🡪 Cu(s) [ Here 𝐸 2+ (=0.34V) > 𝐸 + (= 0.00V) ]
𝐶𝑢 /𝐶𝑢 𝐻 /𝐻2
At Anode (oxidation) : Cu 🡪 Cu2+ + 2e [ Here, Standard oxidation potential Cu/Cu2+( = - 0.34V) > H2O/O2,
H+ ( = -1.23V) ]

Try: (1) Using Pt electrodes, the blue colour of CuSO4 fades out on electrolysis, but using Cu electrodes, the
blue colour of solution does not fade out. Why?
(2) Can we suitably add dilute HCl to acidify water before electrolysis to get H2 & O2?
(3) Suggest a list of metals that are extracted electrolytically.

Faraday’s Laws of Electrolysis

1. First law of electrolysis:
The amount of a chemical substance which occurs at any electrode during electrolysis by a current is
directly proportional to the quantity of electricity passed through electrolyte (molten or solution).
W ∝ I x t or, w = Z.I.t = Z.Q where Q (in coulomb) = I (in ampere) x t (in second)
& w is the mass of chemical substance in gram.

Z is a constant known as electrochemical equivalent (ECE).

When current of 1 ampere in 1 sec or charge in Q = 1 coulomb charge flows through the solution or
molten state of an electrolyte, mass of the substance deposited or liberated is called its electrochemical
equivalent,
( If Q = 1C or I = 1A & t = 1s, w = Z ).

[ Charge of 1 mole of electron = 1F (faraday) = 6.023 x 1023 x 1.6021 x 10-19 = 96487 C mol-1 ≈ 96500 C
mol-1.]
Al3+(aq) + 3e 🡪 Al(s)
1 mol 3F 1 mol = 27 g Al
i,e. 3F or 3 x 96500 C of charge is required to form 1 mole or 27 g of Al.
27
So, ECE of Al = ZAl = 3𝑥96500 g

Example: A solution of CuSO4 is electrolysed for 10 minutes with a current of 1.5 A. What is the mass of
copper deposited at cathode? (Atomic mass of Cu = 63.5 u)
Solution: I = 1.5 A, t = 10 x 60 s = 600 s Charge Q = I.t = 1.5 x 600 = 900 C
We have: Cu2+ + 2e 🡪 Cu
2F 1 mol = 63.5g ⇒ 2 F = 2 x 96500 C charge
2 x 96500 C charge deposits 63.5 g Cu
 63.5 𝑥 900
900 C charge deposits 2 𝑥 96500
= 0.2961 g of Cu (Ans)

2. Second law of electrolysis:

When the same quantity of electricity is passed through different electrolytes, in series, the amounts of the
substances deposited or liberated at the electrodes arc directly proportional to their equivalent weights,
Thus,
When Q amount of charge is passed in series through different electrolytes A & B are deposited.
According to second law,

𝑀𝑎𝑠𝑠 𝑜𝑓 𝐴 (𝑊𝐴 ) 𝐸𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑚𝑎𝑠𝑠 𝑜𝑓 𝐴 (𝐸𝐴) 𝑊𝐴 𝐸𝐴 𝑄.𝑍𝐴 𝑍𝐴

𝑀𝑎𝑠𝑠 𝑜𝑓 𝐵 (𝑊𝐵 )
= 𝐸𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑚𝑎𝑠𝑠 𝑜𝑓 𝐵 (𝐸𝐵)
or 𝑊𝐵
= 𝐸𝐵
= 𝑄,𝑍𝑏
= 𝑍𝐵
Hence, electrochemical equivalent (Z) ∝ equivalent weight (E).

Numerical Problems for practice:

(1) How many coulombs are required to deposit 40.5 g of Al when the cathode reaction is
Al3+(aq) + 3e 🡪 Al(s) [Ans. 434250C]
(2) How many coulombs of electricity are required for
(i) oxidation of 1 mol of H2O to O2.
(ii) oxidation of 2 mol of FeO to Fe2O3
−
(iii) reduction of 1 mol of 𝑀𝑛𝑂4 to Mn2+. [Ans. 1.93 x 105C, 96500 C, 4.825 X 105 C]
(3) How many hours does it takes to reduce 3 mol of Fe3+ to Fe2+ with 2.0Acurrent / (1F = 96500 C).
[Ans. 40.21 hours]
(4) In the electrolysis of acidified water, it is desired to obtain H2 gas at the rate of 1mL per second at STP.
What should be the current passed? (Ans. 8.616 A]
(5) Two electrolytic cells containing silver nitrate solution & dilute sulphuric acid were connected in series. A
steady current of 2.5 A was passed through them till 1.078 g of silver was deposited. (i) How much
electricity was consumed? (ii) What was the weight of oxygen gas liberated?
[Ag = 107.8 g mol-1, O = 16 g mol-1]
(6) How many moles of mercury will be produced by electrolysing 1.0M Hg(NO3)2 solution with a current of
2.0A for 3 hours. [Ans. 0.112 mol]
HOTS** (7) A current of 1.5A is passed through 500 mL of 0.25 M ZnSO4 solution for 1 hour with a current
efficiency of 90%.Calculate the final molarity if Zn2+ ions assuming volume of solution to be constant.
[Ans. 0.2 M]
**(8) An aqueous solution of an unknown salt of palladium is electrolysed by a current of 3.0 A passing for 1
hour. During electrolysis, 2.977g of palladium ions are reduced at the cathode. What is the charge on the
palladium ions in solutions? [Ans. Charge on Pd = +4]

Batteries:
These are source of electrical energy which may have more than cells connected in series.
A good quality battery, should be reasonably light. compact and its voltage should not vary appreciably
during its use.

TYPES:
Primary Batteries
In the primary batteries. the cell reaction occurs only once and after use over a period of time battery
becomes dead and cannot be reused again. Examples: (i) Dry cell or Leclanche cell, (ii) mercury cell etc

Secondary Batteries:
In secondary cell after ist use can be recharged by passing current through itin opposite direction so that it
can be reused again. A good secondary cell should have a large number of discharging & charging cycles.
Example: Lead Storage battery, (ii) Nickel-cadmium cell etc.

(i) Dry cell or Laclanche cell:

Anode - Zinc container; Cathode - Graphite rod surrounded by MnO2 powder (depolariser)
Electrolyte-Paste of NH4Cl + ZnCl2

(ii) Mercury cell

Anode-Zn-Hg amalgam, Cathode-Paste of (HgO + C)
Electrolyte-Moist paste of KOH - ZnO

Cathode reaction: HgO(s) + H2O(l) + 2e 🡪 Hg(l) + 2OH-(aq)

Anode reaction: Zn(Hg) + 2OH-(aq) 🡪 ZnO(s) + H2O + 2e
Net reaction: Zn(Hg) + HgO(l) 🡪 ZnO(s) + Hg(l)

# Cell Potential = 1.35 V

(Cell potential is constant during its life as the overall reaction
does not involve any ion in solution whose concentration does not
change during its life time.
# Used in hearing aids, watches, calculators etc

(i) Lead Storage battery (Secondary Batteries)

Anode-Spongy lead, Cathode-Grid of lead packed with PbO2
Electrolyte: 38% H2SO4 by mass
(ii) Nickel-cadmium storage cell
Anode – Cadmium, Cathode - Metal grid containing NiO2 Electrolyte-KOH solution

Fuel Cells
Galvanic cells use fuel energy of combustion of fuels like H2, CH4, CH3OH, etc., directly as the source to
produce electrical energy. The fuel cells are pollution free and have high efficiency > 70%, but costly, heavy
& has corrosive chemicals. Example: H2 – O2 fuel cells, CH4 – H2 fuel cell, CH3OH – H2 fuel cell etc.

The H2 – O2 fuel cell was used for providing electrical power in the APOLLO Space programme.

Hydrogen-Oxygen Fuel Cell

Electrodes-Made of porous graphite impregnated with catalyst (Pt, Ag or a metal oxide).

Electrolyte-Aqueous solution of KOH or NaOH

Oxygen and hydrogen are continuously fed into the cell.
…

Some application of electrochemistry

(1) Electro-refining of metals like Cu, Ag etc. (2) Electroplating of metals with Ag, Au, Cu, Cr
etc.
Example: Cathode: pure Cu,
Anode: impure Cu & Electrolyte: Cu2+(aq)

(iii) Corrosion:
Slow formation of undesirable oxidised compounds such as oxides, sulphides or carbonates at the surface
of metals by reaction with moisture, oxygen and other atmospheric gases is known as corrosion.
Example: (i) Fe : Rust (Fe2O3.xH2O) a reddish brown solid.
(ii) Cu: Cu(OH)2. CuCO3 green coating on Cu.
(iii) Al : Al2O3, dirty white coating
Factors Affecting Corrosion
1. Reactivity of metals: More reactive metals are corroded faster than less reactive metals
2. Presence of moisture and atmospheric gases like CO2, SO2, etc rate of corrosion increases.
3. Presence of impurities: increases the tare of corrosion.
4. Strains in the metal surface helps water droplets to accumulate where an electrochemical cell is formed.
5. Presence of electrolyte helps to increase the rate of electrochemical reaction.

Rusting of Iron- Electrochemical Theory (Rusting is an electrochemical process)

Corrosion of iron is called rusting of iron.
An electrochemical cell, also known as corrosion cell, is developed at the stains of iron surface in presence
of dissolved air (containing CO2, SO2 etc) in water droplets where a local cell is formed as given below:-

Anode- Pure iron Cathode- Impure Fe surface (containing dissolved air in water droplets)

Rusting of iron can be prevented by the following methods :

1. Barrier protection through coating of paints or by chemicals like bisphenol or electroplating with less
reactive metals.
2. Through coating by metal zinc called galvanisation or coating of surface with tin metal or chromium..
3. By the use of antirust solutions (alkaline sodium chromate or phosphate).
4. By cathodic or sacrificial protection in which a metal is protected from corrosion by connecting it to
another metal that is more easily oxidised e.g. Mg, Al, Zn etc. These metals corrodes itself by oxidation,
prevents Fe to oxidise & save from rusting. Here, these metals have lower standard reduction potential
values compared to that of iron.

Some concept based questions:

θ
(1) What are the signs of ΔG, equilibrium constant K & 𝐸𝐶𝑒𝑙𝑙 for an electrochemical cell.
(2) Why is a salt bridge or a porous plate not needed in a lead storage battery?
(3) Blocks of magnesium are often hanged in chains to the ocean going ships. Why?
(4) Rusting is prevented in an alkaline solution. Why?
(5) On the basis of the following data: (i) Co3+ + e 🡪 Co2+ : E0 = +1.82 V, (ii) 2H2O 🡪 O2 + 4H+ + 4e E0 = +1.23
V
Explain why Co3+ salts are unstable in water.
(6) Why a dry cell becomes dead after a long time even if it has not been used?
(7) Why does the cell potential of Mercury Cell remain constant throughout its life?
(8) How will the pH of brine (aqueous NaCl solution) be affected when it is electrolysed?
(8) Why is alternating current used for measuring resistance of an electrolytic solution?
(9) How will the pH of the solution be affected when acidified water (dil. H2SO4) is electrolysed?
(10) What advantage do the fuel cells have over primary and secondary batteries?
(11) Why on dilution, the molar conductivity of CH3COOH increases drastically, while that of CH3COONa
increases gradually?
**(12) Show that foe two half reactions having potentials E1 & E2 which are combined to give a third half
𝑛1𝐸1+𝑛2𝐸2
reaction having potential E3 is E3 = 𝑛3
where n1, n2 & n3 are no. of electrons involved in the half
reactions respectively.