index

Introduction Galvanic Cell

Representation of Cell, Reference Electrodes

Electrochemical Series

Nernst Equation

Electrolysis

Faraday’s Law of Electrolysis

Batteries

Conductance
Conductometric Titration
 Real life importance of electrochemistry

Electrochemistry holds significant importance in various real-life

applications. It’s crucial in battery technology for powering devices,
electric vehicles, and storing renewable energy. It’s also pivotal in
corrosion prevention, metallurgy, industrial processes like
electroplating, and even in biological systems, like nerve impulses and
muscle contractions.

College related importance of electrochemistry

Understanding batteries for electrical system. Corrosion prevention in

engineering materials. Energy storage principles for technologies.
Electroplating processes in industries.
 JEE Main Exam

Electrochemistry
Percentage Weightage (2019-23) 9.8%
Physical Chemistry
 JEE Advanced Exam
Physical Chemistry: Relative Weightage (2019-23)

Electrochemistry
13 %
Pre-requisite chapters

Mole Concept

Thermodynamics

Equilibrium
 Electrochemistry

Electrochemistry is the branch of physical chemistry which deals with

the study of inter conversions of chemical energy into electrical
energy and vice versa.
ELECTROCHEMISTRY

Electrochemical Cell Conductance

Galvanic cell Electrolytic

or cell
Voltaic cell
 Electrochemical cells

Galvanic cell or Voltaic cell Electrolytic cell

Chemical energy is converted into Electrical energy is converted into
electrical energy. chemical energy.

Eg: Daniel Cell, dry cell, lead Application: Electroplating, Refining of

storage battery metals

Spontaneous redox chemical Current drives a non-spontaneous redox

reaction (DG < O) generates current reaction (DG > O)
Anode → –ve charged Anode → +ve charged
Cathode → +ve charged Cathode → –ve charged
Electrode Potential

When a metal rod is dipped into its own ion solution, there occurs
either oxidation or reduction due to which a potential difference
exist between electrode (metal rod) and solution on interface (on
surface of metal), Called electrode potential

Electrode potential is a tendency to lose or to gain electron when an

electrode is dipped into its own ion solution.
Electrode Potential

Types of electrode potential

Electrode Potential

Oxidation Potential Reduction Potential

Oxidation Potential

Potential developed in oxidation half cell is called oxidation potential.

Metal(M)
+ ⊝
+
+ ⊝
+
+ ⊝
+
Oxidation + ⊝
+
M s M n+ aq. + ne− + ⊝
+
+ ++𝒏
𝑴+𝒏 𝐚𝐪. 𝑴+𝒏 𝐚𝐪. 𝑴+𝒏 𝐚𝐪. 𝑴 𝐚𝐪.
𝑴+𝒏 𝐚𝐪. EM/Mn+ = Oxidation potential 𝑴+𝒏 𝐚𝐪.

Higher the tendency to get oxidised higher will be oxidation potential

and Stronger the reducing agent.
Reduction Potential

Potential developed in reduction half cell is called reduction

potential.
Metal(M)
-  -
-  -

-  -
Reduction -  -
M +n aq. + ne− M(s) -  -
𝑴+𝒏 𝐚𝐪. 𝑴+𝒏 𝐚𝐪. - - - -
𝑴+𝒏 𝐚𝐪. EMn+ /M = reduction potential

Higher the tendency to get reduced higher will be reduction potential

and Stronger the oxidising agent.
Note

Oxidation potential and reduction potential of half cell are taken equal in
magnitude but opposite in sign.

For same electrode : Reduction Potential = —Oxidation Potential

Galvanic cell

In a galvanic cell, the gibbs energy of the spontaneous redox

reaction is converted into electrical work.

Electrical work obtained from a galvanic cell = DG = -q × V

= -n × F × ECell

DG = -n × F × ECell
Where,

n = no. of mole of electron

F = Faraday’s constant = Charge present on 1 mole of electron
= 96,500 coulomb
ECell = electrode potential or cell potential
Working principle of Galvanic cell (Daniel Cell)

Voltmeter
Zn rod e- I Cu rod
(-) (+)
Anode Cathode
(Oxidation) (Reduction)
Salt bridge

Zn(s)|ZnSO4(aq)||CuSO4(aq)|Cu(s)
 Working principle of Galvanic cell (Daniel Cell)

Oxidation half cell Reduction half cell

Or Or
Negative electrode Positive electrode
Or Or
Anode Cathode

Zn(s) Zn2+(aq) + 2e– Cu2+(aq) + 2e– Cu(s)

Complete Cell reaction : Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)

 Description of Galvanic Cell (Daniel Cell)

Anode Cathode
Reaction Oxidation Reduction
Sign -ve +ve
Direction of electron flow Out of cell Into cell

In Daniel Cell, with time mass of Zn rod decreases, concentration of

Zn2+ increases, mass of Cu rod increases, and concentration of Cu2+
decreases.
 SALT BRIDGE

It is an inverted u-shaped tube containing an electrolyte filled with

highly viscous (gel like) Solution with agar agar.

Function of salt bridge

 To maintain anode half cell and cathode half cell electrically

neutral.

 To minimize liquid junction potential.

 SALT BRIDGE

Characteristics of salt bridge

 Suitable electrolyte of salt bridge should have equal or nearly

equal ionic mobility of their ions E.g: KCl is a suitable electrolyte
for such purpose.

 Electrolyte of salt bridge should be inert towards the components

of anode / cathode parts (i.e, No ppt, No complexation reaction).

 Some other electrolyte may be used into salt bridge is KNO3,

NH4NO3 etc.
EMF of cell

ECell = ERP,cathode – ERP,anode

Or
ECell = ERP,cathode + EOP,anode
Or
ECell = EOP,anode – EOP,cathode
Note

For Spontaneous working of galvanic Cell, 𝐄𝐂𝐞𝐥𝐥 should be positive.

(DG)Cell = -n × F × ECell

Negative Positive

Electrode potential (Cell potential) is an intensive property.

 Application of electrochemical series

(8) Feasibility of redox reaction

Reactions at standard-state conditions DG Ecell

Spontaneous <0 >0

Non-Spontaneous >0 <0

Reversible and Equilibrium 0 0

Note DG = -nF𝐸𝑐𝑒𝑙𝑙
Representation of Cell,
Reference Electrodes
Representation of cell (IUPAC)

Represent anode part to the left side and cathode part at the
right side, both parts are separated by a double vertical line (∥)
representing presence of salt bridge.

Zn s ห Zn2+ aq || Cu2+ aq | Cu(s)

Anode half Cathode half

cell cell

Salt Bridge

𝑬°𝒄𝒆𝒍𝒍 = 𝑬°𝑪𝒖𝟐+ | 𝑪𝒖 + 𝑬°
𝐙𝐧ቚ 𝐙𝒏𝟐+
 Example

Given that the standard potentials (Eº) of Cu2/Cu and Cu/Cu are 0.34
V and 0.522 V respectively, the Eº of Cu2/Cu is : [JEE (Main) 2020]
(1) +0.158 V (2) 0.182 V (3) –0.182 V (4) –0.158 V

Solution

Ans. (1)
 Example
What is the standard reduction potential (E) for Fe3 → Fe ?
Given that : [JEE (Main) 2017]

Fe2 (aq) + 2e⊝ → Fe(s) ; 𝐸𝐹𝑒

𝑜
2⊕ /𝐹𝑒 = −0.47𝑉

Fe3 (aq) + e⊝ → Fe2(aq); 𝐸𝐹𝑒

𝑜
3⊕ /𝐹𝑒 2⊕ = +0.77𝑉

(1) +0.30 V (2) +0.057 V (3) –0.057 V (4) –0.30 V

Solution

Ans. (3)
Reference Electrodes

Note

Absolute value of electrode potential cannot not be determined.

rather relative electrode potential of various half cells are
measured w.r.t a reference electrode, called standard hydrogen
electrode (S.H.E) whose standard electrode potential at all temp.
is assigned zero.
 Reference Electrodes

1. Standard Hydrogen Electrode-S.H.E.

If S.H.E. electrode work as anode : If S.H.E. electrode work as

cathode :

Half Cell representation and Half Cell representation and

reaction reaction

Pt(s) | H2(g) 1 bar | H+ (1 M) H+ (1 M) | H2(g) 1 bar | Pt(s)

H2 (g ; 1 bar) → 2H+(aq ; 1 M) + 2e– 2H+(aq ; 1 M) + 2e–→H2 (g ; 1 bar)

°
Ereference = 0.00V °
Ereference = 0.00V
 Reference Electrodes

2. Secondary Reference Electrodes

The most commonly used reference electrode is the hydrogen

electrode. There are a few more reference electrodes (Ag-AgCl,
Calomel electrode etc.) available which are standardized using
standard hydrogen electrode (S.H.E)

1. Ag-AgCl electrode

2. Calomel electrode
Reference Electrodes

1. Ag-AgCl electrode

Electrode is a glass tube that contains

a paste of AgCl over a silver wire
immersed in a 1.0 M solution of KCl.
 Reference Electrodes

1. Ag-AgCl electrode

If Ag-AgCl electrode work as anode If Ag-AgCl electrode work as cathode

Half Cell representation and Half Cell representation and

reaction reaction

Ag(s), AgCl(s) | Cl– Cl–| AgCl(s), Ag(s)

Ag(s) + Cl–(aq) ⎯→ AgCl(s) + e– AgCl(s) + e– ⎯→ Ag(s) + Cl–(aq)

o
Ecell = 0.222 volt
Reference Electrodes

2. Calomel electrode

It is prepared by a Pt wire in contact with a paste Hg and Hg2Cl2

present in a KCl solution

Platinum Wire

(Hg & Hg2Cl2)

Paste

1M KCl Solution

Mercury
 Reference Electrodes

2. Calomel electrode

If Calomel electrode work as anode - If Calomel electrode work as cathode -

Half Cell representation and Half Cell representation and reaction

reaction

Hg(l) | Hg2Cl2(s) | Cl–(c M) Cl–(c M) | Hg2Cl2(s) | Hg(l)

2Hg(l) + 2 Cl– (aq) ⎯→ Hg2Cl2(s) + 2e– Hg2Cl2(s) + 2e– ⎯→ 2Hg(l) + 2 Cl– (aq)

o
Ecell = 0.280 volt
Electrochemical
Series
 Electro chemical series

Standard electrode potential (or standard reduction potential

(S.R.P.)) of various half cells are measured at 25°C w.r.t S.H.E. these
electrode potentials are arranged in increasing order of S.R.P., the
series formed is called electro chemical series.

Electrode Reduction Standard electrode

Reaction Reduction potential or S.R.P. (at 298 K)
Li+ + e → Li – 3.05
K+ + e– → K – 2.93
Ba+2 + 2e– → Ba – 2.90
Ca+2 + 2e– → Ca – 2.87
Na+ + e– → Na – 2.71
Mg+2 + 2e– → Mg – 2.37
Al+3 + 3e– → Al – 1.66
Mn+2 + 2e– → Mn – 1.18
H2O + e– → ½ H2 + OH – 0.83
 Electro chemical series
Electrode Reduction Standard electrode
Reaction Reduction potential or S.R.P. (at 298 K)
Zn+2 + 2e– → Zn – 0.76

Increasing strength of oxidising agent

Cr+3 + 3e– → Cr – 0.74
Fe+2 + 2e– → Fe – 0.44

Increasing strength of reducing agent

Cd+2 + 2e– → Cd – 0.40
Ni+2 + 2e– → Ni – 0.25
Sn+2 + 2e– → Sn – 0.14
Pb+2 + 2e– → Pb – 0.13
2D+ + e– → D2 – 0.01 V
2H+ + 2e– → H2 0
AgBr(s) + e– → Ag(s) + Br– +0.09 V
AgCl + e– → Ag + Cl– 0.22 V
Cu+2 + 2e– → Cu + 0.34
¼ O2 + ½ H2O + e– → OH– +0.401 V
I2 + 2e– → 2I– + 0.54
Q + 2H+ + 1e– → H2Q + 0.70
Electro chemical series

Electrode Reduction Standard electrode

Reaction Reduction potential or S.R.P. (at 298 K)
Hg2+2 + 2e → 2Hg + 0.79
Ag+ + e– → Ag + 0.80
Hg+2 + 2e– → Hg + 0.85
Br2 + 2e– → 2Br– + 1.08
¼ O2 + H+ + e– → ½ H2O + 1.23 V
Cl2 + 2e– → 2Cl– + 1.36
Pt+2 + 2e– → Pt + 1.20
Au+3 + 3e → Au + 1.50
Au+ + e → Au + 1.69
S2O8–2 + 2e– → 2SO4–2 + 2.0 V
F2 + 2e– → 2F– + 2.87
 Application of Electrochemical Series

(1) Electropositive nature of metal

The metal which has low standard reduction potential (S.R.P.) is more
electropositive.

In the E.M.F. series activity of metal decreases from top to bottom

and activity of non-metal increases from top to bottom.
 Application of Electrochemical Series

(2) Reactivity

The metals which have low S.R.P. value are highly reactive.

 Alkali metal and alkaline earth metal have low S.R.P. value, so they
are highly reactive and evolve H2 from cold water.

 Moderately electropositive metal are less reactive and evolve H2

from steam.

 Weakly electropositive metal are not able to evolve H2 from water.

“Example
“
1. Na + H2SO4 ⎯→ Na2SO4 + H2

1
2. Na + H2O ⎯→ NaOH + H 
2 2

3. Cu + dil.H2SO4 ⎯→ CuSO4 + H2 

Cu + conc.H2SO4 ⎯→ CuSO4 + H2O + SO2

 Application of Electrochemical Series

(3) Displacement of one metal by another metal

Metal present above in the E.M.F. series displace the metal
present below in the E.M.F. series from their salt solution.

“Example “
Zn can replace Cu2+ from an aq. solution of CuSO4. But Cu cannot
displace Zn2+ from solution.

Zn(s) + CuSO4(aq.) ⎯⎯→ ZnSO4(aq.) + Cu(s)

In the same way.
2AgNO3 + Cu ⎯⎯→ Cu(NO3)2 + 2Ag
CuSO4 + Ag ⎯⎯→ Ag2SO4 + Cu
 Application of Electrochemical Series

(4) Displacement of one non-metal by another non-metal

Non-metal present below in the E.M.F. series displace the

non-metal present above in the E.M.F. series from their compound.

“Example “
F2 can displace all halide ion from solution.

F2 + 2KCI ⎯→ 2KF + Cl2

Cl2 + 2KI ⎯→ 2KCl + I2

 Application of Electrochemical Series

(5) Oxidising & reducing powers

The metals placed above hydrogen in the electrochemical series are

strong reducing agents whereas non-metals placed after hydrogen,
are strong oxidising agents.

Metals which have low S.R.P. (more negative) value are strong
reducing agents (Li is strongest reducing agent in aqueous solution).

Non metal which have more positive value of SRP are good oxidising
agent.
Application of electrochemical series

Note

Cation having higher S.R.P. value will discharge first at cathode and
anion having low S.R.P. value discharge first at anode.

 K+ < Ca+2 < Na+ > Mg+2 < Al+3 < Zn+2 < Fe+2 < H+ < Cu+2 < Ag+ < Au+3

(Order of discharging at cathode)

4 < OH < Cl > Br < I

 SO−2 – – – –

(Order of discharging at anode)

 Example
The standard reduction potential (E°) of the following systems are
System E°(volts)
(i) MnO− + −
4 + 8H + 5e → Mn
2+
+ 4H2 O 1.51
(ii) Sn4+ + 2e− → Sn2+ 0.15
(iii) Cr2 O2− + −
7 + 14H + 6e → 2Cr
3+ + 7H O
2 1.33
(iv) Ce4+ + e− → Ce3+ 1.61
The oxidising power of the various species decreases in the order
(A) Ce4+ > Cr2 O2−
7 > Sn
4+ > MnO−
4 (B) Ce4+ > MnO− 2−
4 > Cr2 O7 > Sn
4+

(C) Cr2 O2−

7 > Sn
4+ > Ce4+ > MnO−
4 (D) MnO−
4 > Ce
4+ > Sn4+ > Cr O2−
2 7

Solution
 Example
Comparison between oxidizing/reducing nature of couples (standard condition)
Electrode potential data are given below.

(aq) + e ⎯→ Fe(aq) ; E° = + 0.77 V

Fe3+ – 2+

(aq) + 3e ⎯→ Al(s); E° = – 1.66 V

Al3+ –

Br2(aq) + 2e– ⎯→ 2 Br(aq)

–
; E° = – 1.08 V

Based one the data given above, reducing power of Fe2+, Al and Br– will
increase in the order :
(A) Fe2+ < Br– < Al (B) Fe2+ < Al < Br–
(C) Al < Br– < Fe2+ (D) Al < Fe2+ < Br–

Solution
 Nernst
Equation
Nernst equation

It gives relation between electrode potential and concentration of

electrolytic solution.

DG = DG0 + RT ln Q ••••••• (1)

From Equation (1),

–nFECell = –nFE0Cell + RT lnQ

0 2.303 RT
ECell = E𝐶𝑒𝑙𝑙 − log Q
nF

0.0591
ECell = 𝐸𝐶𝑒𝑙𝑙
0
− logQ
n
Calculation of equilibrium constant (Keq) and DG°

aA+ bB ⇌ mM + nN (reversible reaction)

From Nernst equation –

0 2.303RT
ECell = ECell − log Q
nF

At equilibrium, ECell = 0 and Q = Keq

0 0.0591
ECell = log K eq
n
Concentration
Cell
Concentration Cell

A galvanic cell in which cathode and anode halves are made up of

same material. Current flows in outer circuit due to difference in
concentration of solution or partial pressure of gases involves.

Example

Zn(s) | ZnSO4(aq.)(C1) // ZnSO4(aq.)(C2) | Zn(s) (C1  C2)

Note
0
ECell is always zero for a concentration Cell.
Concentration Cell
Anode (Oxidation) M(s) ⎯→ M+n (CA) + ne⊝

Cathode (Reduction) M+n (CC) + ne⊝ ⎯→ M(s)

Cell reaction M+n (CC) ⎯→ M+n (CA)

From Nernst equation,

0.0591
Ecell = 𝐸𝐶𝑒𝑙𝑙
0
– log Q (At 25°C)
𝑛

0.059 CA
ECell = 0 − log
n CC

Cell reaction is spontaneous if Ecell > 0 therefore CC > CA

 Concentration Cell

Pt | H2(P1 atm)| H(C1) // H (C2) | H2(P2 atm) | Pt

Anode (Oxidation) H2(P1 atm) ⎯→ 2H (C1) + 2e⊝

Cathode (Reduction) 2H (C2) + 2e⊝ ⎯→ H2(P2 atm)

Cell reaction H2 (P1 atm) + 2H (C2) ⎯→ H2 (P2 atm) + 2H (C1)

0.0591 𝐶2 2 ×𝑃
ECell = log 2 ×𝑃
1
2 𝐶1 2

Cell reaction is spontaneous if ECell > 0 therefore 𝐶2 2

× 𝑃1 > 𝐶1 2
× 𝑃2
 Example

For the following electrochemical cell at 298K,

Pt(s) | H2(g, 1bar) | H (aq, 1M) || M4(aq), M2(aq) | Pt(s)

𝑀2⊕ 𝑎𝑞.
Ecell = 0.092 V when =10x
𝑀4⊕ 𝑎𝑞.

𝑅𝑇
Given : 𝐸𝑀
0
4⊕ /𝑀2⊕ = 0.151V ; 2.303 = 0.059V
𝐹

The value of x is - [JEE (Advanced) 2016]

(A) –2 (B) –1 (C) 1 (D) 2

Solution

Ans. (D)
 Example
For the electrochemical cell, [JEE (Advanced) 2018]

Mg(s) | Mg2(aq, 1 M) | | Cu2 (aq, 1M) | Cu(s)

the standard emf of the cell is 2.70 V at 300 K. When the
concentration of Mg2 is changed to x M, the cell potential changes
to 2.67 V at 300 K. The value of x is____.
𝐹
(Given, 𝑅= 11500 KV–1, where F is the Faraday constant and R is the
gas constant, ln(10) = 2.30)

Solution

Ans. (10)
 Example

If the standard electrode potential for a cell is 2 V at 300 K, the

equilibrium constant (K) for the reaction

Zn(s) + Cu2(aq)  Zn2(aq) + Cu(s) [JEE (Main) 2019]

at 300 K is approximately. (R = 8 JK–1 mol–1, F = 96000 C mol–1)

(1) e160 (2) e320 (3) e–160 (4) e–80

Solution

Ans. (1)
 Example

At 298 K, the standard reduction potentials are 1.51 V for

MnO4⊝|Mn2, 1.36 V for Cl2|Cl⊝, 1.07 V for Br2 | Br⊝, and 0.54 V for
𝑅𝑇
I2|I⊝. At pH = 3, permanganate is expected to oxidize = 0.059𝑉 : −
𝐹

(1) Cl⊝ and Br⊝ (2) Cl⊝, Br⊝ and I⊝

(3) Br⊝ and I⊝ (4) I⊝ only [JEE (Main) 2015]

Solution

Ans. (3)
 Example

In the cell :
Pt(s) | H2(g, 1 bar) | HCl (aq) | AgCl(s) | Ag(s) | Pt(s)
the cell potential is 0.92V when a 10–6 molal HCl solution is used. The
standard electrode potential of (AgCl/Ag, Cl⊝) electrode is :
2.303𝑅𝑇
{given, = 0.06Vat298K} [JEE (Main) 2019]
𝐹

(1) 0.20 V (2) 0.76 V (3) 0.40 V (4) 0.94 V

Solution

Ans. (1)
 Example
How much will the potential of Zn/Zn2+ change, if the solution of Zn2+ is
diluted 10 times ?
(A) Increases by 0.03 V
(B) Decreases by 0.03 V
(C) Increases by 0.059 V
(D) Decreases by 0.059 V

Solution

Ans. (A)
 Metal- Metal sparingly soluble salt-salt anion electrode

It consists of a metal rod coated with metal insoluble salt and

dipped into an aqueous solution containing anion of insoluble salt.

If electrode function like an If electrode function like a

anode cathode
Representation Ag(s) | AgCl(s) |Cl-(aq.) Cl-(aq.) | AgCl(s) |Ag(s)

Reaction Ag(s) + Cl-(aq.) ⎯→ AgCl(s) + 𝑒 − AgCl(s) + 𝑒 − ⎯→ Ag(s) + Cl-(aq.)

 Metal- Metal sparingly soluble salt-salt anion electrode

Determination of standard potential (E ∘ ) of metal – metal sparingly

soluble salt-salt anion electrode

Example :

AgCl(s) + e− ⎯→ Ag(s) + Cl-(aq.) ∘

Ecell =?

Solution
∘ + ∘
Ag+(aq.) + e− ⎯→ Ag(s), EAg ∆G1∘ = −n × F × EAg
/Ag ,
+ /Ag

AgCl(s) ⎯→ Ag+(aq.) + Cl-(aq.), ksp(AgCl) , ∆G2∘ = −2.303RT log k sp

Cell reaction :
AgCl(s) + e− ⎯→ Ag(s) + Cl-(aq.) ∆G3∘ = ∆G2∘ + ∆G1∘
Metal- Metal sparingly soluble salt-salt anion electrode

∆G3∘ = ∆G2∘ + ∆G1∘

∘ ∘
−n × F × Ecell = −n × F × EAg+ /Ag − 2.303RT log K sp

∘ ∘
n × F × Ecell = n × F × EAg+ /Ag + 2.303RT log K sp

∘ ∘ 2.303RT
Ecell = EAg+ /Ag + log K sp
n×F

∘ ∘ 0.0591
Ecell = EAg+ /Ag + log K sp
n
 Example

Estimate the E ° reduction for Cu | CuS | S-2 electrode.

Given : Ksp of CuS = 8.0 × 10–36 ; ECu

°
| Cu2+ = −0.34 V

Solution

Ans. (–0.71)
Electrolysis
 Electrolytic cell

Electrolytic cell is the cell which converts electrical energy into

chemical energy. Cations move towards the negative electrode i.e.,
cathode and anion moves towards the positive electrode i.e., anode. This
process is known as electrolysis.
Electrolysis/ electrolytic cell

In electrolysis

Anode (+ve) : Oxidation take place

–ve ion of electrolyte deposited

Cathode (–ve) : Reduction take place

+ve ion of electrolyte deposited
Qualitative
Electrolysis
 (a) Qualitative electrolysis

Study of possible products formed at cathode and anode.

Factors affecting electrolysis and Products of Electrolysis

Nature of electrolyte

Molten Aqueous

Only the ions of the Water is also involved in

electrolyte are involved in electrolysis besides the ions of
electrolysis. electrolyte.
Nature of electrode

Inert Active

Those that do not involve in Those that also take part in

electrolysis and only conduct oxidation and reduction besides
electricity. conducting electricity.

Example : Platinum electrode, Example : Copper electrode,

Graphite electrode Nickel electrode

Note

When electrode is not mentioned, assume it to be Pt (inert electrode).

Discharge of ions at cathode

For species competing for reduction at cathode, higher reduction

potential or higher SRP greater will be its ease to undergo reduction
at cathode.

Based on discharge potential (reduction potential or SRP)

K+, Ca+2, Na+, Mg+2, Al+3, H2O(l), Zn+2, H, Cu+2, Ag+, Au+3

→ Ease of reduction at cathode.

Discharge of ions at anode

For species competing for oxidation at anode, higher oxidation

potential or higher SOP greater will be its ease to undergo oxidation at
anode.
Based on discharge potential (oxidation potential or SOP)

4 , NO3 , H2O(l), OH , Cl , Br , I
SO−2 − – – – –

→ Ease of oxidation at anode.

Electrolysis
(Inert Electrodes)
 Electrolysis using inert electrodes

Electrolysis of molten or fused electrolyte – NaCl

Cell reaction :

Anode : 2Cl⊝ ⎯→ Cl2(g) + 2e– [Oxidation]

Cathode : Na⊕ + e⊝ ⎯→ Na(s) [Reduction]

Overall reaction : 2Na⊕ + 2Cl⊝ ⎯→ 2Na(s) + Cl2(g)

 Note

Electrolysis of Anode Cathode

Molten KCl 2Cl⊝ ⎯→ Cl2(g) + 2e⊝ 2K+ + 2e⊝ ⎯→ 2K(s)

Molten MgCl2 2Cl⊝ ⎯→ Cl2(g) + 2e⊝ Mg+2 + 2e⊝ ⎯→ Mg(s)

Molten K2SO4 4 ⎯→ S2 O8 + 2e
2SO−2 −2 ⊝ 2K+ + 2e⊝ ⎯→ 2K(s)

Molten Na2S2O3 3 ⎯→ S4 O6 + 2e
2S2 O−2 −2 ⊝ 2Na+ + 2e⊝ ⎯→ 2Na(s)
 Electrolysis of Water

1. The electrode and overall cell reactions are

Anode : 2H2 O l → O2 g + 4H +aq + 4e−

⊝
Cathode : 4H2 O l + 4e− → 2H2 g + 4O H(aq)

⊝
Overall cell reaction : 6H2 O l → 2H2 g + O2 g + 4H +aq + 4O H(aq)

2. The net electrolysis reaction is therefore the decomposition of

water, a process sometimes used in the laboratory to produce small
amounts of pure H2 and O2.

2H2O(l) ⎯→ 2H2(g) + O2(g)

 Electrolysis of aqueous electrolyte - NaCl(aq)

Cathode :

O Na⊕(aq) + e– ⎯→ Na(s) ENa⊕ | Na = −2.71 V

⊝
P 2H2O(l) + 2e– ⎯→ H2(g) + 2O H(aq) 
EH 2
O | H2 = −0.83 V

Anode :

P 2Cl⊝(aq) ⎯→ Cl2(g) + 2e– 

ECl ⊝ | Cl = −1.36 V
2

O 2H2O(l) ⎯→ O2(g) + 4H⊕(aq) + 4e– 

EH 2
O | O2 = −1.23 V

⊝
Overall reaction : 2H2O(l) + 2Cl⊝ (aq) ⎯→ H2(g) + Cl2(g) + 2O H(aq)
 Oxidation of Cl⊝ is kinetically favourable but that of H2O is thermo-
dynamically favourable.

In order to make the oxidation of H2O kinetically feasible, some

additional voltage has to be applied. This addition voltage is called
overpotential or over-voltage.

In production of NaOH by Castner-Kellner cell. Na+ are reduced on

Hg(l) cathode.
In preference to liberation of H2 from H2O (due to overvoltage)

Note

At Hg(l) cathode Na+ reduced but H2 gas not liberate due to over voltage.
 Aqueous NaCl Solution (using Hg electrode)

At Cathode :

P Na⊕(aq) + e– → [Na(s) -Hg] (Sodium amalgam) 

ENa ⊕ | Na = −2.71 V

⊝
O 2H2O(l) + 2e– → H2(g) + 2O H(aq) 
EH 2
O | H2 = −0.83 V

At Anode :

P 2Cl⊝(aq) → Cl2(g) + 2e– 

ECl ⊝ | Cl = −1.36 V
2

O 2H2O(l) → O2(g) + 4H⊕(aq) + 4e– 

EH 2
O | O2 = −1.23 V
 Aqueous NaCl solution (very dilute using inert electrode)

Cathode :

O Na⊕(aq) + e– ⎯→ Na(s) 
ENa ⊕ | Na = −2.71 V

⊝
P 2H2O(l) + 2e– ⎯→ H2(g) + 2O H(aq) 
EH 2
O | H2 = −0.83 V

Anode :

O 2Cl⊝(aq) + e– ⎯→ Cl2(g) + 2e– 

ECl ⊝ | Cl = −1.36 V
2

P 2H2O(l) ⎯→ O2(g) + 4H⊕(aq) + 4e– 

EH 2
O | O2 = −1.23 V

When NaCl is highly dilute, there is a very less chance of Cl– (due to
their less availability) getting oxidized. So, instead H2O will get
oxidized to O2 gas.
 Electrolysis of aqueous electrolyte - AgNO3(aq)

1. Reactions possible at anode

2H2 O l → O2 + 4H +aq + 4e− ; °

EOxd,H = −1.23 V
g 2O

Please note that oxidation of NO3– is not possible as nitrogen is present

in its highest oxidation state.

2. Reactions possible at cathode

P Ag+ + e– → Ag ; E°Red = 0.80 V

⊝
O 2H2O(l) + 2e– → H2(g) + 2O H(aq) ; °
ERed,H = −0.83 V
2O
 Aqueous Na2SO4 solution

Cathode :

O Na⊕(aq) + e– ⎯→ Na(s) 
ENa ⊕ | Na = −2.71 V

⊝
P 2H2O(l) + 2e– ⎯→ H2(g) + 2O H(aq) 
EH 2
O | H2 = −0.83 V

Anode :

O 2SO42–(aq) ⎯→ S2O82–(aq) + 2e– 

ESO = −2.01 V
2− | S 2−
4 2 O8

P 2H2O(l) ⎯→ O2(g) + 4H⊕(aq) 

EH 2
O | O2 = −1.23 V

⊝
Overall reaction : 6H2O(l) ⎯→ 2H2(g) + O2(g) + 4H⊕ (aq) + 4O H(aq)
 Aqueous CuSO4 solution

Cathode :

P Cu2+(aq) + 2e– ⎯→ Cu(s) 

ECu2+ | Cu = +0.34 V

⊝
O 2H2O(l) + 2e– ⎯→ H2(g) + 2O H(aq) 
EH 2
O | H2 = −0.83 V

Anode :

P 2H2O(l) ⎯→ O2(g) + 4H+(aq) + 4e– 

EH 2
O | O2 = −1.23 V

O 2SO42–(aq) ⎯→ S2O82–(aq) + 2e– 

ESO = −2.01 V
2− | S 2−
4 2 O8

Overall reaction : 2H2O(l) + 2Cu2+(aq) ⎯→ 2Cu(s) + O2(g) + 4H⊕(aq)

Aqueous H2SO4 solution (using inert electrode)

Reactions possible at cathode

P 2H⊕ + 2e– → H2(g)

Reactions possible at anode

O 2SO42–(aq) → S2O82–(aq) + 2e– 

ESO 2− | S O 2− = −2.01 V
4 2 8

P 2H2O(l) → O2(g) + 4H⊕(aq) + 4e– 

EH 2
O | H2 = −1.23 V
 Aqueous HCOONa solution (using inert electrode)

Reactions possible at cathode

O Na⊕(aq) + e– → Na(s) 
ENi ⊕ | Ni = −2.71 V

⊝
P 2H2O(l) + 2e– → 2O H(aq) + H2(g) 
EH 2
O | H2 = −0.83 V

Reactions possible at anode

P 2HCOO⊝(aq) → H2(g) + 2CO2(g) + 2e–

O 2H2O(l) → O2(g) + 4H⊕(aq) + 4e–

⊝
Overall reaction : 2HCOO⊝ (aq) + 2H2O(l) ⎯→ 2H2(g) + 2CO2(g) + 2O H(aq)
Electrolysis of Anode Cathode

R–COONa(aq) R–R, CO2 H2, NaOH

CH2—COONa
CH2 CH2, CO2 H2, NaOH
CH2—COONa
Sodium Succinate

HC—COONa
HC CH, CO2 H2, NaOH
HC—COONa
Sodium maleate
 Electrolysis
(Active Electrodes)
Aqueous CuSO4 solution (using Cu electrode)

Reactions possible at cathode

P Cu2+(aq) + 2e– → Cu(s) 

ECu2+ | Cu = 0.34 V

⊝
O 2H2O(l) + 2e– → H2(g) + 2O H(aq) 
EH
2
O | H = −0.83 V
2

Reactions possible at anode

O 2SO42–(aq) → S2O82–(aq) + 2e– 

ESO 2− | S O 2− = −2.01 V
4 2 8

O 2H2O(l) → O2(g) + 4H⊕(aq) + 4e– 

EH 2
O | H2 = −1.23 V

P Cu(s) → Cu2+(aq) + 2e– 

ECu | Cu2+ = −0.34 V
 Aqueous AgNO3 solution (using Ag electrode)

Reactions possible at cathode

P Ag⊕(aq) + e– → Ag(s) 
EAg⊕ | Ag = 0.8 V

⊝
O 2H2O(l) + 2e– → H2(g) + 2O H(aq) 
EH 2
O | H2 = −0.83 V

Reactions possible at anode

O 2H2O(l) → O2(g) + 4H⊕(aq) + 4e– 

EH 2
O | O2 = −1.23 V

O NO3⊝(aq) → (No reaction)

P Ag(s) → Ag⊕(aq) + e– 
EAg|Ag⊕ = −0.8 V