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 Explain chemical reaction (Spontaneous and non spontaneous )

Chemical reaction Maximum non-expansion work that

can
be obtained from a process = − ∆G
Spontaneous Non-spontaneous
∆G < 0 ∆G > 0

By Arvind Arora
Electrical work is just electrons
running through the wire

Electrical Work = Charge × Potential difference

 What is Electrochemistry ?

Electrochemistry

A branch of Chemistry which deals with the study of relationship

between
electrical energy and chemical energy and interconversion of the
above By Arvind Arora
two forms.
What is Galvanic or voltaic cell ?
Galvanic or Voltaic Cell

The device in which Chemical energy is converted in to

Electrical energy by spontaneous redox reaction is called Galvanic cell
or Electrochemical cell or Voltaic cell.

In Galvanic cell
These cells have been named in
By Arvind Arora
Honorof Italian scientists
⇓ Luigi Galvani and Alessandro Volta
What is Galvanic or voltaic cell ?

–
Zn –

By Arvind Arora

Cu –
Cu2+
–
What is Galvanic or voltaic cell ?

By Arvind Arora
What is Salt Bridge and explain function of salt bridge ?

Salt Bridge
Salt Bridge is U-shaped tube which completes the circuit by
facilitating the flow of ions.
It contains semi-solid paste of some inert electrolyte like
KCl, KNO3, NH4Cl etc. in agar–agar & gelatin
By Arvind
Ends of the salt-bridge are plugged Arora
with glass wool
Ions of the electrolyte do not react with ions of electrode
solution.
Neither oxidized nor reduced at the electrodes.
What is Salt Bridge and explain function of salt bridge ?
Function of salt bridge
Transfer of electrons Anode cathode

By Arvind Arora
What is Salt Bridge and explain function of salt bridge ?

– – Function of salt bridge

At anode Zn Zn2+ + 2e–

Zn There is net positive charge around anode due to
increase in the concentration of cation (Zn2+)
The
By positive
Arvindcharge
Aroraaround anode
SO42– will prevent electrons to flow from it.
––
–
Zn2+
Zn
Zn2+

Zn2+ SO42– 1 M ZnSO4

2+
SO42– Zn solution
What is Salt Bridge and explain function of salt bridge ?
Function of salt bridge
– – – At Cathode Cu2+(aq) + 2e– Cu(s)
–
At the cathode there is increase in
concentration of anions (–ve charge) in
Cu the solution.

This negative charge around the cathode

By Arvind Arora
SO42– SO4
2– will prevent acceptance of electrons from
Cu2+2+
anode. The reaction, thus, would stop
SO42–
SO42– ∴ No current will flow
Cu 2+
SO42– Cu2+ 1 M CuSO4
Cu2+
2+
Cu SO42– solution
 Salt bridge prevents accumulation of charges and maintains flow of current

By Arvind Arora
K+ ions move to Cathode Compartment; Cl– ions move to Anode compartment.

The positive charge K+ is moving towards copper half cell

So you can see the Loop now
 Representation of a cell
Anode is represented on LEFT
Cathode is represented on RIGHT
Salt bridge is represented by double vertical lines
Single vertical line ( ) represents phase
boundary
Anode Cathode By Arvind Arora
Example Zn(s) ZnSO4 (aq) CuSO4 Cu(s)
OR
Zn(S) Zn2+ (aq) Cu2+ (aq) Cu(s)
SALT
ANODE BRIDGE CATHODE
What is Electrode potential ?
Electrode potential
The potential difference which facilitates the flow of electrons between two phases is
called electrode potential.
Types of Electrode potential
Higher is the value of electrode potential,
Reduction electrode potential Ered Higher is the tendency of reaction to take place
Oxidation electrode potential Eox
A2++ 2e– A Ered By Arvind Arora
A A2+ + 2e–Eox
Eox = – Ered
Reduction potential represents tendency to gain electrons
Oxidation potential represents tendency to lose electrons
Explain Standard Reduction Potential ?

Standard Reduction Potential : (E°red/E °)

Reduction potential of an electrode when the concentration of the ions in the solution
Is 1 mol/L (partial pressure for gases is 1 atm) and the temperature is 298 K is called
standard reduction potential

Concentration = 1M
For gases = 1 atm
Temperature = 298 K By Arvind Arora
E0 = E0red

If nothing is mentioned the type of electrode potential then it

is assumed to be reduction electrode potential
What is Cell Potential or EMF ?

Cell Potential or EMF

The difference between the electrode potential of the two half cells is known as
cell
potential or cell voltage.
Ecel = Eoxidation +
E
l = Ereduction
red, cathode By Arvind Arora
+ Eox, anode
= Ered, cathode – Ered , anode

E0cel = E0cathode – E0anode

l
 What is Cell Potential or EMF ?

Eg. EMF of Daniell Cell

Zn(s) + Zn+2(aq) + Cu electrode =

0
Cu+2(aq) Cu Cathode
E Cu2+,Cu or = 0.34 (s)V Zn electrode =
E00Cu2+⏐Cu or = –0.76 V Anode
Zn2+,Zn
E0Zn2+⏐Zn
E0cel = E0cathode – E0anode
l = E0Cu – E0Zn
By Arvind Arora
= 0.34 – (– 0.76)
E0Cel = 1.1V
l
 Electrochemical series :

The arrangement of various half reactions in decreasing order of S.R.P.

Strongest Oxidizing Agent Weakest Reducing Agent

F2 + 2e– 2F– 2.81 V

Increasing power of oxidizing agent

MnO4– + 8H+ + 5e– Mn+2 + 4H2 1.51 V

Cl2 + 2e– 2Cl– 1.36 V

Increasing power of reducing

Cr2O7–2 + +
14H + 6e –
2Cr +3
+ 7H2O 1.33 V
Will take some examples &
Br2 + 2e– 2Br– 1.09 V
explain strength of O.A &
Fe+3 + e– Fe+2 0.77 V
R.A.
I2 + e– 0.54 V
2H+ + e–
2I –
H2
By Arvind0V
Arora
Mg+2 + 2e– Mg –2.36 V
Na+ + e– Na –2.71 V

agent
K+ + e– K –2.93 V
Li+ + e– Li –3.05 V
Weakest Oxidizing Agent Strongest Reducing Agent
 Electrochemical series :

➢ Elements at higher position in the EMF series have higher Reduction Potential

➢ They can be easily reduced. Hence stronger OA

➢ Fluorine being at the top is strongest OA

➢ Also, elements at lower position inthe EMF series have lower Reduction Potential
values and Higher Oxidation Potential
By Arvind Arora
➢ They can be easily oxidized. Hence stronger RA

➢ Lithium being at the bottom acts as strongest RA

 What is relationship between Gibb’s Free energy change and emf of cell ?

Relationship between Gibb’s free energy change and EMF of cell

⇒ Electrical work = Decrease in free energy change

How do we calculate electrical work?

→ Only e– are flowing so we calculate total charge of 1 mol e–s.

Charge on 1 mol of electron By= Arvind

NA × e Arora
So we can say = 6.022 × 1023 × 1.6 × 10–19 C
≈ 96500 C = 1 faraday
1 faraday = Charge on 1 mol of electrons
 What is relationship between gibb’s Free energy change and emf of cell ?

Let ‘n’ moles of electrons required for balancing the redox reaction.
Charge of ‘n’ moles of electrons =q = nF

Let the EMF of the cell be = Ecell

What is the electrical work ?

Electrical work done = Charge × Potential difference

By Arvind Arora
nFE = –ΔG ΔG = –nFEcell
cell
What is relationship between gibb’s Free energy change and emf of cell ?

ΔG = –nFEcell

ΔG Ecell Condition of the process

–Ve +V Spontaneous
e
+Ve –Ve Non-spontaneous

0 0 By Arvind Arora
Equilibrium

For standard ΔG0 =

condition –nFE0cell
What are effect of concentration on emf of a cell ?

By Arvind Arora
NERNST EQUATION
 What are effect of concentration on emf of a cell ?

Effect of Concentration on EMF of Cell

Q :- Reaction Quotient
We learned that We also know that
ΔG = ΔG0 + RT ln Q ΔG = –nFE and
ΔG = ΔG0 + 2.303RT log10 Q ΔG0 = –nFE0
From both equation we get
Put the values of constants.
–nFE =–nFE0 + 2.303RT log10 Q
F = 96500 C
2.303RT
By Arvind Arora
R = 8.314 J/K–1mol–1
E = E0 - log10 Q
nF
T = 250C or 298 K
0.059
E= E – n logQ NERNST EQUATION
0
n = No. of electrons transacted in half reaction
 What are effect of concentration on emf of a cell ?

1 If standard condition are given Concentration = 1M

.
Q=1 E = E0 Partial Pressure = 1atm

At equilibrium
2 Q=K ΔG = 0 E=0
.
0.059
E0 = log K
n By Arvind Arora
0.059
E = E0 – n logQ
 Explain different types of Concentration cells

Concentration Cells : Electrolyte concentration cell

Silver-Silver ion electrode: Where we are considering Ag as cathode
and
Cathode Ag+(aq) + e– Ag(s
Anode as well.
:- C1M
)
Anode: Ag(s Ag+(aq) + e–
- C2M
)
+ +
By Arvind Arora
Overall: Ag (aq
Ag (aq
- C1M C2M
) )

E0cell =
?
 Explain different types of Concentration cells

Concentration Cells : Electrolyte concentration cell

Silver-Silver ion electrode: In this case E0cathode and E0anode will be
Cathode Ag+(aq) + e Ag(s same so
:- C1M – E0cell = 0V
)
Anode: Ag(s Ag+(aq) + e– Concentration in Nernst equation
- C2M will change
) By Arvind Arora
Overall: Ag+(aq Ag+(aq
- C1M C2M
) )

Nernst equatonn for this will be +

0 0.059 [Ag ](A)
Ecel = E cell
– log
n [Ag+](C)
 Explain different types of Concentration cells

0 0.059 [Ag+](A) Expressions for other examples will

Ecell = E cell
– log be
n [Ag+](C)
C2 Same, only number of electrons will
0.059
=0– log change
1 C1

0.059 C1
Ecell = log
1 C2 By Arvind Arora
General expression for concentrations cell :-

0.059 [Cathode]
Ecell = log
n [Anode]
 What are application of relationship between ΔG And E0 ?

Application : Relationship between ΔG and E0

1. Finding E0 for a half reaction

1 Fe3+(aq) + Fe(s) ; E01 Does this problem reminds of

3e – Hess’s law of thermodynamics
2 Fe2+(aq) + Fe(s) ; E02 ??
2e–
3 Fe3+(aq) + e– FeBy
2+
Arvind
(aq)
; E03 =Arora
?

In order to solve, Can we say

3= 1 – 2
E 03 = E 01 – E 02
 Application : Relationship between ΔG and E0

1. Finding E0 for a half reaction

1 Fe3+(aq) + 3e– Fe(s) ; E 01 Does this problem reminds of

Hess’s law of thermodynamics ??
2 Fe2+(aq) + 2e– Fe(s) ; E 02

3 Fe3+(aq) + e– Fe2+(aq) ; E03 = ?

In order to solve, Can we By Arvind

WeArora
have to use Gibb’s free energy change,
say as ΔG is extensive property.
3 = 1 – 2
ΔG03 = ΔG01 – ΔG02
E 03 = E 01 – E 02 OR
–F E03 = –3FE01 – (–2FE02)
As reactions are not balance
we can't use direct relationship. E03 = 3E01 – 2E02
 What are Electrolytic Cells ?
Electrolytic Cells :
An electrochemical cell in which
a non spontaneous reaction is forced to occur
by passing a direct current from an external source into the solution
is called an Electrolytic Cell. VBatter
y–
–
Used to carry out electrolysis reaction Anode + – Cathode
We supply electrical energy to carry out a
non-spontaneous reaction. By Arvind Arora (Graphi
– + (inert el
Electrical energy appears as increase in free energy. Cl Na

Molten NaCl
What are Electrolytic Cells ?

Electrolytic Cells :
Anion is attracted towards
anode.
Cation is attracted towards
cathode.

Anode 2Cl–(l) By2eArvind

Cl2(g)+ –
Arora
:
Cathode Na+(l)+ e– Na(l)
:
Overall 2Na+(l) + 2Cl–(l) 2Na(l) + Cl2 (g)
: Or 2 NaCl(l) 2Na(l) + Cl2 (g)
 What are different cases of electrolysis ?

Different cases of electrolysis

1) Molten NaCl or Molten PbBr2

2) Aqueous NaCl
3) Acidulated water
By Arvind Arora
4) Aqueous CuSO4 Solution
a) Pt
b) Cu electrode.
 Explain Faraday’s 1st law
Faraday’s Law

Fe+2(aq) + 2e– Fe What is charge of 1 mol of e– = 1F

2 mol of e–s discharges
(s) 1 mol Fe+2 1F will discharge 1 equivalent
1 1 mol of
discharg 1
mol Fe+2
F e– e 2
MW ⇓
∴EW of Fe+2 1 eq
= 2
Fe+3(a +3e– Fe (s) By Arvind Arora
3q)mol of e–s discharges 1 mol Fe+3
1F 1 mol of e– discharge 1
mol Fe+2
3
MW ⇓
∴EW of Fe+3 1 eq
3
=
Explain Faraday’s 1st law

Faraday’s First law of Electrolysis

Mass of any substance discharged should be proportional to the charge
passed.
Let ‘m’ mass discharged
‘q’ : Charge passed
Therefore, electrochemical
m∝q q = It equivalent
I = current is mass deposited or liberated
m ∝ It
t = time By Arvind Arora
due to passage of 1 C charge.
m = ZIt
If 1A current is passed for 1 second
Electrochemical
1C of charge is passed equivalent
Z=m of a substance
Explain Faraday’s 1st law

1C m
96500 C 96500 m

1F 1 eq of substance Equivalent weight (E)

96500 m = E

E
By Arvind Arora
m
= 96500

E
Z =
96500
What is Current efficiency ?

Current Efficiency :

It is defined as the ratio of the mass of a substance liberated by

a current to the theoretical mass as predicted by faraday law

Actual mass liberated

%C.E = × 100
Theoretical mass predicted
By Arvind Arora
.
 Faraday’s Second law

Current will flow though the entire circuit

i + – q is same on each electrodes. No. of F passed through
+ – + –
each electrode is same
Mass of substance discharged at electrode 1,2,3 and 4
is W1, W2, W3 and W4 respectively.
Equivalent masses are E1, E2,
1 2 3 4 EBy
3
, EArvind
4
Arora

i E
Faraday’s Second law

W1
so Will represent No. of equivalent and so on.
E1
No. of equivalent = No. of Faraday

W1 W2 W W4
No. of Eq = = = 3 =
E1 E2 E3 E4
By Arvind Arora
Statement of Second Law:
The amounts of different substances liberated by the
same quantity of electricity passing through the
electrolytic solution are proportional to their chemical
equivalent weights.
 What are Batteries?

BATTERIES
Batteries are arrangement of galvanic cells connected in series to obtain a higher
voltage.
Primary Batteries
Which can be used only once and can’t be recharged.
Examples Leclanche cell (Dry cell), Mercury cells
also called as irreversible cells.
(which means that they can beBy onlyArvind
used asArora
galvanic
cells and not as electrolytic cells).
Secondary Batteries
Which can be used more than once i.e. it can be
recharged. Lead- acid battery, Li-ion battery,
Examples
Ni-Cd battery (Reversible cells).
 Primary Batteries Dry Cell (Leclanche cell)

Anode Zn container Cathode Carbon (graphite) rod surrounded

by powdered MnO2 and C
Electrolyte Moist paste of NH4Cl and ZnCl2

Reactions Anode
Zn(s) Zn2+(aq)+ 2e–
Cathode
By Arvind Arora
MnO2(s) + NH4+(aq) + e– MnO(OH)(s) + NH3(aq)
Manganite
Cell Reaction
Zn(s) + 2MnO2(s) + 2NH4+(aq) [Zn(NH3)2]2+(aq) + 2MnO(OH)(s) EMF = 1.5V
Secondary Batteries Nickel – Cadmium Storage cell

Cathode Metal grid Containing NiO2

Reaction Anode Cd
s
Anode Electrolyte KOH
Cd(s) + 2OH–(aq) Cd(OH)2(s)+ 2e– solution

Cathode
NiO2 + 2H2O(l) + 2e– Ni(OH)2(s) + 2OH–(aq)
By Arvind Arora
Cell Reaction
Cd(s) + NiO2(s) + Ni(OH)2(s) + Cd(OH)2(s)
2H2O(l)
EMF ≈ 1.4 V
LEAD – STORAGE BATTERY

6 Voltaic cells connected in

series

By Arvind Arora
Cathode : Grid of Pb packed with PbO2
Anode : Pb
Electrolyte : 38 % w/w H2SO4
 LEAD – STORAGE BATTERY
Battery is acting
Discharging reaction :- Anode :
like a galvanic cell
Pb(s) + SO42–(aq) PbSO4(s) + 2e– E0 = – 0.36 V
Cathode :
PbO2(s) + SO42–(aq) + 4H+(aq) + PbSO4(s) + 2H2O(l) E0 = 1.68 V
2e–Reaction :
Cell
Pb(s) + PbO2(s) + 2H2SO4(aq) 2PbSO4(s) + 2H2O(l) E0 = 1.68 – (–0.36) = 2.04V

Charging Reaction Anode :

:-
By Arvind Arora
2–
PbSO4(s) + 2H2O(l) PbO2(s) + SO4 (aq)
+ 4H+(aq) +
2e–
Cathode
Battery is acting like
: PbSO4(s) + 2e– Pb(s) + SO42–(aq) a electrolytic cell
Cell Reaction :
2PbSO4(s) + 2H2O(l) Pb(s) + PbO2(s)
 FUEL CELLS

(BACON CELLS) Galvanic cells

– e– e– + Electrodes Porous carbon electrodes
H2 O2
e– e
:- containing metallic catalyts
Electrolyte Concentrated aq. NaOH
Porous carbon electrodes
OH–
Containing metallic
:- solution (or KOH)
e e
KOH catalyst
e e
H2O H2O

Cathode
:O
2(g
+ 2H2O(l + 4e By4OH
Arvind
–
(aq
; E°Arora
= 0.40V
–
Anode
) ) )
: 2H + 4OH–(aq 4H2O(l + 4e ; E° = –0.83V
2(g
–
Cell
) Reaction) )
: 2H + O2(g 2H2O(l E°cell = 1.23 Efficiency of fuel cell =
2(g
) ) ) 70%
What is Conductance ?

Conductance
Any solution having an electrolyte contains cations and anions which can flow
through the solution between the electrodes. This flow of ions is not a free flow
but has some resistance associated with it.

l ρ : Resistivity or specific resistance

R =ρ l : length of resistor
A
A : Area of cross-section of resistor
Unit: ohm (Ω)
By Arvind Arora
Conductance is the reciprocal of the resistance.
1 1 A It is denoted by G
G= = ρ× –1
R l Unit = mho (Ω ), Siemens (S)

κ= 1 κ(Kappa) = conductivity or specific conductance

ρ
What is Conductance ?

l l
κ =G× is cell constant
A A

Specific conductance = Conductance × Cell constant

S S By Arvind Arora
Unit of κ =m or cm
 Conductivity cell

Batter
y
Non
conducting
plates Metal
Plates
Area of this phase
(A)
By Arvind Arora
l
A
Will be same for a Conductivity cell
A l
G= κ × κ will change and κ represents
l
the nature of electrolyte. So….
 Conductivity cell
Batt
Non ery
l conductin
κ= G×
A g Metal
We can say plates Plates
Amount of current will depend upon nature of electrolyte
Higher is the value of κ, more is its conductance
l
l By Arvind Arora
= constant Area of this
A
phase (A)
If A= 1cm2 & l=1cm Volume of electrolyte =1cm
3

κ=G
κ is the conductance of 1cm3 of electrolyte solution
 Types of conductance:

1) Molar conductance (Λm): It is conductance of 1 mol of Electrolyte solution

2) Equivalent conductance (Λeq): Conductance of 1eq. of Electrolyte solution

By Arvind Arora
 Molar Conductance

1000 × κ S – cm2
Λm =
M mol

Equivalent conductance

1000 × κ S – cm2
Λe = e Arvind Arora
N By
q q
Relation between Λm and Λeq
Λe M 1 M×Z=N
= =
Λ
q m N Z
Λm
Λe =
Z
What are effect of dilution on Λm And κ ?

Effect of dilution on Λm and κ

Arrhenius Arrhenius has given an equation to calculate the degree of

Equation dissociation

Λm = Molar conductance of the

α =
Λm By Arvind Arora
electrolyte at given conc.
Λ m∞
Λm∞ = Molar conductance of the
electrolyte at infinite dil.
at infinite dilution, electrolyte is 100%
ionized.
 For weak electrolyte as we
For strong
increase electrolyte
dilution the no. of ions
∞
In this equation as C increases Λm go Λ
on = Λm – b√csignificantly
m increasing
is like and
decreases y = mx + c
hence conductance increases
equation of a straight
Weak line
electrolyte
(CH3COOH)
Λ∞m
Λm Where slope = –b
Strong
electrolyte
and y intercepts = Λm∞
(KCl,NaCl)
By Arvind Arora
Λm = Λ∞m – b√ c
Effect of dilution on conductivity (specific conductance )
Specific conductance (κ) = conductance of 1cm3 of solution
On dilution, no of ions per unit volume decreases, κ decreases on
dilution
What is Kohlrausch’s law ? Kohlrausch’s Law

Λm of electrolytes increases with

dilution till a limiting value,
Λm∞ is obtained at infinite
dilution
In this limit, the positive and
negative ions may be thought of
as behavingBy Arvind Arora
essentially
independent
of each other
What is Kohlrausch’s law ? Kohlrausch’s
Law
At infinite dilution the total conductance of a solution is a sum of cationic and
anionic conductance. This is valid because at infinite dilution the ions are far
away from each other and there is no effect of their interactions on the movement of
the ions.
n+ : No of cations
n– : No of anions
By Arvind Arora
Λ∞+ : Molar conductance at infinite dilution for cation
Λ–∞ : Molar conductance at infinite dilution for anion
ΛT∞ = n+Λ+∞ + n–Λ–∞
ΛT∞ : Total Molar conductance at infinite dilution
 Exampl
e
∞ ∞
NaCl ΛT∞ = Λ (Na+ + Λ (Cl – )
MgCl2 ; ΛT∞ = )Λ∞(Mg2+) + 2Λ∞(Cl –
)
CH3COOH ΛT∞ = Λ∞(H +) + Λ∞(CH3COO–
; ∞
NaKC2O4 ; ΛT∞ = Λ (Na+ + )Λ∞(K + ) + Λ∞(C2O42–
) ∞
Na2SO4 ; ΛT∞ = 2Λ (Na+ + Λ∞(SO42–)
K2SO ⋅ Al2(SO4)324H)2O ; By) Arvind Arora
(Potash Alum) ∞
4 ΛT∞ = 2Λ (K+ + 2Λ∞(Al 3+ + 4Λ∞(SO42–
) ) ) infinite
For calculating equivalent conductance at
dilution
First calculate the molar conductance at infinite dilution
and then divide it by Z- factor of overall compound
 Arvind Arora

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