ELECTROCHEMISTRY

BY KAVITA YADAV

Vidyanidhi Junior College Of Science

1
Electrochemistry is the branch of chemistry
which is concerned with the
interconversion of chemical and electrical
energy.

2
 What is electric conduction?
 Electric current represents a charge transfer

 A charge transfer or flow of electricity occurs through a

substance called conductors.

3
4
 Types of conduction

Metallic or electronic Electrolytic or

conduction ionic conduction

Flow of electrons present in Charge transfer occurs due to movements

conduction band of metals of ions through molten electrolytes or aq.
under the influence of solution of electrolytes
applied electric current

5
6
 Difference between Electronic Conductors and
Electrolytic Conductors
Electronic conductors Electrolytic conductors
The flow of electricity takes place by direct The electron transfer takes place by the
flow of electrons through the conductors. migration of ions of the electrolyte.

Conduction does not involve transfer of Conduction involves transfer of matter

matter

No chemical change Chemical changes are involved

Resistance of conductor increase and Resistance of conductor decreases and
conductivity decrease by increase in conductivity increases by increase in
temperature temperature

Conductance of metallic conductor is very Conductance of electrolyte is

high comparatively low

Ex:- solid or molten metals such as Al, Cu, Ex:- aq. Solutions of acids , bases or salts
etc.

7
 Electrolytes: compounds that conduct electricity in molten or in
aqueous solution

Strong electrolyte Weak Electrolytic

Electrolyte dissociate Electrolyte dissociate to very small extent

completely in aq. solution and in aq. solution and hence show lower
hence conductivity is high conductivity

Ex:- ionic salts , strong acids and bases Ex:- weak acids and weak bases
8
No dissociation to form Complete dissociation Low degree of
ions to form ions dissociation to form ions
Hence non conductivity Hence high conductivity Hence low conductivity
9
 Electrical Resistance

10
Electrical conductance of solution -G
V (Volt )
 According to Ohm’s law R (Ohm) 
I (ampere)

 Electrical resistance is ohm denoted by

Symbol (omega) thus  = VA-1

 The electrical conductance G of a solution is

reciprocal of resistance

 G = 1/R

 SI unit of G is siemens denoted by S which is -1 and

the dimensions are expressed in m. 11
 Conductivity - k

 Electrical Conductance of sample (G) decreases as

its length increases with its area of cross section
a a
 ∴ G a or G  k
l l
l 1 l 1
k G   because G 
a R a R
 Proportionality constant k is called conductivity of
the conductor.
 If l = 1m and a = 1m2 then k = G
 ∴Conductivity is defined as the conductance of unit
cube of material.

12
 Resistivity - 
 Also l
R
a
 Or l
R 
a
 Where  is called resistivity for specific resistance of
the conductor.
a
ρ=R×
l
 If l = 1m, a =1m2
 =R

13
………….Lets try to relate conductivity (k) with
resistivity ()

l 1 l
R  And k  
a R a

SI unit of conductivity (k) = S m-1 OR -1 m-1

1 When dimensions are in cm then…
 k= -1 cm-1


Thus conductivity is inverse of resistivity.

14
 Molar Conductivity
High concentrated
More ions Higher conductivity
solution

Low concentrated
Less ions Less conductivity
solution

Introduced new
term
George Kohlrausch Denoted by ʌ
MOLAR
CONDUCTIVITY

Molar conductivity is defined as the electrolytic conductivity k

divided by the molar concentration C of the dissolved electrolyte.

k SI unit S m-1
Unit of ʌ is..S m2 mol-
Λ= 1
C Mol m-3
15
 Molar Conductivity Unit

SI

CGS

16
 Molar
Conductivity
conductivity
It is the measure of
ability of an electrolytic
electrolyte’s ability to
solution measured per
Definition conduct electricity
unit molar concentration
through it

Unit S/m OR -1 /m Sm2/mol OR -1 cm2 /mol

Molar concentration of Molar concentration of

Molar Conc.
solution is not considered solution is considered

helps to determine
Mainly used to determine the
Uses presence of conductive ions
dissociation constant of
weak electrolyte as a
in the solution function of concentration in
Ostwald’s law of dilution
17
Variation of Molar conductivity with concentration
 Molar conductivity reaches the limiting value at
0.001M and 0.0001M
 Limiting value means that further dilution will
not affect the molar conductivity
 The maximum limiting value of molar
conductivity is the conductivity at zero
concentration or infinite dilution
Λ0
 It is denoted as
 ∴ Λ= Λ 0 + a c
 WhereΛ a is constant , c is molar concentration and
0
is molar conductivity at zero concentration.
18
 Kohlrausch law of Independent migration

At infinite dilution, each ion migrate

independently of its co-ion and makes
its own contribution to the total molar
conductivity of an electrolyte
irrespective of the nature of other ion
with which it is associated.

0 0
Λ 0 =λ +λ+ -

Where ℷ+ and ℷ- are the molar

conductivities of cation and anion
respectively at infinite dilution 19
• In general for an electrolyte,
BxAy giving x number of cations and y
number of anions,

0 0
Λ 0 =xλ +yλ+ -

20
 Application of Kohlrausch law

Calculation of molar conductivity of solution at infinite

dilution

Calculation of degree of dissociation ∝ = ʌ / ʌ₀

Calculation of dissociation constant for weak electrolyte

K = ∝2 C/1-∝ OR K = ʌ2 C/ ʌ₀ (ʌ₀ - ʌ)

Calculation of ionic product of water (Ksp),

solubility and solubility product of water of
sparingly soluble salt
21
How to determine conductivity of a
solution??????????????
Lets first try to understand the basics by
knowing……………..
What is conductivity cell?
What is cell constant?
What are the steps followed to calculate
conductivity of given solution?

22
 So lets begin with………………
What is conductivity cell???????

23
 Conductivity cell

The conductivity cell

consists of a glass tube
with two platinum plates
coated with a thin layer of
finely divided platinum
black.
This is achieved by the
electrolysis of solution of
chloroplatinic acid.
The cell is dipped in a
solution whose resistance
is to be measured.

24
Lets move ahead to understand about ……….
Cell Constant

25
 Cell Constant and
conductivity
We know that conductivity of an electrolytic solution is
given as 1 l
k  
R a

For a given cell l/a is cell constant

l
Cell constant =
a

SI Unit of cell constant is m-1 and cm-1

∴ Conductivity of solution can be given as:
Cell constant
k =
R 26
Three steps to determine molar conductivity

1 • Determination of Cell
constant

• Determination of
2 conductivity of given
solution

3 • Determination of Molar
Conductivity

27
 Determination of cell constant using
reference solution KCl of Concentration
0.1M or 0.01M and Wheatstone Bridge
Principle

28
According to Wheatstone bridge principle
R(solution) Rx
=
R(AC) R(BC)

The resistance of a conductor is proportional to its length.

Hence, R(AC) = length AC and R(BC) = length of BC

R(solution) Rx
=
l(AC) l(BC)
l(AC)
R(solution) = R ×
l(BC)
By measuring the lengths of AC and BC and
knowing Rx , the resistance of KCl solution can be
calculated.
The cell constant is given as ………
b=kR b……cell constant
k……conductivity of KCl
hence cell constant can be calculated.
29
Determination of conductivity of
given solution

30
 The reference solution KCl is then replaced by
the solution whose conductivity is to be
determined

 By using the wheatstone bridge principle the

resistance (R) of the given solution is
determined.

 Condutivity of the given solution can be

calculated by using the formula,
k=b/R 31
 Since concentration of the solution is already
known
 ∴Molar conductivity can be
calculated as
k
Λ=
C

32
 Lets Revise all the Formulae
V(Volt)
Resistance R(Ohm) =
I(ampere)
1
Electrical conductance G =
R
l 1 l
Conductivity k = G or k = ×
a R a
a
Resisitivity ρ = R ×
l
1
 k=

k
Molar Conductivity Λ =
C

OR Λ= Λ 0 + a c where Λ 0 is conductivity at zero concentration

33
 Λ 0 = xλ 0+ + yλ -0 where λ o+ and λ -0 are molar conductivities
of cation and anion at zero concentration

OR Λ 0 = xλ 0+ +yλ -0 x and y are

number of cations and anions of electrolyte

Cell Constant b = k . R

34
Lets solve some
numerical…

35
A conductivity cell has two electrodes
20 mm apart and of cross section
area 1.8 cm2 . Find the cell constant
Solution:
Given: Distance between two electrodes = l = 20 mm
= 2 cm
Cross section area = a = 1.8 cm2
Cell constant = b = ?

l 2 -1
b= = = 1.11cm
a 1.8
-1
cell constant = 1.11cm
36
A conductivity cell filled with 0.1 M KCl gives at 25°C a resistance of 85.5 ohms
and conductivity of 0.01286ohms-1. The same cell filled with 0.005 M HCl gives
a resistance of 529 ohms. What is the molar conductivity of HCl solution.

Conductivity of HCl solution,

RKCl = 85.5
b
kHCl =
kKCl = 0.01826ohm-1 cm-1 RHCl
1.1
C (HCl) = 0.005M =
529
R (HCl) = 529 ohms = 2.08×10-3ohm -1cm -1
Find Molar conductivity = ʌ
=? cell constant Molar Conductivity of HCl solution,
Conductivity =
resistance kHCl × 1000
Λm(HCl) =
b C
kKCL =
RKCl 2.08×10-3 × 1000
=
b = kKCl × RKCl 0.005
b = 0.01286 × 85.5 =416 ohm -1 cm 2 mol-1
b = 1.1cm -1 37
38
 e-

AA + Oxidized state

Loss of electron is called oxidation

39
 e-
Na +
Na Oxidized state

oxidation number increased from 0 to +1

40
 e-

B +
B Reduced state

oxidation number decreased from +1 to 0

41
 e-

Zn2+
Zn Reduced state

e-
oxidation number decreased from +2 to 0

42
 e-

red
u ce
stat d
e- e
Oxid
A
iz
A+ stat ed
e B+
B

43
 OXIDATION REDUCTION

OXIDATION IS LOSS REDUCTION IS GAIN

OIL RIG

44
Lets check what we learned…….

Lets check our answers …….

45
 Electrochemical cells

Electrolytic
Voltaic cells
cells

46
Electrolysis of Fused NaCl

47
 Reduction half reaction at cathode
Na+ (l) + e- Na(s)

Oxidation half reaction at anode

2Cl- (l) + 2e- Cl2(g)

Net cell reaction

2Na+ (l) + 2e- 2Na(s)
2Cl- (l) + 2e- Cl2(g)

Cl2(g) 2 Na+ (l) + 2Cl- (aq) 2Na(s) + Cl2(g)

Na(s)
Aqueous NaCl
Na+
Cl-

Graphite electrodes 48
 Electrolysis Of Aqueous NaCl
 The water involved in electrolysis of aqueous NaCl, leads to
electrode reactions that differ from electrolysis of molten
NaCl.
 (A) Reduction half reaction at cathode: At cathode, two
reduction reactions compete.
 i) the reduction of Na+ ions as in case of molten NaCl.
 ii) reduction of water
 The standard potential for the reduction of water is higher
than that for reduction of Na+. This implies that water has
much greater tendency to get reduced than the Na+ ion.
Hence reaction (ii), that is, reduction of water is the cathode
reaction when the aqueous NaCl is electrolysed.
 2 H2O(l) + 2e- H2(g) + 2OH-(aq)
49
 (B) Oxidation half reaction at anode: At anode there will be
competition between oxidation of Cl- ion to Cl2 gas as in case
of molten NaCl and the oxidation of water to O2 gas. From
experiments it is proved that the gas produced at anode is
Cl2 and not O2
 2Cl-(aq) Cl2(g) + 2e-
 Overall cell reaction

50
APPLICATIONS

51
Quantitative Aspects Of
Electrolysis

52
Faraday’s first law of electrolysis: The amount of substance that
undergoes oxidation or reduction at each electrode during
electrolysis is directly proportional to the amount of electricity that
passes through it.

According to the law: W ∝ Q

53
54
Steps to calculate mass of the
substance produced during electrolysis
by Faraday’s first law of electrolysis

Step 1- Calculation of quantity of electricity passed

Step 2 – Number of moles of electrons passed

Step 3 – Number of moles of product formed

Step 4 – Mass of product formed

55
Step 1- Calculation of quantity of electricity passed
The amount of charge passed through the cell (Q) = Current X Time
= Ixt
Coulombs = Ampere X Seconds
Q=IXt

Step 2 – Number of moles of electrons passed

The charge carried by one mole of electronis 96500 C.

96500 C (F)  1 mol of electrons
Q Q
Q=  moles of electrons
96500 F

56
Step 3 – Number of moles of product formed

Mole ratio = Number of moles of product formed at the electrode

Number of moles of electron involved in half reaction

Step 4 – Mass of product formed

Q
Moles of product formed = × Mole ratio
F
Q
Mass of product formed = × Mole ratio × molar mass of substance
F

57
 Faraday’s second law of electrolysis
When the same quantity of electricity is passed through different electrolytes,
arranged in series , then the amount of substances produced by oxidation or
reduction at the respective electrodes are directly proportional to their
chemical equivalent masses .

M1 E1
=
M2 E2

58
Deducing mathematical expression for Faraday’s second
law

For substance A mass deposited W1

For substance B mass deposited W2
W1
Number of moles of A =
M1
W2
Number of moles of B =
M2

Now from half cell reactions at two electrodes,

Moles of A produced = Moles of electron passed × mole ratio of A in half reaction

Moles of B produced = Moles of electron passed × mole ratio of B in half reaction

Hence Faraday's second law can be expressed as:

Moles of A produced mole ratio of A in half reaction

Moles of B produced mole ratio of B in half reaction

59
60
 When the tendency
of metal atom to go
into the solution
delectronation leaving electrons on
the metal plate is
higher

When metal plate

is dipped in its salt
solution
When the tendency of
positive ions in the
solution to deposit on
electronation the metal plate by
removing electron is
higher

61
 Electrode potential
It is defined as the difference of electrical potential
between metal electrode and solution around it
under equilibrium condition.

Cell potential Ecell = Eoxi(anode) + Ered(catode) 62

 Standard cell potential or
standard emf
The standard cell potential is the potential of the galvanic cell
when all the substances involved in the cell reaction are in
their standard state is solutions are at 1M concentrations,
gases at 1M at 1 atm pressure and solids and liquids are in
pure form with all at 25°C.
Standard Cell potential E°cell = E°oxi(anode) + E°red(catode)
According to IUPAC conventions standard reduction potential of
an electrode is simply called standard potentialof the
electrode..
∴ the standard cell potential is written in terms of standard
reduction potentials of both the electrode.
Standard Cell potential E°cell = E°cathode(RHE) - E°anode(LHE)

63
 Nernst Equation
• The cell potential and electrode potential depends on
temperature, concentration of solutesand partial pressure of
gases
• This dependence of potential is given by Nernst equation:
RT
E = E0 - lnQ
nF

[products]
where Q is reaction quotient given by Q =
[reactants]
RT [products]
E = E0 - ln
nF [reactants]
0 2.303RT [products]
E=E - log
nF 10 [reactants]

0 0.0592 [products]
E=E - log
n 10 [reactants]
64
 Gibbs energy changes for cell
reactions
• Electrical work done in galvanic cell:
• Electrical work = amount of charge X cell potential
= nF x Ecell
=nFEcell
Reversible electrical work done in galvanic cell is equal to
decrease in Gibbs energy
Electrical work = -∆G
∴ - ∆G° = nFE°cell OR ∆G° = -nFE°cell
E° = ∆G° / nF ……. ∆G° is standard Gibbs
enrgy change.

65
Standard cell potential and equilibrium constant

• ∆G° = -nFE°cell and

• ∆G° = -RTlnK
• Combining two eqn:
• -nFE°cell = -RTlnK
 RT
E = lnK
nF
2.303RT
= log10 K
nF
 0.0592
E = log10K at 25 C
n
66
 METAL ELECTRODE
HALF CELL
Cu|CuSO4
Cu

cu
Aqueous solution cu
cu
containing metal cu
ions Cu2+ cu
cu cu
SO42- cu cu
CuSO4
Cu2+ SO42-

67
 METAL ELECTRODE
HALF
HALF CELL
CELL ?????
Zn|ZnSO 4

Zn

Zn Zn
Zn
Zn
Aqueous solution Zn
containing metal Zn
ions Zn2+ Zn
Zn
SO42- Zn

ZnSO4
Zn2+ SO42-
68
EXERCISE:- represent the half
cell
 Copper metal dipped in copper chloride of 0.1 M
 Nickel metal dipped in nickel sulphate of 1 M
 Magnesium dipped in magnesium chloride of 0.01M
 Hydrogen gas of 1 atm passed through solution of
hydrochloric acid of I M concentration

69
 Can you identify what is common in the
given two examples below???????

Chemical energy is Chemical energy is

converted in electrical converted in electrical
energy energy
70
Daniel Cell / Voltaic CELL

71
 Potential difference is created
Switch

ON

Salt Bridge

Cl- K+
Cl-
K+

Cu electrode
Zn electrode

Cu(s)
SO42- Zn2+ Zn2+
CuSO4 soln SO42- Zn
Cu+2 Zn2+
SO42- Zn2+ Zn2+
SO42-
SO42- Zn2+ SO42-
SO4 2-

ZnSO4 soln 72
 Potential difference is created

ON

Thickness
decreases

Cl- K+
Cl-
K+

Thickness
Cu(s)
increases SO42- Zn2+ Zn2+

SO42- Zn2+ Zn
Cu+2

SO42- Zn2+ Zn2+

SO42-
SO42- Zn2+ SO42-
SO4 2-

73
74
Cell representation :
-
Zn(s) | Zn2+ (aq)(1.0M)|| Cu2+ (aq)
(1.0M)| Cu(s) +

Zn(s) Zn2+ + 2e- … anode reaction

Cu2+ (aq) + 2e- Cu(s) …. cathode
reaction
Zn(s) + Cu2+ (aq) Zn2+ + Cu(s) …..net
reaction

Potential of the cell:- 1.1 V

75
 Functions Of Salt Bridge
 It provides electrical contact between two solutions
and there by completes the electrical circuit.
 It prevents mixing of two solutions.
 It maintains electrical neutrality in both the solutions
by transfer of ions.
 It eliminates liquid junction potential

76
 Distinguish between Electrolytic cell and electrochemical cell

Electrolytic cell Voltaic cell

1. An electric current is passed to
bring about non spontaneous 1. A spontaneous chemical reaction
chemical reaction produces electrical energy

2. Electrical energy is converted to 2. Chemical energy is converted to

chemical energy electrical energy
3.In this cell cathode is positive and
3.In this cell cathode is negative and
anode is negative
anode is positive

4. These cells are irreversible 4. These cells are reversible

5. Oxidation takes place at negative

5. Oxidation takes place at positive electrode and reduction takes place
electrode and reduction takes place at positive electrode
at negative electrode

77
 TYPES OF ELECTRODES

REFERENCE ELECTRODE INDICATOR ELECTRODE

78
 REFERENCE ELECTRODES

 POTENTIAL VALUES ARE ARBITARILY TAKEN AS ZERO OR

EXACTLY KNOWN

 USED TO FIND THE POTENTIAL OF OTHER ELECTRODES

 THEY CAN BE REVERSIBLE OR IRREVERSIBLE

 EXAMPLES:- STANDARD HYDROGEN ELECTRODE AND

CALOMEL ELECTRODE

79
 Standard Hydrogen Electrode
 Reversible electrode
Platinum wire  Representation
H2(g) H+(1M) | H2(g,1 atm) | Pt

 If serving as an anode:
H2(g,1 atm) 2H+(1M) +2e- E° = 0.00V
Glass jacket
 if serving as cathode :

Mercury 2H+(1M) + 2e- H2(g,1 atm) E° = 0.00V

Platinised For SHE the half reaction written in

Pt foil either direction is assigned an
arbitrary potential of exactly
1M H+ ions ZERO potential

80
 Difficulties in setting SHE

Difficult to obtain pure and dry hydrogen gas

Pressure of hydrogen gas cannot be
maintained at exactly 1 atm
Concentration of H+ cannot be exactly
maintained at 1 M

81
Application of SHE

82
 Galvanic cells OR Voltaic cells

Primary voltaic cell Secondary voltaic cell

83
Different types of dry cells

Mercury cell Nickel cadmium cell

84
Nickel- Cadmium cell
 It is a secondary dry cell
Rechargeable and
reversible cell
Cadmium electrode in
contact with alkali act as
anode
Nickel (IV) oxide, NiO2 is
cathode
The electrolyte solution is
basic

85
Nickel- Cadmium cell
Anodic Reaction
Cd (s) + 2OH -(aq) Cd(OH) 2(s) + 2e -
Cathodic Reaction
NiO 2(s) + 2H 2O + 2e- NiOH 2(s) + 2OH -(aq)

Net Reaction
Cd (s) + NiO2(s) + 2H 2O(l) Cd(OH)2(s) + Ni(OH)2(s)

86
87
88
 Working (Cell Reaction)
Oxidation at anode
2H2 (g) + 4OH- (aq) 4H2 O + 4e-
H2O O2(g)
H2(g) Reduction at cathode:
O2 + 2H2O + 4e- 4OH-
Net Cell reaction:
2H2 (g) + O2 2H2 O

Cathode (+)
Anode (-)
H2 O

KOH
OH- Cell representation:
-
Pt | H2(g) | NaOH(aq) |O2(g) |Pt+
OH-
OH-
OH-

Porous carbon electrodes with

platinum 89
Advantages: Drawbacks:
1. Operates continuously 1. Requires expensive
as long as H2 and O2 electrodes such as Pt,
gases are supplied to Pd.
the electrodes 2. Voltage is less than
2. Do not cause any 1.23 volt due to
pollution spontaneous reactions
3. 70% efficiency as at the electrodes
compared to other 3. H2 gas is expensive
galvanic cell and hazardous

90
 Applications
1. Used in automobiles on experimental basis
2. Providing electrical power in the space programme
3. Pure water obtained is used for drinking for
astronauts in space craft
4. Likely to be used as power generators in future
5. Fuel cells along with methanol as fuel might also
become available in small electronic gadgets such
as cell phones, laptops, and computers.

91
 ELECTROCHEMICAL SERIES

Arrangement of a series of electrodes of

elements with the electrode half reactions in
the decreasing order of their standard
reduction potentials.

92
ELECTROCHEMICAL SERIES(EMF)

SRP SOP
F2
Down the EMF series
Au Red n pot. -ve Standard Reduction Potential
Ag +ve (SRP) decreases
Cu
H2 Zero Zero DEFINITION OF EMF
Fe SERIES
Zn
It is defined as the series
Al Red n pot +ve
– ve
of elements arranged in
K
a definite order of their
Li
decreasing SRP.
94
 APPLICATION OF EMF SERIES

 relative strength of oxidizing agents in terms

of E°red values .
 relative strength of reducing agents in terms
of E°red values
 identifying the spontaneous direction of
reaction
 calculation of standard cell potential E° cell

95
Thank you

96