CHB 301(B)

Physical Chemistry II

Kanak Roy
kanak.roy@bhu.ac.in

1
Course contents

• Electrochemistry
• Phase equilibria
• Solid state

2
Electrochemistry

Electrical Chemical
energy energy

3
 Electrolysis

Electric Chemical
energy energy

Galvanic cell 4
What is the free energy change
for a) electrolytic cell b) galvanic
cell?

5
Electrolysis
The use of electric current to
stimulate a non-spontaneous
reaction.

Can you guess

which tube contains
which gas?
Electrolysis of water
produces H2 and O2 6
Electrolysis
electric current is sent through an
electrolyte and into solution in order
to stimulate the flow of ions
necessary to run an otherwise non-
spontaneous reaction

7
Setup of Electrolysis
- +
DC Electrodes
Anodes
Cathodes

Electrolyte
- Anions
+
Cations
8
Setup of Electrolysis

# called an Electrolytic Cell

# Charge carrier is an ion

9
Interests
“Electrolysis”
“Cathode”
“Anode”
“Ion”

Jane Marcet
Michael Faraday Conversations on chemistry
Electrolytes
Substances whose solution in water
conducts electric current.
Examples are salts, acids and bases.

Substances whose aqueous solution does not

conduct electricity are called
non-electrolytes.
Examples are solutions of cane sugar, glucose,
urea etc. 11
Types of Electrolytes
highly ionized in the
Strong solution.
Electrolytes HCl, H2SO4, NaOH, KOH
etc

Weak feebly ionized in the

Electrolytes solution.
H2CO3, CH3COOH, NH4OH
etc
12
Metallic Conductors &
Electrolytic Conductors
Metallic Electrolytic

Conduction is
Conduction is
because of
due to the flow
movement of
of electrons
ions
13
Metallic Conductors &
Electrolytic Conductors
Metallic Electrolytic
Flow of electricity
Ions are oxidized
takes place
or reduced at
without the
electrodes i.e.
decomposition of
chemical reaction
substance i.e. no
takes place
chemical change
14
Metallic Conductors &
Electrolytic Conductors
Metallic Electrolytic

Conduction Conduction
decreases with increases with
increase in increase in
temperature temperature
15
Resistance
▪ Resistance refers to the obstruction to the
flow of current.
▪ For a conductor of uniform cross section(a)
and length(l); resistance R is given by,
a
1
▪ 𝑅 ∝ 𝑙 ; 𝑎𝑛𝑑 𝑅 ∝
𝑎
𝑙 l
▪ 𝑅= 𝜌 Cell constant=
𝑙
𝑎 𝑎

where “ρ” is called resistivity or specific

resistance. Pronounced as “rho”
Conductance
▪ The reciprocal of the resistance is
called conductance. It is denoted by C.
1
𝐶=
𝑅
▪ Unit of conductance is ohm-1 or mho or
Siemens(S)
▪ Ernst Werner von Siemens
Specific conductance
▪ Specific conductance or conductivity is defined as the
conductance of unit volume of a cell. It is reciprocal of
resistivity.
1 𝑎
▪𝜅 = and 𝜌 = 𝑅
𝜌 𝑙

1 𝑙
𝜅=
𝑅 𝑎
Specific conductance has unit ohm–1cm–1. SI
Unit of specific conductance is Sm–1 where S
is Siemens.
Equivalent Conductance
▪ It is the conductance of all ions
furnished when 1 gram-equivalent of an
electrolyte is dissolved in V cc of the
solution. Equivalent conductance is
represented by λeq
Mathematically, λeq= κ x V
1000
λeq = x V=  x
𝑛𝑜𝑟𝑚𝑎𝑙𝑖𝑡𝑦
▪ A decinormal solution of NaCl has
specific conductivity equal to 0.0092.
Calculate the equivalent conductance.

1000
λeq = x V=  x
𝑛𝑜𝑟𝑚𝑎𝑙𝑖𝑡𝑦
Molar Conductance
▪ It is the conductance of all ions furnished
when one mole of the electrolyte is
dissolved in V cc of the solution. Molar
conductance is represented by λm
1000
▪ λm = x V=  x
𝑚𝑜𝑙𝑎𝑟𝑖𝑡𝑦

Where, κ = Specific conductivity

V = Volume of solution in cc containing one
mole of the electrolyte.
Factors affecting electrolytic conduction
▪ Nature of electrolyte:
Strong electrolytes ionize almost
completely in the solution whereas weak
electrolytes ionize to a small extent.

▪ Size of ions:
larger the ion, smaller will be its
conductance.
Factors affecting electrolytic conduction

• Nature of solvent and viscosity:

Greater the polarity of the solvent,
greater is the conductance.
Greater the viscosity, lesser will be the
conductance.
Example of polar solvent?
Example of non-polar solvent?

23
Factors affecting electrolytic conduction

• Concentration of solution: Higher the

concentration of the solution, less is
the conduction.

• Temperature: On increasing the T,

the dissociation increases and the
conduction increases.

24
Variation of Conductance with dilution

Electrolytic conductance increases with

increase in dilution

✓ As with dilution, more ions are

produced in solution, conductance
increases.

25
Variation of Conductance with dilution

Specific conductivity decreases on

dilution.

Equivalent and molar conductance both

increase with dilution and reaches a
maximum value.

26
Variation of Conductance with dilution

Specific conductivity decreases on

dilution.

✓ Upon diluting the solution, the

concentration of ions per unit cell
volume decreases and therefore, the
conductivity decreases.
27
Variation of Conductance with dilution
Equivalent and molar conductance both
increase with dilution and reaches a
maximum value.
✓Λ=κ×V
On dilution, conductivity decreases but
volume containing one mole of an electrolyte
increases. The increase in volume on
dilution is much more than the decrease in
conductivity. As a result molar conductivity
increases with dilution.
28
Conduction in Strong electrolytes

weakening of
intermolecular
forces upon dilution

Follow Debye-
Huckel theory

29
Conduction in Weak electrolytes
The molar and
equivalent
conductance at
infinite dilution
can be
obtained by
Kohlrausch’s
Law
30
Kohlrausch’s Law

The difference of m of different pairs

of electrolytes having a common cation
or a common anion was almost same.

Λ∞m (KCl) = 149.9, Λ∞m (NaCl) = 126.5

Λ∞m (KNO3) = 145, Λ∞m (NaNO3) = 121.6

Λ∞m (KBr) = 151.6, Λ∞m (NaBr) = 128.2

31
Kohlrausch’s Law
Λ∞m (KCl) = 149.9, Λ∞m (KF) = 129.2 20.7

Λ∞m (NaCl) = 126.5, Λ∞m (NaF) = 105.8 20.7

32
Kohlrausch’s Law

at infinite dilution, each ion makes a

definite contribution towards molar
conductivity of the electrolyte irrespective
of the nature of the other ion with which it
is associated

33
Kohlrausch’s Law

The molar conductivity at infinite dilution for

a given salt can be expressed as the sum
of the individual contributions from the ions
of the electrolyte.

Λ∞m = v+ λ∞+ + v- λ∞-

34
 ∞ ∞
𝜆𝑚 𝑜𝑓 𝑁𝑎𝐶𝑙 𝜆𝑚 𝑜𝑓 𝐴𝑙2 𝑆𝑂4 3

∞ + ∞ +3
1. 𝜆𝑚 (𝑁𝑎 ) 2. 𝜆𝑚 (𝐴𝑙 )
+ +
∞ − ∞ −2
1. 𝜆𝑚 (𝐶𝑙 ) 3. 𝜆𝑚 (𝑆𝑂4 )

35
Applications of Kohlrausch Law

•Determination of Λ∞m for weak

electrolytes:
Λ∞CH3COOH = Λ∞CH3COONa + Λ∞HCI - Λ∞NaCI

36
Applications of Kohlrausch Law
Λ∞NH4OH = Λ∞NH4Cl + Λ∞NaOH - Λ∞NaCI

37
Applications of Kohlrausch Law
•Determination of degree of
ionisation for weak electrolytes:
If λcm = molar conductivity of a weak
electrolyte at any concentration c
Λ∞m = molar conductivity of an electrolyte at
infinite dilution. the degree of ionization is
given by,
α = Λcm / Λ∞m

38
Applications of Kohlrausch Law
• Determination of the ionization
constant of a weak electrolyte :
Weak electrolytes in aqueous solutions
ionize to a very small extent. The extent of
ionization is described in terms of the
degree of ionization ( α ).

39
Applications of Kohlrausch Law
For example, for a weak electrolyte AB, the
ionization equilibrium is,
AB ⇔ A++ B-
Then, the ionisation constant of AB is given
by
K = [A+] [B-]/[AB]
=C α C α /C (1 - α)
= C α2/( 1 - α )

40
Applications of Kohlrausch Law
We know, that at any concentration C, the
degree of ionisation (α ) is given by,
α = Λcm / Λ∞m

K = C(Λcm/Λ∞m)2/[1 - (Λcm/Λ∞m)]
= C(Λcm)2/Λ∞m - Λcm);

Thus, knowing Λ∞m and Λcm at any

concentration, the ionisation constant (K)
of the electrolyte can be determined.
41
• Determination of the solubility of a
sparingly soluble salt :
Salts such as AgCl, BaSO4, PbSO4, etc which
dissolve to a very small extent in water are called
sparingly soluble salts. As they dissolve very little,
even a saturated solution of such a salt can be
assumed to be at infinite dilution.
Then, the molar conductivity of a sparingly
soluble salt at infinite dilution can be
obtained from the relationship,
Questions
1) Equivalent conductance of NaCl, HCl and
C2H5COONa at infinite dilution are 126.45,
426.16 and 91 ohm–1 cm2 respectively.
Calculate the equivalent conductance of
C2H5COOH.
2) A decinormal solution of NaCl has specific
conductivity equal to 0.0092.If ionic
conductance of Na+ and Cl– ions are 43.0
and 65.0 ohm–1 respectively, calculate the
degree of dissociation of NaCl solution.
Homework 1
3) The molar conductivity of saturated
solution of AgCl at 298 K is found to be 1.382
x 10-6 S cm-1. Find its solubility. Given that
the molar ionic conductances of Ag+ and Cl-
at infinite dilution are 61.9 S cm2 mol-1 and
76.3 S cm2 mol-1 respectively.
TOPICS
Migration of ions
Relative speed of ions (Hittorf’s Rule)
Transport Number
Determination of transport number
Conductometric titration
Faraday’s laws of electrolysis
Redox
Migration of ions

the speeds
of cations
and
of anions
are not
necessarily
the same
Relative speed of ions: Hittorf’s Rule

the loss of
concentration
around any
electrode is
proportional to the
speed of the ion
moving away from it
Relative speed of ions: Hittorf’s Rule

Imaginary planes dividing the cell into

3 compartments
Lets assume 13 ion pairs in the cell
Relative speed of ions: Hittorf’s Rule

II. When only anions are capable to migrate

Relative speed of ions: Hittorf’s Rule

III. Let the anions and cations move at the

same rate
Relative speed of ions: Hittorf’s Rule

IV. Let the cations move at twice the speed

of the anions
Relative speed of ions: Hittorf’s Rule

the loss in concentration around any

electrode is proportional to the speed of the
ion moving away from it
Question
In an experiment, the increase in
concentration of AgNO3 around the silver
anode was 5.6 mg of silver. 10.73 mg of
silver were deposited by the same current in
the silver coulometer placed in series. Find
the speed ratio of Ag+ and NO3- ions.
WHAT IS TRANSPORT NUMBER ?
The fraction of the total current carried by the
cation or the anion is termed its Transport
number or Hittorf’s number.
Transport Number
v+
The transport number of cation (t+ ) =
v+ + v-
v-
The transport number of anion (t- ) =
v+ + v-

t+ v+
= t+ + t-=1
t- v-
Question
The speed ratio of silver and nitrate ions in a
solution of silver nitrate electrolyzed between
silver electrodes is 0.916. Find the transport
number of the two ion.
Determination of Transport Number

Or Coulometer
 + _

MILLI-AMMETER
VARIABLE
+ RESISTENCE + _

--- ---
EXPERIMENTAL
SOLUTION

VOLTAMETER Or
COULOMETER
Determination of Transport Number
Case I: When electrodes are unattackable (Pt electrode)

After passing electric current

Let the anodic solution taken out = a g
Weight of AgNO3 present in it = b g
Weight of water= (a-b) g

Before passing current,

Let AgNO3 present in (a-b) g water is = c g
Determination of Transport Number

Fall in concentration
= (c-b) g AgNO3
= (c-b)/170 g.eqvt. AgNO3
= (c-b)/170 g.eqvt. of Ag = d g. eqvt. of Ag

Let the silver deposited in Ag coulometer

= w1 g
= w1/108 g. eqvt. of Ag
=W
Determination of Transport Number

Transport number of Ag+ (tAg+)=

Fall in concentration around Anode in g. eqvt
Amount of Ag deposited in g. eqvt.
= d/W

Transport number of NO3- (tNO3-)

= 1-(d/W )
Determination of Transport Number
Case II: When electrodes are attackable (Ag electrode)
Increase in concentration of anodic solution
= (b-c) g. of AgNO3
=(b-c)/170 g. eqvt. of AgNO3= e
If no Ag+ would have been migrated from the
anode, the increase in concentration of Ag+
would have been= W
Fall in concentration due to migration of Ag+ ion=W-e

Transport number of Ag+ (tAg+)=

W-e
All in g-eqvt.
W
Transport number of NO3- (tNO3-)=
W-e
1-
W
Problem

A solution of silver nitrate containing 12.14 g

of silver in 50 ml of solution was electrolysed
between platinum electrodes. After
electrolysis, 50 ml of the anode solution was
found to contain 11.55 g of silver, while 1.25 g
of metallic silver was deposited on the
cathode.
Calculate the transport number of Ag+ and
NO3- ions.
Solution
Conductometric Titration

Titrations in which conductance

measurements are made use of in
determining the end-point of acid-
alkali reactions, some displacement
reactions or precipitation reactions
are called Conductometric titrations.
Conductometric Titration
Conductance of a solution at a
constant temperature depends upon the
number of ions present in it and their
mobility
Conductometric Titration

the titrant is added from a burette into a

measured volume of the solution to be titrated
which is taken in a conductance cell and the
conductance readings corresponding to the
various additions are plotted against the
volume of the titrant. In this way two linear
curves are obtained, the
point of intersection of which is the end-point.
Strong acid with strong base
Weak acid with strong base
Strong acid with weak base
Weak acid with weak base
Precipitation reaction
JAM 2017

75
JAM 2019

JAM 2008

76
JAM 2009

7
7
JAM 2009

7
8
JAM 2010

7
9
 Faraday’s First Law of Electrolysis
Statement: The amount of
chemical reaction and hence the
mass of any substance
deposited or liberated at any
electrode is directly proportional
to the quantity of electricity
passed through the electrolyte
(solution or melt)
 Faraday’s First Law of Electrolysis
If W grams of the substance is deposited by Q coulombs of
electricity, then
W α Q or W = ZQ
Where Z is a constant of proportionality and is called
electrochemical equivalent of the substance deposited
If a current of I amperes is passed for t seconds, then Q = I x t
So that W = Z x Q = Z x I x t
Thus, if Q = 1 coulomb or I = 1 ampere and t = 1 second, W = Z.

Hence, Electrochemical equivalent of a substance may be

defined as the mass of the substance deposited when a
current of one ampere is passed for one second.
Problem:
On passing 0.1 Faraday of electricity through
aluminium chloride what will be the amount
of aluminium metal deposited on cathode
(Al = 27)
27
w = 0.1 = 0.9 g
3
Solution:
Problem:
How many atoms of calcium will be deposited
from a solution of CaCl2 by a current of 25
milliamperes flowing for 60 s?
 Faraday’s Second Law of Electrolysis

Statement: When the same quantity of electricity

is passed through different electrolytes the
masses of different ions liberated at the
electrodes are directly proportional to their
chemical equivalence.

W1 E1 Z It E
= or 1 = 1
W2 E2 Z2It E2
Z E
Hence, 1 = 1
Z2 E2
 Example

For AgNO3 solution and CuSO4 solution

connected in series, if the same quantity of
electricity is passed,
Consider the electrolysis of molten NaCl, i.e.
NaCl Na + ½ Cl2
Thus, we have Na+ + e- Na
This means that one electron produces one sodium atom.
Therefore, passage of one mole of electrons will produce
one mole of sodium.
Similarly, looking at the reactions Cu2+ + 2e- Cu;
Al3+ + 3e- Al
Thus, we conclude that two moles of electrons produce one
mole of Cu, three moles of electrons will produce one of
Al.
If “n” electrons are involved in the electrode
reaction, the passage of n Faradays of
electricity will liberate one mole of the
substance/one Faraday of electricity
deposits one gram-equivalent of the
substance.

The charge associated with one mole of

electrons, 9.6485x104 C/mol, is the
FARADAY CONSTANT, F
Problem:
How much charge is required for the
following reaction?
1) 1 mol of Al3+ to Al
2) 1 mol of Cu2+ to Cu
3) 1 mol of MnO4- to Mn2+
Problem:
How much Cu will be deposited on the cathode
of an electrolytic cell containing CuSO4
solution by the passage of a current of 2
amperes for 30 minutes? (Atomic Mass of Cu =
63.5)
Redox Review
▪ Oxidation-reduction: “Redox”

▪ Redox reactions:electron transfer processes

▪ Oxidation: loss of 1 or more e-

▪ Reduction: gain of 1 or more e-

▪ Oxidation numbers: imaginary charges

(Balancing redox reactions)
Oxidation Numbers (O.N.)
▪ 1. Pure element O.N. is zero

▪ 2. Monatomic ion O.N. is charge

▪ 3. Neutral compound: sum of O.N. is zero

▪ Polyatomic ion: sum of O.N. is ion’s charge

▪ *Negative O.N. generally assigned to more

electronegative element
Oxidation Numbers (O.N.)
▪ 4. Hydrogen
▪ assigned +1
▪ (metal hydrides, -1)
▪ 5. Oxygen
▪ assigned -2
▪ (peroxides, -1; OF2, +2)
▪ 6. Fluorine
▪ always -1
Oxidation-reduction

▪ Oxidation is loss of e-
▪ O.N. increases (more positive)

▪ Reduction is gain of e-
▪ O.N. decreases (more negative)

▪ Oxidation involves loss

▪ Reduction involves gain
Molten NaCl
- + e-
DC

95
Aqueous solution of NaCl
- + e-
DC

96
DEBYE-HUCKEL THEORY

▪ The first successful attempts to explain the

variation of equivalent conductance of strong
electrolytes with dilution was made by Debye
and Huckel(1923).
▪ The fundamental idea underlying their work is
that because of electrical attraction among the
oppositely charged ions.
INTERIONIC EFFECTS

▪ The electrical attractions among the oppositely

charged ions which affect the speed of an ion in
the electric field are called “interionic effects”.
There are two such effects :-
❖Relaxation effect or Asymmetry effect
❖Electrophoretic effect
 RELAXATION EFFECTS OR ASYMMETRY
EFFECTS
- + -
-
_ -
-

- + - + -
-
- -
- -
- -
(a) (b)

Symmetrical ionic atmosphere Ionic atmosphere becoming

around a positive ion asymmetrical when central ion moves
FIG:1
ELECTROPHORETIC EFFECT

_
_
_

+
_
_

_ _
FIG:2
DEBYE-HUCKEL-ONSAGER EQUATION
Debye and huckel (1923)derived a mathematical
expression for the variation of equivalent conductance
with concentration. This equation was further
improved by Onsager(1926-1927) and is known as
Debye-Huckel-Onsager equation.
Λc = Λ0-[82.4/(DT)1/2 ή +8.20X105/(DT)3/2 λ0]√C
Where Λc =Equivalent conductance at concentration c.
Λ0 =Equivalent conductance at infinite dilution.
D = Diectric constant of the medium.
ή =Coefficient of viscosity of the medium.
T =Temperature of the solution in degree absolute.
c = Concentration of the solution in moles/litre.
As D and ή are constant for a particular solvent.Therefore,at constant
temperature, the above equation can be written in the form:
Λc= Λ0-(A+BΛ0)√c where A and B are constants for a particular solvent
 VERIFICATION OF THE ONSAGER EQUATION
Two tests can be readily HCI ACID
performed to verify the
onsager equation.These KCl
are:-

Equivalent conductance
❖ The plot of Λc vs √c
should be linear.
AgNO3
❖The slope of the line
should be equal to A+B
Λ0, calculated by
substituting the value of NaCl
various constants directly.

√concentration c
FIG:3 TESTS OF ONSAGER