Thermodynamics of Materials

MM-231

Dr. Rashid Ali

Fall 2022

Lecture # 1

GHULAM ISHAQ KHAN INSTITUTE OF ENGINEERING

SCIENCES & TECHNOLOGY

FACULTY OF MATERIAL & CHEMICAL ENGINEERING

 PROGRAMME LEARNING OUTCOMES
1. Engineering knowledge (CLO – 1)
2. Problem Analysis (CLO – 2,3) Bloom’s
3. Design/Development of solutions Taxonomy
4. Investigation Levels
5. Modern tool usage 1. Remembering
6. The Engineer and Society 2. Understanding
7. Environment and sustainability 3. Applying
8. Ethics
4. Analyzing
9. Individual and team work
10. Communication 5. Evaluating
11. Project management 6. Creating
12. Lifelong learning

https://www.pec.org.pk/downloads/Accreditation/1/Manual%20of%20Ac 2
creditation%20%E2%80%93%20Third%20Edition%202019%20(Amende
d%20Ver.%20of%20Manual-2014)_152.pdf
 Course Learning Outcomes
Sr. No Course Learning Outcomes PLOs Blooms Taxonomy

Students will be able to

describe and apply laws of
thermodynamics related to
C 2 : Understanding
CLO_1 problems in materials PLO1
C3: Applying
engineering and explain the
basic concepts of phase
equilibria.
Students will be able to
explain and use the different
thermodynamic properties of C 2 : Understanding
CLO_2 PLO2
materials in the context of state C3: Applying
functions using classical and
statistical approach.
Students will be able to solve 3
CLO_3 thermodynamic problems PLO2 C3: Applying
related to reaction equilibria.
 Course Contents
Week Topics Wise Course Contents
Classical Thermodynamics
Materials thermodynamics and its applications, molecular view of energy,
1
thermodynamics state functions.
The First Law of Thermodynamics: Energy transfer, pressure-volume and work
relationship, reversible and irreversible process, intensive and extensive
2
properties, state and non state functions, Enthalpy and heat capacity, Enthalpy
change.
The second law of Thermodynamics: free energy, heat engines (heat pumps and
3
refrigerators), entropy, Carnot Cycle.
Statistical Thermodynamics
Energy dispersion and entropy, Equilibrium criterion and entropy, Partition
4 function, Entropy changes and entropy productions, Statement of second law of
Thermodynamics.
Free Energy Functions: Energy functions, Helmholtz energy, Gibb’s energy,
5 Effect of pressure and temperature on Gibb’s energy change, Some useful
4
equations.
 Course Contents
Week Topics Wise Course Contents
The Third Law of Thermodynamics: Statement of the Third Law, Corollaries
6
to the Third law, Absolute Entropies, Molecular interpretation.
Enthalpy and Gibbs Energy Changes: Standard states, heat of formation, heat
7
of reaction, adiabatic flame temperature, Gibb’s energy changes.
8 Behavior of Gases: Ideal gases, Real gases and Fugacity.
Classical and Statistical Applications
Reaction Equilibria: Equilibrium constants, Criteria of reaction equilibrium,
9
Effect of temperature and pressure on equilibrium constant.
Le Chatelier’s Principle, alternative standard states, interaction coefficients,
10 Ellingham diagram, Absorption equilibria.
Ideal gases, Gibbs energy of mixing, Entropy of mixing and Enthalpy of
mixing, Real gases and fugacity, compressibility factor, vander Walls
11
equation, Thermodynamic functions of Mixing, fugacity for condensed phase
(liquid and solid), activity, molar Gibbs energy.
Activity coefficient, Partial properties, partial molar volume. Reaction
12 Equilibria, Equilibrium constant, Effect of temperature on Equilibrium5
constant, Van’t Hoff equation,
 Course Contents
Week Topics Wise Course Contents
Effect of pressure on Equilibrium constant, Le Chatelier’s
13 Principle, Ellingham Diagram. 1.Relative stability of compound, 2.
Relative stability (carbon reduction)
Ellingham diagram, 1. Oxygen partial pressure, 2. Equilibrium
14
partial pressure, 3. Stability diagram (phase diagram),
Phase rule, degree of freedom, definition of phase and component,
15 Equation of Gibb’s phase rule, Degree of freedom from phase
diagram, 2. Degree of freedom of reaction system.
Final Exam

6
 Text Book

Materials Thermodynamics:
With Emphasis on Chemical Approach 77
Publisher : World Scientific
Author : Hae-Geon Lee, 2012
 Reference Book

Thermodynamics of Materials (Volume-1)

Author : David V. Ragone 8
8
Publisher : John Wiley & Sons
 Reference Book

Introduction to the Thermodynamics of Materials

9
Author : David R. Gaskell, 2005
 Course Grading Policy
Assignments (02) 4%

Quizzes (06) 24 %

Mid Term Exams 30 %

Final Term Exams 42 %

o Attendance as per GIKI Policy is 80% and is compulsory

to appear in final exams

10
 Lab Experiments
o Modelling of Materials Phase Change behavior

o Differential Scanning Calorimetry (DSC)

o Thermal conductivity of Metals

11
 Class Schedule
MM231-A Lecture
Day
Thermodynamics of Materials Hall

Tuesday 10:30-11:20 LH3 (FMCE)

Thursday 4:30-5:20 LH3 (FMCE)

Friday 8:00-9:00 LH3 (FMCE)

MM231-B Lecture
Day
Thermodynamics of Materials Hall

Monday 2:30-3:20 LH1 (FMCE)

Thursday 2:30-3:20 LH3 (FMCE)

12
Friday 12:00-1:00 LH1 (FMCE)
 Class Schedule
MM231-A+B Lecture
Day
Thermodynamics of Materials Hall

Tuesday 9:00-9:50 LH1 (FMCE)

Wednesday 10:30-11:20 LH1 (FMCE)

Friday 11:00-11:50 LH1 (FMCE)

13
 Class Rules
 No attendance will be marked after five minutes entry
in class.

 No noise in the class.

 All the quizzes will be considered.

 Any student can visit the course instructor during office

hours.

14
Contact Information
E-mail: [email protected]
Phone Ext: 2423

15
Thermodynamics
What is thermodynamics?
Thermodynamics is science concerned with:
o Transfer of energy
o Conversion of energy
In any process:
o Physical
o Chemical
For example:
o Work is perform in the form of electricity to perform work
as in refrigerator.
o Heat by fuel burning is used to provide work as in automobile.

Thermodynamic is all about energy:

16
o How energy is used
o How energy changes from one form to another form.
Thermodynamics of Materials
MM-231
Dr. Rashid Ali
Fall 2022

Lecture # 2

GHULAM ISHAQ KHAN INSTITUTE OF ENGINEERING

SCIENCES & TECHNOLOGY

FACULTY OF MATERIAL & CHEMICAL ENGINEERING

►We are dealing with Materials
made up of Atoms, Molecules, Ions
►They are ceaselessly moving
►This ceaseless motion has different modes:
Electronic, Vibrational, Rotational, Translational

Question:
Do atoms possess
Rotational and Vibrational modes of motion ?

Question:
What happens to molecules when they
either absorb or emit a photon or
when they hit each other? 18
How Fluorescent Light Works

19
20
2349.3 cm-1 1330 cm-1

667.3 cm-1

21
Summary
 Why monoatomic atoms (argon and helium) only
have translational mode of motions?

 What is thermodynamic?

 Difference between Classical versus Statistical

Thermodynamics?

1
 Usually in nm

Usually in Hz ( or s-1)

Convert energy in Joule to energy in wavenumber

Find units of
23
 Thermodynamics of Materials
MM-231
Dr. Rashid Ali
Fall 2022

Lecture # 3

GHULAM ISHAQ KHAN INSTITUTE OF ENGINEERING

SCIENCES & TECHNOLOGY

FACULTY OF MATERIAL & CHEMICAL ENGINEERING

https://pern-
my.sharepoint.com/:f:/g/personal/rashidali_giki_edu_pk/Es6lveSPKmJAgi42HUWdZe
mFpPc6-Ho8voQ10zZOJi_g?e=Cc2YZ5
Convert 500 J.mol-1 into wavenumber ⱱ.. Express your
answer in units of cm-1.

500𝐽/𝑚𝑜𝑙
=
6.6 × 10−34𝐽. 𝑆 × 3 × 1010 𝑐𝑚 Τ𝑠
= 25.50 × 1024 𝑐𝑚−1/mol
25.25 × 1024 𝑐𝑚−1/mol
=
6.02 × 1023 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒/𝑚𝑜𝑙
= 41.94 = 𝑐𝑚−1 per molecule 25
Convert 10,000 𝑐𝑚 −1 into Joule per photon

= 6.6 × 10−34𝐽. 𝑆 × 3 × 1010 𝑐𝑚Τ𝑠 × 10,000 𝑐𝑚−1

= 6.6 × 10−34𝐽 × 3 × 1014

= 19.8 × 10−20 𝐽

= 1.98 × 10−19 𝐽/𝑝ℎ𝑜𝑡𝑜𝑛

26
Vibrational Spectrum of HBr

Convert 2500 cm-1 wave numbers into nanometers?

1
= 25,00 𝑐𝑚−1=
𝜆
𝟏
𝝀=
𝟐𝟓,𝟎𝟎 𝒄𝒎−𝟏
𝒄𝒎 𝟏𝒎 𝟏×𝟏𝟎𝟗 𝒏𝒎
𝝀= × × 27
𝟐𝟓,𝟎𝟎 𝟏𝟎𝟎 𝒄𝒎 𝟏𝒎
𝟏 𝟏×𝟏𝟎𝟗 𝒏𝒎
𝝀= × = 4 × 𝟏𝟎𝟑 𝒏𝒎
𝟐𝟓𝟎,𝟎𝟎𝟎 𝟏
Representation of Energy States of Molecules

28

Draw energy level diagram using horizontal bars to represent energy levels of molecule and show first
two electronic levels along with vibrational & rotational levels belonging to these electronic levels.
How Microwave Cooks the Food

29
𝜆

30
Notice: The units of energy written next to each vibration
They are called wavenumbers

31
What is the relation between global warming and
667.3 cm-1 ?
How Does CO2 Heat up the Earth’s Atmosphere?

32
2349.3 cm-1 1330 cm-1

667.3 cm-1

33
The restless
Molecules
Vibration

34
35
Outline of Lecture
➢ Potential Energy, Kinetic Energy, Internal
Energy,

➢ Macroscopic Properties: T, P, V,

➢ Classical and Statistical thermodynamics

➢ Molecular View of Pressure

36
Energy of System
Potential energy: The potential energy is the energy that atoms and
molecules possess in the form of bonds associated with the intermolecular
attractive forces.
CH4 + 2 O2 → 2 H2O + CO2; ∆H = - 802 kJ.mol-1
Kinetic energy: The motions of individual atoms or molecules are random
and chaotic. The motions are classified into three different modes; namely,
translation, rotation and vibration.

1330 cm-1

37

2349.3 cm-1
667.3 cm-1
Internal Energy

38
Thermodynamics of Materials
MM-231
Dr. Rashid Ali
Fall 2022

Lecture # 4

GHULAM ISHAQ KHAN INSTITUTE OF ENGINEERING

SCIENCES & TECHNOLOGY

FACULTY OF MATERIAL & CHEMICAL ENGINEERING

Molecular View of Pressure (P)
Show that PV = 1/3 Nm𝑉 2

40
Molecular View of Pressure (P)
1
Show that PV = Nm𝑉 2
3
The Change in momentum of molecule in single collision:
= After – Before
= – m𝑉𝑥 – m 𝑉𝑥 = – 2 m𝑉𝒙
Number of Collisions/ molecule/second (one round trip):
𝟐𝒙
t=
𝑽𝒙

Newton’s 2nd Law (Force exerted/molecule/second):

𝑑𝑝
𝐹𝑥 = … … … 𝐸𝑞. 1
𝑑𝑡

As we know: S = 𝑉𝑥 t
2𝑥
t= 41
𝑉𝑥
𝑉𝑥
𝐹𝑥 = – 2 m 𝑉𝑥 ×
2𝑥
Molecular View of Pressure (P)
1
Show that PV = Nm𝑉 2
3
𝑉𝑥
𝐹𝑥 = – 2 m 𝑉𝑥 ×
2𝑥

m 𝑉𝑥2
𝐹𝑥 = −
𝑥
2 2
𝑣1+ 𝑣2+⋯……….
Rate of force on wall: 𝑉𝑥2 =
𝑁
m 𝑉𝑥2
𝐹𝑥 = 𝑉𝑥2 is the mean of sequare of normal
𝑥
component of velocity in x − dirction
Pressure: m 𝑉𝑥2
𝑃𝑥 =
𝐴𝑥

m 𝑉𝑥2
𝑃𝑥 =
V
𝑃𝑥 V = m 𝑉𝑥2 By single molecule
42
𝑃𝑥 V = mN 𝑉𝑥2 … … … 𝐸𝑞. 2 By N molecule
𝐸𝑞. 𝑓𝑜𝑟 𝑡ℎ𝑒 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑖𝑛 𝑜𝑛𝑒 − 𝑑𝑖𝑚𝑒𝑛𝑠𝑖𝑜𝑛𝑎𝑙
Molecular View of Pressure (P)
1
Show that PV = Nm𝑉 2
3
Remember: 𝑉 2 = 𝑉𝑥2 + 𝑉𝑦2 + 𝑉𝑧2 = 3 𝑉𝑥2

Since: 𝑉𝑥2 = 𝑉𝑦2 = 𝑉𝑧2 No reason of favor one dimension over

other
1
𝑉𝑥2 = 𝑉 2
3

1
𝑉𝑥2 = 𝑉 2
3

𝑃𝑥 V = mN 𝑉𝑥2 … … … 𝐸𝑞. 2 By N molecule

1
PV = Nm 𝑉 2 … … … 𝐸𝑞. 3 43
3
Internal Energy of Ideal Gas-Molecular View
What is internal energy of monoatomic ideal gas?

… … … 𝐸𝑞. 4

What is N, m and
1
PV = Nm 𝑉 2 … … … 𝐸𝑞. 3
3

From Eq. 3:

Find how U depends on temperature?

Determine how U is independent of both P and V at

constant T ? 44
Contents of the Lecture
➢ Thermodynamics System

➢ Heat and Work

➢ Laws of thermodynamics: 0, 1st

➢ Processes such as:

Isobaric, Isochoric, Isothermal, Adiabatic

➢ Reversible and Irrevsible Processes

45
Thermodynamic System
System: The part of the Universe that we choose to study.
Surroundings: The rest of the Universe.
Boundary: The surface dividing the System from the
Surroundings.
Systems can be:
Open: Mass and Energy can transfer between the System and the
Surroundings
Closed: Energy can transfer between the System and the
Surroundings, but NOT mass
Isolated: Neither Mass nor Energy can transfer between the46
System and the Surroundings
Types of System

a) A pan of water neither energy nor mass exchange with

surrounding thus isolated system.
b) In closed system, contents of pan are closed with air tight lid, but
heat energy enters the pan from burner.
47
c) Water (mass) enters the pane by crossing system boundary.
Thermodynamics of Materials
MM-231
Dr. Rashid Ali
Fall 2022

Lecture # 5

GHULAM ISHAQ KHAN INSTITUTE OF ENGINEERING

SCIENCES & TECHNOLOGY

FACULTY OF MATERIAL & CHEMICAL ENGINEERING

Heat (Q)
➢ Heat flows by virtue of temperature difference.
➢ Heat flows until temperature gradient disappears.
➢ When heat flows energy is transferred.
➢ One calori is amount of heat that raise the
temperature of 1 g of water by 1°C from 14.5 to
15.5 °C.
Sign Convention:
➢ Heat is positive (+) when it flows into system.
➢ Heat is negative (-) when it flows out of system.

49
Work (W)
➢ Work is transfer of energy by interaction between
system and surroundings.

Sign Convention:

➢ Work is positive (+) when it is done on system.

➢ Work is negative (-) when it flows out of system.

50
Work (W)
➢ If a gas in cylinder expands and pushes the piston
against external pressure:
F = APex

➢ Work under these conditions is called reversible work.

➢ What does integral means in PV work? 51

➢ What –Ve sign means?

First Law of Thermodynamics
➢ Energy can not be created or destroyed
➢ The total energy of universe can not change.
➢ But you can transform from one form to another.
For example:

o Electric motor converts electrical energy into

mechanical energy. Dynamo does just the
opposite.

o Fuel burning converts chemical energy into work

performed by internal combustion engine.
52

dU = δQ + δW
Zeroth Law of Thermodynamics
➢ How many laws of Thermodynamics?

53
Isothermal Process

54
Thermodynamics of Materials
MM-231
Dr. Rashid Ali
Fall 2022

Lecture # 6

GHULAM ISHAQ KHAN INSTITUTE OF ENGINEERING

SCIENCES & TECHNOLOGY

FACULTY OF MATERIAL & CHEMICAL ENGINEERING

Heat, Work and Internal Energy
Calculate changes in heat, work, U for ideal gas
expanding reversibly via paths from :
1. A (Isothermal)
2. B+ C (Adiabatic + Isochoric)
3. D+E (Isobaric+ Isochoric)

56
Heat, Work and Internal Energy
Calculate changes in heat, work, U for ideal gas
expanding reversibly via paths from :
1. A
Path A:

57
 2 bar 4 bar
Change in P: Pi = 2 to Pf = ? bar 1 dm3 0.5 dm3
Change in V: Vi = 1 dm3 to Vf = 0.5 dm3
T is constant

How much work is involved?

58
Reversible vs Irreversible Isothermal Compression

1. Irreversible compression (work done on system)

2. Reversible compression (work done on system)

59

= 139 J
Isothermal Compression

0.667 dm3
0.5 dm3 at 3 bar
4 bar

Vf = (2 bar x 1 dm3) / 3 bar = 0.667 dm3

60
Summary
1. Irreversible compression

2. Reversible compression in two steps

3. Reversible compression in very small steps

61
Thermodynamics of Materials
MM-231
Dr. Rashid Ali
Fall 2022

Lecture # 7

GHULAM ISHAQ KHAN INSTITUTE OF ENGINEERING

SCIENCES & TECHNOLOGY

FACULTY OF MATERIAL & CHEMICAL ENGINEERING

Work done in Compression or Expansion
depends on Path

63
Expansion of an Ideal Gas
Expanding gas can do maximum work
if (Pext - Pint ) = ∆P is kept infinitesimally small

64
 ∆P → 0

Name the process carried out on the right? 65

Compression of an Ideal Gas
Show that minimum work is required to be done on the gas if it
is reversibly compressed

66
67
 68

Work out this problem for carbon dioxide gas

Thermodynamics of Materials
MM-231
Dr. Rashid Ali
Fall 2022

Lecture # 8

GHULAM ISHAQ KHAN INSTITUTE OF ENGINEERING

SCIENCES & TECHNOLOGY

FACULTY OF MATERIAL & CHEMICAL ENGINEERING

Example 2.2

70
Example 2.2
→ 2 Fe + 3/2 O2 → Fe2O3 ; δQ = -831.08 kJ (Exothermic)
→ T constant at 298K, O2 pressure constant at one atm.
→ Given: δQ = - 831 kJ / mol & ∆U = δQ + δW = - 827.36 kJ + 3.72
→ Calculate ∆U, q, and w
R = 8.314 J.K-1mol-1
→ Determine w, then q, then ∆U = 0.0821 L.atm. K-1mol-1

= ∆H

71

Why dU is negative?
Enthalpy
→ Heat, Work, and the First law
dU = δQ + δW
Where,
δQ is thermal energy supplied or removed as heat
δW is mechanical energy supplied or removed as work

1. For isochoric change: Since, dV = 0, δW = - PdV = 0

dU = δ Q
2. For isobaric change: dU = δQ + δW

U2 – U1 = δQ - P ( V2 – V1 ) = δQ - (PV2 – PV1)
72
(U2 + PV2 ) – (U1 + PV1) = δQ = H2 – H1 = dH

dH = δQ
Characteristics of State function such as U

dU = δQ + δW
Changes in state functions are independent of the path

73
Heat, Work & Internal Energy: Path Vs State Function
Calculate changes in heat, work, U for ideal gas
expanding reversibly via paths from :
1. A
Path A:

74
Heat, Work & Internal Energy: Path Vs State Function
2. B+ C (Adiabatic + Isochoric)
For adiabatic process (Path B): 𝜹𝑸 = 0

𝒅𝑼 = 𝜹𝑸 + 𝜹𝑾

𝒅𝑼 = 𝜹𝑾
For Path C: 𝑷𝟑, 𝑽𝟐, 𝑻𝟐 → 𝑷𝟐, 𝑽𝟐, 𝑻𝟏

75
Heat, Work & Internal Energy: Path Vs State Function
3. D+E (Isobaric+ Isochoric)
For Path D: 𝑷𝟏, 𝑽𝟏, 𝑻𝟏 → 𝑷𝟏, 𝑽𝟐, 𝑻𝟑

76
Using ideal gas equation, show that pressure and77
volume are state function
Change in Internal Energyy U as function of V & T

T constant

V constant
78
How to Calculate ∆U from ∆H?

Remember that: 0.082 L.atm.mol-1.K-1 = 8.314 J mol-1.K-1

79
Where other energy 3.1 KJ goes? That energy does
work against external pressure.
Characteristics of State function such as U
➢ State functions depend on the mass of material which are called
extensive properties. (e.g., U, V).

➢ On the other hand, some state functions are independent of the

amount of materials. These are called intensive properties (e.g.,
P, T).

Using ideal gas equation, show that pressure and

volume are state function
80
Thermodynamics of Materials
MM-231

Lecture # 9

GHULAM ISHAQ KHAN INSTITUTE OF ENGINEERING

SCIENCES & TECHNOLOGY

FACULTY OF MATERIAL & CHEMICAL ENGINEERING

Heat Capacity, Specific Heat, Molar Heat Capacity
Thermal energy requirement which increases U or H
When T changes by one degree

𝒅𝑼 = 𝜹𝑸 + 𝜹𝑾

𝑽
𝒅𝑼 = 𝜹𝑸 − ‫𝑽𝒅𝑷 𝟐 𝑽׬‬
𝟏

𝑽
𝜹𝑸 = 𝒅𝑼 + ‫𝑽𝒅𝑷 𝟐 𝑽׬‬
𝟏

𝜹𝑸 = 𝒅𝑼
82
Show, for an ideal gas, that Cp – Cv = R

83
Show, more rigorously, for an ideal gas, that
Cp – Cv =R

84
85
Quiz-1Solution
Q.1 (a) Consider one mole of CH4 with Van der Waals constants are: a = 2.283L2
.bar/mol2; b = 0.04278 L/mol Calculate the work done when the gas expands
reversibly from 5 L to 10 L at constant temperature of 27⁰C:
(1). Expansion as an ideal gas obeying PV = RT (4pts)
Given: R = 8.314 J/K/mol = 0.0821 L.atm. K-1mol-1

𝟓𝑳
𝒘 = (1 mol) 8.314 J.K -1 mol-1 . 300 K ln
𝟏𝟎𝑳

𝟓
𝒘 = 8.314 J. 300 ln
𝟏𝟎

𝟓
𝒘 = 8.314 J. 300 ln
𝟏𝟎

𝒘 = - 1728.84 J
86
Quiz-1Solution
Q.1 (a) Consider one mole of CH4 with Van der Waals constants are: a = 2.283L2
.bar/mol2; b = 0.04278 L/mol Calculate the work done when the gas expands
reversibly from 5 L to 10 L at constant temperature of 27⁰C:
(2). Expansion as a Van der Waal gas obeying (P + a/V2) (V-b) = RT. (7pts)
Given: R = 8.314 J/K/mol = 0.0821 L.atm. K-1mol-1

𝟏𝟎𝑳−𝟏𝒎𝒐𝒍 ×𝟎.𝟎𝟒𝟐𝑳.𝒎𝒐𝒍−𝟏
𝒘𝒓𝒆𝒗 = - (1 mol) 0.0821 L.atmp. K-1 mol-1 . 300 K ln 𝟓𝑳−𝟏𝒎𝒐𝒍 × 𝟎.𝟎𝟒𝟐𝑳.𝒎𝒐𝒍−𝟏
𝟏 𝟏
+ 2.283L2 .bar.mol-2 (1 mol-2) 𝟏𝟎𝒍
− 𝟓𝒍
𝟏𝟎𝑳− 𝟎.𝟎𝟒𝟐𝑳 𝟏 𝟏
𝒘𝒓𝒆𝒗 = - 0.0821 L.atmp. 300 ln + 2.283L2 .bar −
𝟓𝑳− 𝟎.𝟎𝟒𝟐𝑳 𝟏𝟎𝒍 𝟓𝒍
87
𝒘𝒓𝒆𝒗 = - 17.176 L.atmp – 0.228 L .bar 1 atm = 1.01325 bar

𝒘𝒓𝒆𝒗 = - 17.176 L.atmp – 0.225 L .atmp = -17.20 L.atm = -1742.95 J

Quiz-1Solution
Q.1 b) A gas absorbs 200 J of heat and expands against the external
constant pressure of 1.5 atm. from a volume of 0.5 L to 1.0 L. Calculate
the change in internal energy in Joules. Given: R=8.314 J/K/mol = 0.0821
L.atm. K-1mol-1 (5pts)

𝒅𝑼 = 𝜹𝑸 + 𝜹𝑾
88
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90
91
In a reversible, adiabatic process of a system comprising
of one mole of an ideal gas, prove the following
relationships:

92
Heat Capacity of Solids as Function of T at Room
Temperature

Molar Heat capacity of copper = 24.45 J /K / mol

Molar Heat Capacity of Water = 75.31 J / K / mol

What does thermal energy supplied to water do?

1. Breaking hydrogen bonds.

2. Increase Translation, Rotations, vibration of molecules

What about solid copper ? 93

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Molar Heat Capacity of Solids near room T
One mole copper = 24.4 J mol-1 K-1

One mole NaCl: = 51 J mol-1 K-1

One mole CaF2: = 72 J mol-1 K-1
Classical mechanics calculates C v (T) near room T
Using law of Equipartition of Energy
Oscillation with the same frequency
Consider Cu:
N atoms oscillating each in 3-Dimension
Average E / oscillator in 1-Dimesion = (1/2 kT + 1/2 kT)
Total E = NA (6/2kT) = 6/2RT ( in 3 – Dimension X, Y, Z ) 95
E / T = Cv = (6/2)(8.314JK-1mol-1) = 24.9 J K-1 mol-1
Total E of classical harmonic oscillator: K(kinetic) + U(x) (potential)

= 5 x 1012 s-1

96
Determine the degree of freedom for one mole CaF 2 crystal and show that the
molar heat capacity of CaF2 at room temperature is 72 J. mol-1. K-1. R = 8.314 J.K-
1.mol -1

97
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Experiment shows dependence of Cv on T
Cv of copper = 24.9 J mol-1 K-1
oscillation frequency, f = 5 x 1012 s-1

99

Einstein Model:
Degrees of freedom and energy storage by molecules

100
Degrees of freedom for storing energy

1/2kT is unit i.e 2(1/2kT)

101
No. of vibrations = 3 N – 6 for nonlinear
= 3 N – 5 for linear
Degrees of freedom of diatomic gas molecule:
7(1/2 kT)

1 / 2 KT = 1/2 (1.38x
10-23 JK-1 molec.-1 )
(300K)
= 2.1x10-21 J/molec.
per degree of freedom

• At low temperature, di-atomic molecule acts like monoatomic gas, Cv =

3R/2
• At high temperature, Cv increases to 5R/2 consistent with adding rotational
energy and not vibrational energy. 102

• At still high temperature, Cv = 7R/2 consistent with adding rotational energy

as well as vibrational energy.
Molar Heat Capacity of Solids

k is large for diamond

According to Dulong & Petits law, molar heat capacity of solids at room and
high temperature is nearly equal to 3R. This can be explained using law of
equipartition. Each atom can vibrate about its equilibrium position. But in 103
reality, molar heat capacity of solids varies with temperature as shown in
figure.
104
Standing waves
in solids with discrete frequencies
Integral number of half wavelength fit
into the solid medium

(1/2) λ, 2(1/2)λ , 3(1/2)λ, 4(1/2)λ = m λ/2

m = 1, 2, 3, ……..

1/2f, 3/2f, 5/2f, 7/2f………

105
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Distribution of oscillators
among energy levels:

k = 1.381x10-23 JK-1 per molecule

kT = (1.38x10-23 Jk-1 molec-1 )(300 K) = 414x10-23 J/molecule

hν = (6.6x10-34 Js ). (5x1012 s-1 ) = 33x10-22 J / spacing

hν /kT = (6.6x10-34). (5x1012) / (1.38x10-23)(300)= 0.797

Contribution to Cv can be considered only when

kT > hv
107
How are levels populated?
 Quantized energy levels
of oscillators
Energy spacing = hν

Boltzmann Distribution e- 6(0.797)

at 300 K
e- 5(0.797)
Nn/N0 = e- n.(hν)/(kT) = e- n.(0.797) = 0.451 e- 4(0.797) = 0.041
e- 3(0.797) = 0.092
e- 2(0.797) = 0.203
For n = 1 e- (0.797)= 0.451
108

1
 Quantized energy levels of
oscillators
Energy spacing = hν
Boltzmann Distribution
at 300 K

41

Ni = N0 Exp( - n.(hν)/(kT) ) 92

203

kT vs hv
451

hν /kT = (6.6x10-34). (5x1012) / (1.38x10-23)(300)= 0.797

1000
109
Average Energy of Planck’s Oscillator
➢ What is the Planck’s expression for the average energy of
the harmonic oscillator?
➢ How is it compared to the classical average value?
Planck’s suggested that energy of quantum is proportional to frequency
of oscillator:

All the oscillators in solid having same fundamental vibration

frequency.

The energy distribution is given by Boltzmann equations:

110

Where N 0 is number of oscillator with zero energy & k is Boltzmann constant

Average Energy of Planck’s Oscillator

For n = 0 , which is ground state

Ni = 𝑁𝑜
For n = 1 , which is first energy state (hν)
ℎν
𝑁1 = 𝑁𝑜 𝑒 −𝑘𝑇

For n = 2, which is first energy state (hν)

2ℎν
𝑁2 = 𝑁𝑜𝑒 − 𝑘𝑇

The total number of oscillator in all states:

ℎν
𝑊ℎ𝑒𝑟𝑒 𝑥 = 𝑒 − 𝑘𝑇
The series 111
Average Energy of Planck’s Oscillator
The total number of oscillator in all states:

The total energy in all states:

The series is is expansion of:

112
Average Energy of Planck’s Oscillator
➢ What is the Planck’s expression for the average energy of
the harmonic oscillator?
➢ How is it compared to the classical average value?

When hν is much less than kT

ℎ𝑣
ℎ𝑣
𝑒 𝑘𝑇 =1+
𝑘𝑇

ℎ𝑣
𝜖 ҧ = ℎ𝑣
−1+1
𝑘𝑇

113
Einstein’s Model of Heat Capacity
The average energy of Harmonic oscillator according to Planck’s theory
is:

For Einstein’s solid consisting of N atoms:

114

Cv approaches to zero, which quantitatively explains Cv 0 as T 0

Einstein’s Model of Heat Capacity
As T ∞

𝑥2 𝑥3
We know 𝑒 𝑥 −1= 𝑥 + + +…….
2! 3!

For small 𝑥 ∶ 𝑒 𝑥 − 1≈ 𝑥 𝑎𝑛𝑑 =1

Cv = 3 Nk where N = NA

Cv = 3 NA k = 3R 115
Heat Capacity of Solids as Function of T - Summary

At sufficiently high temperatures, the molar heat capacities of

mono-atomic solid approach the classical Dulong-Petit law of 3R =
24.9 J K-1 mol-1. For a collection of N atoms, there are 3N – 6 ≈ 3N
(for very large N) vibrational modes. Each vibrational mode
contributes kBT to the internal energy. Each mole of atoms is
therefore expected to contribute 3R to the specific heat by the 116
energy equipartition theorem.
117
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Enthalpy Changes (ΔH)
Calculation of ΔH in Phase transformation
and Chemical Changes

119
Heating curve for one mole ( 18 g ) of water
And change of physical state

120
MP

121
122
123
Quiz-2 Solution
Q.1 (a) One mole of H2O(g) at 1 atm. and 100 °C occupies a volume of 30.6 L.
When one mole of H2O(g) condensed to one mole of H2O(l) at 1atm. and 100 °C,
40.66 k.J of heat is released. If the density of H2O(l) at this temperature and
pressure is 0.996 g/cm3, calculate the change in internal energy in Joules for
the condensation of one mole of water at 1atm. and 100 °C. (14pts)
Given: R = 8.314 J. K-1mol-1 = 0.0821 L.atm. K-1mol-1 and 1L = 1000 cm3

124
Quiz-2 Solution
Q.1 (b) Given: R = 8.314 J.K -1.mol-1. Show that Cv is roughly 25 J.mol -1.k-1 for a
monoatomic solid at room temperature. (6pts)

125
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Enthalpy of reactions, ∆Hr , can be calculated
from tabulated enthalpies of formation, ∆Hf
Oxy-acetyline welding

127
 1 L . bar = 1x10-3 m3 x 105 Pa

1 L . bar = 102 J

(not per mole) 128

ΔH accompanying Phase Change

129
∆H = - 2100 J / mol
Enthalpy of Reaction: ΔHr

CH4 (g)+ 2O2 (g)→ 2H2O (l) + CO2 (g)

Enthalpy of formation: ∆Hf
2H2(g) + O2 (g) → 2H2O (l); ∆Hf = - 286kJ

C (graphite ) + O2 (g)→ CO2 (g); ∆Hf = - 393.5kJ

What about the backward reaction?

130
131
Compound ΔHf (kJ/mol) Compound ΔHf (kJ/mol)
AgBr(s) -99.5 C2H2(g) +226.7
AgCl(s) -127.0 C2H4(g) +52.3
AgI(s) -62.4 C2H6(g) -84.7
Ag2O(s) -30.6 C3H8(g) -103.8
Ag2S(s) -31.8 n-C4H10(g) -124.7
Al2O3(s) -1669.8 n-C5H12(l) -173.1
BaCl2(s) -860.1 C2H5OH(l) -277.6
BaCO3(s) -1218.8 CoO(s) -239.3
BaO(s) -558.1 Cr2O3(s) -1128.4
BaSO4(s) -1465.2 CuO(s) -155.2
CaCl2(s) -795.0 Cu2O(s) -166.7
CaCO3 -1207.0 CuS(s) -48.5
CaO(s) -635.5 CuSO4(s) -769.9
Ca(OH)2(s) -986.6 Fe2O3(s) -822.2
CaSO4(s) -1432.7 Fe3O4(s) -1120.9
CCl4(l) -139.5 HBr(g) -36.2
CH4(g) -74.8 HCl(g) -92.3
CHCl3(l) -131.8 HF(g) -268.6
CH3OH(l) -238.6 HI(g) +25.9
132
CO(g) -110.5 HNO3(l) -173.2
CO2(g) -393.5 H2O(g) -241.8
133
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 What if heat of formation
Cannot be determined experimentally
Hess’s Law

135
 2C(s) + H2(g) → C2H2(g); ∆Hf
1.
2.

3.
Multiply R-1 by 2. Add R-1 and R-2.
Add the reverse of R–3 to the sum of R-1 and R-2

136
DH°f (4) = 2 DH°rxn(1) + DH°rxn(2) + reverse of DH°rxn(3)
= (2)(–393.5 kJ·mol–1) + (–285.8 kJ·mol–1) + (+1300.2 kJ·mol-1 = +227.4 kJ·mol-1
 Excess reagent

60 g
Moles of Fe2O3 = = 0.37 mole (Given)
[2(56) + 48]
15g
Moles of Al = = 0.555 moles (Given)
26.98
= 0.74 moles of Al (Required)

For what purpose can this reaction

can be used ? 137
 Example Problem
How much Al (in gram) will be consumed in the following reaction if
474 kJ of heat is to evolve in this reaction at 25 C and at constant
pressure of one bar. Given: At. Masses (amu): Fe = 56; Al = 27; O
=16.

Heat release against consumption of 2 moles of Al = -851.5 kJ

−851.5 kJ
…………………………………………………1 mole = = −𝟒𝟐𝟓 𝐊. 𝐉. 𝐦𝐨𝐥−𝟏
𝟐
−𝟒𝟐𝟓 𝐊. 𝐉 heat evolved for no of moles of Al = 1 mole
1 mol
1……………………………………………………….= −𝟒𝟐𝟓 𝐊.𝐉
1 mol
474 k. J…………………………………………..= −𝟒𝟐𝟓 𝐊.𝐉 × 𝟒𝟕𝟒 𝐤. 𝐉 = 1.113 moles

1 mole of Al how many grams of Al = 27 gm

1.113………………………………………= 27 x 1.113 = 30.05 gm 138
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∆Hr = + 10.9 kJ / mol T = -20⁰C

140
 Lattice Enthalpy
Born – Haber Bond dissociation
Cycle
Electron affinity

o The amount of energy Ionization

released, when one
mole of ionic solid is
formed by close
-376
packing of gaseous ions.
o The amount of energy
absorbed when one Sublimation

mole ionic solid is

turned into infinitely
-376 -411 = -787 kJ /mol
separated gas ions
under standard
conditions. 141
 Second Law of Thermodynamics

►Natural processes are spontaneous as a result

of which:
→energy is minimized and dispersed
→entropy is created and reaches a maximum
Minimizing E, dispersing E,
Creating S, Maximizing S
continue
until equilibrium is achieved
►How can spontaneity of a process be predicted
Change in free energy must be negative 142

∆G = ∆H – T.∆S
 Spontaneous Process
Scientists believed: spontaneous process runs to minimize energy
Current view: spontaneous process runs to minimize energy and
maximize disorder

1. Rusting of Iron
They were motivated by the fact that spontaneous process always
lowers energy (Enthalpy) just as stones roll down hill: This
conclusion proved to be wrong
Endothermic but spontaneous
143

Conclusion: systems evolve spontaneously in a direction in which energy

decreases + disorder increases
 Second Law of Thermodynamics
Spontaneous process,
Entropy, Free energy, state functions
Dispersal of energy and matter
Quantization of matter, electricity, energy
Concept of Entropy was defined before the era of:
→Quantization of matter ( atoms, molecules )
→Quantization of electricity ( Electrons )
→Quantization of energy ( Photons )

144
So, entropy was not defined at corpuscular level
Second Law of Thermodynamics

145
Thermal Equilibrium

146
Thermal Equilibrium

Not take place

147
Change in Entropy

148
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Second Law of Thermodynamics

For isolated system

150
 ∆G in Phase Change

∆H = - 2100 J / mol and ∆S = - 7.4 J / mol/ K

∆G = ∆H – T.∆S
151
= -2100 - (10 + 273)(-7.4)
= - 5.8 J/mol
 Another State Function, S (T, V)

: is not state function. : is function of temp. for an ideal gas

Using 1 / T as integrating factor

S turns out to be a state function 152

which depends on T and V

 Mid Exam Solution-2021
Q.1 Fine steel fiber is contained in a cylinder filled with pure oxygen. The cylinder is fitted with a
friction-less piston which maintains the oxygen pressure at 1 atm. The iron in the steel fiber reacts
with oxygen very slowly to form Fe2 O3. Heat generated by the reaction is removed during the process
to keep the temperature constant at 25°C. For the reaction of 2 moles of iron (given below), 831.08
kJ of heat is removed: 2Fe (s) + 3/2 O2 (g) Fe 2O3 (s)
Calculate: (a) The volume occupied by O2 as an ideal gas, (b) Heat involved, work done and change
in internal energy.
→ 2 Fe + 3/2 O2 → Fe2O3 ; ∆H = -831.08 kJ (Exothermic)
→ T constant at 298K, O2 pressure constant at one atm.
→ Given: ∆H= - 831 kJ / mol & ∆U = δQ + δW
→ Calculate ∆U, Q, and W
→ Determine W, then Q, then ∆U

= ∆H 153
 Q.2 Consider one mole of nitrogen with Van der Waals constants: a = 1.39 L2.atm. mol-
2; b = 0.391 L. mol -1 Calculate the pressure of 2 L nitrogen at temperature of 400 K

when:
(a) Nitrogen behaves as Van der Waal gas. (8 pts)
(b) Nitrogen behaves as an ideal gas. (6 pts)
(c) Explain the difference between the pressure of nitrogen being ideal gas and Vander
Waal gas. (4 pts) Given: R = 0.082 L.atm.mol-1.K -1

The pressure exerted by the real gas will be less due to interaction between
molecules as molecules attract each other and prevent the other to cause more 154
pressure on the wall of container.
Q.3 (a) Start from δW = - PdV for one mole of an ideal gas and show that the work
involved is W = Cv (T2-T1) if the gas is adiabatically and reversibly cooled from T1 to
T2. (9 pts)

155
(b) How much Al will be consumed in the following reaction if 474 kJ of heat is to evolve in
this reaction at 25 °C and at constant pressure of one bar. Given: At. Masses (amu): Fe =
56; Al = 27; O =16. (9pts)

Fe 2O3(s) + 2 Al (s) Al2O3 (s) + 2Fe (s) ; ∆H0rxn = - 851.5 KJ.mol-1

Heat release against consumption of 2 moles of Al = -851.5 kJ

−851.5 kJ
…………………………………………………1 mole = 2
= −425 K. J. mol−1
−425 K. J heat evolved for no of moles of Al = 1 mole
1 mol
1……………………………………………………….=
−425 K.J
1 mol
474 k. J…………………………………………..= × 474 k. J = 1.113 moles
−425 K.J

1 mole of Al how many grams of Al = 27 gm

1.113………………………………………= 27 x 1.113 = 30.05 gm

156
Q.4 One mole of super-cooled liquid tin (Sn) is held at constant temperature of 495 K. The
true melting point of tin (Sn) is 505 K. Calculate the fraction of the tin which
spontaneously and adiabatically freezes and convert into solid. Use following
thermodynamic data of Sn: (18pts)
ΔHºfus , (Sn) = 7070 J.mol-1 at Tmelting = 505 K;
CP, Sn (liquid) = 34.7-9.2 x 10-3 T J.mol-1.K-1
CP, Sn (solid) = 18.5 + 26 x 10-3 T J.mol-1.K-1

157
158
42.5 cm3 volume produced energy of = -240.8 kJ

−240.8 𝐾.𝐽
1………………………………………….=
42.5 cm3
−240.8 𝑘.𝐽
2.5 x 105 cm3......................................= x 2.5 x 105 cm3
42.5 cm3

= 14.16 x 105 kJ 159

Thermodynamics of Materials
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Carnot Cycle

161
Reversible Isothermal Expansion

162
 Reversible Adiabatic Expansion
Step: 2 Reversible adiabatic expansion

163
 Carnot Cycle
Step: 3 Reversible isothermal compression

164
 Carnot Cycle
Step: 4 Reversible adiabatic compression

165
Carnot Cycle

Show that: 166

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 Show that: V2 / V1 = V3 / V4

Similarly,

Finally,

168
169
 6x105 Pa
T1 = 1473 K
4x104 Pa
T2 = 573 K
170
171
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 𝑸
A Simple System to Explain :
𝑻
Two systems in Thermal Contact
o Thermally conducting wall
o System isolated from rest of World
Heat transfer from hot to cold
o Qh < 0 and Qc > 0 : same magnitude Q
o Energy dispersal, towards equal T

𝑸𝒉 𝑸𝒄 𝑸
- 𝑻𝒉
+ 𝑻𝒄
>0 : 𝑻
is increasing

No Heat transfer from cold to hot

o Eventhough 1st law of thermodynamics
says this could happen.
o Does not violate energy conservation
173

𝑸𝒉 𝑸𝒄 𝑄
𝑻𝒉
- 𝑻𝒄
<0 : 𝑇
is deceasing
174
175
−

176
177
178
Thermodynamics of Materials
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 Mid Exam Solution-2022
Q.1 Molten copper is super-cooled to 5°C below its true melting point (1084 °C).
Nucleation of solid copper then takes place and solidification proceeds under adiabatic
conditions. Calculate the percentage of the copper that solidified.
(18pts) CLO-2

180
Q.2 One mole of ethane at 25 °C and one atm. is heated to 1200 °C at constant pressure.
Assuming ideal gas behavior, calculate the values of W, Q, ∆U and ∆H. Given the molar
heat capacity of ethane as:
Cp = [0.532 + (1.776 x 10-2) T – 6.870 x 10-7) T2 + (8.513 x 10-9) T3 ] J.mol-1. K -1 ; R = 8.314 k.J.mol-
1.K -1 (18pts) CLO-2

181
182
Q.3 Consider one mole of CH4 with Van der Waals constants are: a = 2.283L2 .bar/mol2 ;
b = 0.04278 L/mol Calculate the work done when the gas expands reversibly from 5 L to
10 L at constant temperature of 27⁰C. CLO-1
(1). Expansion as an ideal gas obeying PV = RT (7pts)
(2). Expansion as a Van der Waal gas obeying (P + a/V2) (V-b) = RT. (7pts)
(3).Explain the difference in the work done in the two cases. (4pts)
Given: R=8.314 J/K/mol = 0.0821 L.atm. K-1mol-1

183
184
Q.4 The mean solar energy flux at the Earth’s surface is about 0.066 Watt.cm-2. Using a
non-focusing collector the temperature of the device can reach a value of about 90 °C. If
we operate a heat engine using the collector as the heat source and a low temperature
reservoir at 25°C, calculate area of collector in square meter needed to produce 746 Watt
(Watt is 1J.S-1 of heat flow). Assume engine operates at maximum efficiency and is ideal
heat engine. Hint: Recall the Carnot Efficiency. (18 pts) CLO-1

0.066 Watt of heat supplied by an area of collector = 1 cm2

1 185
1 Watt = 0.066 cm2
1 1𝑚2
4144 Watt = 0.066 × 4144 cm2 = 62787 cm2 1000 𝑐𝑚2 = 62.7 𝑚2
Q.5 Metals exhibit some interesting properties when they are rapidly solidified from the
liquid state. An apparatus for the rapid solidification of copper is cooled by water. In the
apparatus, liquid copper at its melting point (1356 K) is sprayed on a cooling surface,
where it solidified and cools to 400 K. The copper is supplied to the apparatus at the rate
of one kilogram per minute. Cooling water is available at 20 ℃ , and is not allowed to
raise above 80℃ temperature. What is the minimum flow rate of water in the apparatus,
in cubic meters per minute? CLO-1
Given: Cp (water) = 4.184 J.g-1.k-1, Density of water =1 g.cm-3; Molecular weight of
copper = 63.54 g.mol-1; Cp (copper) = 7 cal.mol-1.k-1, heat of fusion of Copper = 3120
cal.mol-1; 1cal = 4.18 J (18pts)

186
187
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Refrigerator and Heat Pump

189
190
Coefficient of Performance for Refrigerator

𝑞𝑐 𝑞ℎ
+ =0
𝑇1 𝑇2
𝑞ℎ 𝑞𝑐
=−
𝑇2 𝑇1
𝑞ℎ 𝑇2
𝑞𝑐
= −𝑇
1
𝑞 𝑇
1 + 𝑞ℎ = 1 − 𝑇2
𝑐 1

𝑞𝑐 + 𝑞ℎ 𝑇1 − 𝑇2
− =−
𝑞𝑐 𝑇1 191
𝑞𝑐 𝑇1 𝑞𝑐 + 𝑞ℎ 𝑇2 − 𝑇1
− = − =
𝑞𝑐 + 𝑞ℎ 𝑇2 − 𝑇1 𝑞 𝑇
 Example Problem
A refrigerator takes 1000 J of heat from cold reservoir at 273 K and pumps it into hot
reservoir at 293K. Calculate the amount of energy to hot reservoir. How much work is
needed to accomplish.

Refrigerator

Inside

𝑄𝑐 𝑄ℎ 𝑄ℎ 𝑄𝑐
𝑄𝑐 = × 𝑇𝑐 ℎ 𝑇
𝑄 = × 𝑇ℎ PF = 1000 / 73 = 13.7 192
+ =0 𝑇ℎ 𝑐
𝑇𝑐 𝑇ℎ

293/273 = - qh / qc - qh = 293 / 273 x 1000 = 1073 J

Q.1 A domestic food freezer maintains a temperature of -15 °C. The ambient air temperature
is 30 °C. If heat leaks into the freezer at a continuous rate of 1.75 kW (1Watt = 1J.S-1)
what is the least power required to pump this heat out continuously. (15pts)

Tc = -15 °C = -15 + 273 = 258 K

Th = 30 °C = 30 + 273 = 303 K

Qc = 1.75 kW

W=?

𝑄𝑐 𝑄ℎ
+ =0 W = Qh - Qc
𝑇𝑐 𝑇ℎ

𝑄𝑐 W = 2.05 𝑘𝑊 − 1.75 kW
𝑄ℎ = − × 𝑇ℎ
𝑇𝑐
= 0.305 kW
1.75 𝑘𝑊×303 𝑘
𝑄ℎ = −
258 𝑘 193

𝑄ℎ = − 2.05 𝑘𝑊
Q.1 A domestic food freezer maintains a temperature of -15 °C. The ambient air temperature
is 30 °C. If heat leaks into the freezer at a continuous rate of 1.75 kW (1Watt = 1J.S-1)
what is the least power required to pump this heat out continuously. (15pts)

Tc = -15 °C = -15 + 273 = 258 K

Th = 30 °C = 30 + 273 = 303 K

Qc = 1.75 kW

W=?
258 𝑘
𝐶𝑂𝑃 = = 5.73
303 𝑘−258

Qc
𝐶𝑂𝑃 =
𝑊

Qc 1.75 𝑘 𝑊
W= =
𝐶𝑂𝑃 5.73
194

W= 0.30 𝑘𝑊
 Example Problem
A Carnot refrigerator takes 4000 J of heat energy from cold reservoir at 270 K and
pumps it into hot reservoir at 300 K.
1. Calculate the amount of energy transferred to hot reservoir.
2. How much work is needed to accomplish this?
3. Calculate the coefficient of performance of this refrigerator.

195
 Example Problem
A refrigerator uses 1500 J of mechanical work to absorb 4500 J from cold reservoir at
temperature of 250 K. The hot reservoir is at 300 K.
1. What is maximum coefficient of performance by considering it Carnot refrigerator?
2. How much energy is delivered to the hot reservoir?

196
Thermodynamics of Materials
MM-231

Lecture # 26

GHULAM ISHAQ KHAN INSTITUTE OF ENGINEERING

SCIENCES & TECHNOLOGY

FACULTY OF MATERIAL & CHEMICAL ENGINEERING

Coefficient of Performance for Heat Pump
𝑞𝑐 𝑞ℎ
+ =0
𝑇𝑐 𝑇ℎ

𝑞ℎ 𝑞𝑐
=−
𝑞ℎ 𝑇ℎ 𝑇𝑐
𝜂=
𝑤 𝑞𝑐 𝑇𝑐
𝑞ℎ
= −𝑇
ℎ

𝑞𝑐 𝑇1
1+ =1−
𝑞ℎ 𝑇2

𝑞𝑐 + 𝑞ℎ 𝑇1 − 𝑇2 198
𝑞ℎ 𝑇2 − =
− = 𝑞ℎ 𝑇2
𝑞𝑐 + 𝑞ℎ T1− T2
A heat pump removes heat from cold reservoir at 258 K and pump into hot reservoir at
temperature of 303 K.

Heat Pump

𝑞ℎ
𝜂=
𝑤
1000
𝜂= 145
= 6.8

qc / qh = - TC /TH

855 / qh = - 258 /303 199

𝜂=
303𝑘
= 6.8 qh / 855= - 303 /258
258𝑘−303𝑘 qh = 1004 J
Example Problem

200
𝑄2 𝑄4
𝑇1
+ 𝑇2
=0

500𝐽 𝑄4
+ =0
263 298

500𝐽
𝑄4 = - x 298 𝐾 201
263𝐾

𝑄4 = -567𝐽
202
203
q1

q4

204
205
 Carnot Cycle
Step: 3 Reversible isothermal compression

206
 Carnot Cycle
Step: 4 Reversible adiabatic compression

207
Carnot Cycle

Show that: 208

Molecular Statistics
and
Thermodynamics

209
►What is mean by degradation of energy?
►Natural processes are spontaneous as a result
of which:
→energy is minimized and dispersed
→entropy is created and reaches a maximum
Minimizing E, dispersing E,
Creating S, Maximizing S
continue
until equilibrium is achieved
How the matter store and transfer of energy?
What happens to matter in molecular point of view when
thermal energy is transferred to or from the matter? 210

How do we define micro and macro state of matter?

 N molecules
Molecular distribution
in energy levels
Assuming:
4 go into first level
3 go into second level
2 go into third level
and so on

How much energy this =2

system of 9 molecules have?
=3

=4
211
 Quantized energy levels
of oscillators
Energy spacing = hν

Boltzmann Distribution e- 6(0.797)

at 300 K
e- 5(0.797)
Nn/N0 = e- n.(hν)/(kT) = e- n.(0.797) = 0.451 e- 4(0.797) = 0.041
e- 3(0.797) = 0.092
e- 2(0.797) = 0.203
For n = 1 e- (0.797)= 0.451
212

1
Thermodynamics of Materials
MM-231

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GHULAM ISHAQ KHAN INSTITUTE OF ENGINEERING

SCIENCES & TECHNOLOGY

FACULTY OF MATERIAL & CHEMICAL ENGINEERING

 3 units E & 3 Molecules
One unit E to each one Three units E to one of them

Two units E to one and one unit E to second one

214
 3 units of Energy and
3 Molecules of matter
Calculate number of different complexions.

One complexion (Ω =1) Three complexions (Ω =3)

3! 3! 3.2!
Ω = 0!.3! = 1 Ω= = =3
2!.0!.0!.0!1! 2!
N! 215
=
n0! n1! n2! n3!........
216
3 units E & 3 Molecules → Microstates?

Complexions (Ω = 6)
3! 3.2.1
𝑵! Ω= = =6
Ω= 1!.1!.1! 1!
(𝒏𝟎 !.𝒏𝟏 !.𝒏𝟐 !.𝒏𝟑 !…..)

Total no. of complexions compatible

with three energy units = 1+3+6

217
 N
Molecules distributing
among energy levels
Assuming:

3 go into first level

N(N-1)(N-2) / 3!

4 go into second level

(N-3)(N-4)(N-5)(N-6) /4!

2 go into third level =2

(N-7)(N-8)/2! =4

=3
𝑵! 218
Ω=
(𝒏𝟎 !.𝒏𝟏 !.𝒏𝟐 !.𝒏𝟑 !…..)
“configuration” is the collection of microstates that possess identical
distributions of energy among the accessible energy levels without
distinguishing individual molecules.
219
 Collisions among molecules result in
changing one energy state into another one

Energy states (E)

Complexions (Ω)

Microstates (W)

220
 N!
=
n0! n1! n2! n3!........ Add one Unit of E
W rises

4! 4.3!
Ω= = =4
3!.0!.0!.1!.0! 1! 221
4! 4.3.2!
Ω= = = 12
2!.1!.1!.0!.0! 2!
Two System Block 1 and Block 2

222
 28 →21 6 → 10

223

Any process that runs its own is called spontaneous.

28 → 21 → 15 6 → 10 → 15

224
Any process in which microstates increase is called
spontaneous.

21

225
Thermodynamics of Materials
MM-231

Lecture # 28

GHULAM ISHAQ KHAN INSTITUTE OF ENGINEERING

SCIENCES & TECHNOLOGY

FACULTY OF MATERIAL & CHEMICAL ENGINEERING

Example Problem

N!
=
n0! n1! n2! n3!........
5

227
Example Problem

228
229
 Equilibrium Criterion and Entropy

What is W? 230
Under what conditions above equation approximately represent
total number of microstates of system?
Any process in which microstates increase is called?
spontaneous.

21

231
 Summary of Second Law of Thermo
The criterion ∆S > 0 applies to spontaneous process taking place in an
isolated system (example → the universe

How can spontaneity be predicted?

 Example Problem

4! 4! 4.3.2!
W(a) = =1 W(b) = 2!.2!. = =6
4!.0!. 1!

233
Thermodynamics of Materials
MM-231

Lecture # 29

GHULAM ISHAQ KHAN INSTITUTE OF ENGINEERING

SCIENCES & TECHNOLOGY

FACULTY OF MATERIAL & CHEMICAL ENGINEERING

Equilibrium Criterion and Entropy

235
 Equilibrium Criterion and Entropy
For Ten Particles:

For 1,000 Particles what will be the most probable microstate?

236
 Example Problem
Q.1 System A contains three particles and six units of energy; Calculate:
(a) The number of microstates for all the possible configurations and show schematically
(in tabulated form) these configurations?
(b) The number of microstates and configurations (in tabulated form) if one unit of energy
is transferred from system A to system B having three particles and two units of energy?
(c) The change in entropy of system A when one unit of energy is lost. The value of
Boltzmann constant is 1.38x10-23J.K-1 ?
(d) Explain the final change in entropy (Δssystem) of system A in context of 2 nd law of thermodynamics.

𝟐𝟏
𝒅𝑺 = 𝟏. 𝟑𝟖 × 𝟏𝟎−𝟐𝟑 J.K-1 ln = - 0.39 × 𝟏𝟎−𝟐𝟑 J.K-1
𝟐𝟖
237
The change in entropy of system A is negative, and it is possible as second law of thermodynamics
explains that change in entropy of universe for a reversible and irreversible process should be
ΔSuniverse ≥ 0
 Equilibrium Criterion and Entropy
Show mathematically that the number of microstates are maximum for
a fifty-fifty distribution?

𝑙𝑛𝑊 = 𝑛 𝑙𝑛 𝑛 − 𝑛 − (𝑛𝐿 ln𝑛𝐿 - 𝑛𝐿 )- [(n- 𝑛𝐿 )ln (n- 𝑛𝐿 )-(n- 𝑛𝐿 )]

𝑙𝑛𝑊 = 𝑛 𝑙𝑛 𝑛 − 𝑛 − 𝑛𝐿 ln𝑛𝐿 + 𝑛𝐿 - (n- 𝑛𝐿 ) ln (n- 𝑛𝐿 ) + n - 𝑛𝐿

238
 Equilibrium Criterion and Entropy

𝑙𝑛𝑊 = 𝑛 𝑙𝑛 𝑛 − 𝑛𝐿 ln𝑛𝐿- n ln (n- 𝑛𝐿 ) + 𝑛𝐿 ln (n- 𝑛𝐿 )

𝑑𝑙𝑛𝑊 1 −1 −1
𝑑𝑛𝐿
= 0 − [𝑛𝐿 𝑛𝐿
+ 𝑙𝑛 𝑛𝐿 ] − n 𝑛−𝑛𝐿
+[ 𝑛𝐿 𝑛−𝑛𝐿
+ ln (n- 𝑛𝐿 )]

𝑑𝑙𝑛𝑊 𝑛 𝑛𝐿
𝑑𝑛𝐿
= −1 − 𝑙𝑛 𝑛𝐿 + 𝑛−𝑛𝐿
− 𝑛−𝑛𝐿
+ ln (n- 𝑛𝐿 )

𝑑𝑙𝑛𝑊 𝑛− 𝑛𝐿
= −1 − 𝑙𝑛 𝑛𝐿 + [ ] + ln (n- 𝑛𝐿 )
𝑑𝑛𝐿 𝑛−𝑛𝐿

𝑑𝑙𝑛𝑊
𝑑𝑛𝐿
= −1 − 𝑙𝑛 𝑛𝐿 + 1 + ln (n- 𝑛𝐿 )

239
𝑑𝑙𝑛𝑊 𝑛− 𝑛𝐿
𝑑𝑛𝐿
= 𝑙𝑛 𝑛𝐿
=0

This Eq. is true when 𝒏𝑳 = ½ n

 Equilibrium Criterion and Entropy
How the previous procedure can be extended to more
general cases?

240
Equilibrium Criterion and Entropy

241
 Equilibrium Criterion and Entropy
The most probable microstate got this Eq.?

Two conditions/constraints:

242
Equilibrium Criterion and Entropy

243

Maxwell-Boltzmann distribution
 Quantized Energy Levels of Oscillators

Population of state i =
𝒏𝒊 𝒆−𝜷∈𝒊
= 𝑷𝒊 =
𝒏 𝒁
Partition function Z tells how much energy in different
modes of system i. e different vibrational, different
rotational, rotational states

Energy spacing = hν e- 4(0.797) = 0.041

Boltzmann Distribution
at 300 K e- 3(0.797) = 0.092
e- 2(0.797) = 0.203
Nn/N0 = e- n.(hν)/(kT) = e- n.(0.797) = 0.451
e- (0.797)= 0.451
244

For n = 1 1
Thermodynamics of Materials
MM-231

Lecture # 30

GHULAM ISHAQ KHAN INSTITUTE OF ENGINEERING

SCIENCES & TECHNOLOGY

FACULTY OF MATERIAL & CHEMICAL ENGINEERING

 Quantum Mechanics Explaining Entropy:
E quantized & E-Spacing depends on M and V

Lighter mass / Heavier mass /

Particle in cubic box: Smaller volume Larger volume

𝒉𝟐
∆𝑬 = [ n x2 + n y 2 + n z 2 ]
𝟖𝒎𝑽𝟐/𝟑

He is 126 JK-1Mol-1 Energy →

Xe is 170 JK-1Mol-1

246
 Question
a. The equation ΔE = (n2x+ n2y + n2z). h2 / 8mV2/3 is used to calculate the energy
levels for a particle of mass m moving in a box of volume V.
b. Compare energy level diagram for lighter and heavier masses & also smaller
and larger volumes.

Lighter mass / Heavier mass /

Particle in cubic box: Smaller volume Larger volume

∆E =
h2 / 8mv2/3 [ nx 2 + ny 2 + nz2 ]

247
S0 (298 K) increases with Mass
of ideal gas (J / K)

He (126) Atomic mass: 4

Ne (146)

Ar (155) Atomic mass:40

Kr (164)

248
Energy for a particle in a cube
∆E = [h2 / 8mV2/3 ][ nx2 + ny2 + nz2 ]

249
 Question
The equation ΔE = (n2x+ n2y + n2z). h2 / 8mV2/3 is used to calculate the energy
levels for a particle of mass m moving in a box of volume V.
A. Calculate the first four energy levels in units of (ΔE) / (h2 /8mV2/3)
B. Determine the degeneracies of these levels.

250
 ∆E = h2 / 8mv2
Entropy increases with mass
as well as with volume
1.5x1023 5.2x1030
►S0(298K) with Mass

He(126); Ne(146);

Ar(155); Kr(164)

► ∆S with Volume expansion?

251
Quantum Mechanics & Classical Approach

252
Quantum Mechanics & Classical Approach

Microscopic Approach:

Macroscopic Approach:

253
 Summary of Second Law of Thermo
The criterion ∆S > 0 applies to spontaneous process taking place in an
isolated system (example → the universe

How can spontaneity be predicted?