MSE 502:

Thermodynamics of Materials

Welcome
 Education and Professional Experience
2008-2014
2 Undergraduate and Masters in Applied Chemistry and Chemical Engineering, University of Rajshahi, Bangladesh

2016-2020
PhD in Chemical Engineering, from the Hong Kong University of Science and Technology, Hong Kong
Exchange Program (2018-2019): California Institute of Technology (Caltech), USA

Nov’2020-Mar’2024
Postdoctoral Fellow in Chemical Engineering, Stanford University, USA
 Research Interest

3 My research theme bridges concept from quantum mechanics, electrochemistry, and data science to address
challenges in energy and chemical science for the UN global sustainable developments.
 Heterogeneous Electrocatalysis
Rational Design of Atomically Dispersed 2D-supported Single Atom Catalysts for Electrochemical Reactions

Water Splitting CO2 Electroreduction

Extension of Adv. QM Method

Activity Descriptor Adv. QM Method

Hossain MD et al. Chem Catalysis, 3, 100489,

Hossain MD et al., Adv. Energ. Mater., 9 (10), 1803689, 2019
Hossain MD et al., Nat. Common., 2020, 11 (1), 1-14 2023
Koshy, D, Hossain MD et al. J. Am. Chem. Soc. 2022, 144, 47, 21741–21750
Design of Carbon-based Electrode-Electrolyte Interface Next Generation Electrocatalysts (HEOs)
ReaxFF based MD simulation at High-Temp.

Hossain MD et al., Carbon 183, 940-947, 2021

Hossain MD et al., Nature
Commun., 14 (1), 5936

Next Generation Energy Conversion Reactions

Zhao Z, Hossain MD et al., Matter 3 (5), 1774-1790, 2021 Hossain, MD et al., ACS Catalysis 13 (7), 4272-4282, 2023
 Introduction to the Thermodynamic System
6

Thermodynamics
Origin of the term:
Thermodynamics --- Study of how transfer of heat influences matter.
Now:
Thermodynamics --- All of the influences and interrelationships that affect the condition of matter --
- thermal, mechanical, chemical, gravitational, surface, electrical, magnetic, atomic, ...

• Thermodynamics: Thermodynamics is the study of heat Q

and work W, and their relations.
 Thermodynamics (Energy & Entropy)
7

Heat Capacity
T

Example. Wewill alsolearn how a material like aluminum, silicon or

diamond stores heat thanks to the vibration of its atoms.

.
Example. In this course, wewill learn how an internal combustion engine converts heat into work
 Thermodynamics (Cont’d)
8
• The development of thermodynamics w a s an important step in the
history of science and engineering (cf. Industrial Revolution).

• It placed heat on the same footing a s the other forms of energy,

enabling new technologies (locomotives, road vehicles, etc).

• A seminal work is that of Benjamin Thompson who

showed that heat is not conservative (not related Benjamin Thompson
to particle flows but to energy flows). (1753–1814)
 Thermodynamics System
9 • Let’s first review the terminology of thermodynamics.

• System (Definition). Any volume or any collection of matter/

particles whose boundaries c a n be specified.

The collection of material we choose to examine is called the system.

It may be simple, such as “a mole of neon gas”, or a very complicated
process in a complicated apparatus.
 Thermodynamics System
10 Everything outside the system is the surroundings.

The system and surroundings together make up the universe.

The boundary between a system and its surroundings is the system wall.
 Boundaries
11
 An open system can exchange both mass and energy with its surroundings.

Example: Hot water or tea in an open cup.

 A closed system can exchange energy, but not mass, with its surroundings.

Example: Hot water or tea in a close pot.

 An isolated system cannot exchange mass or energy with its surroundings.

Example: Hot water or tea in a insulated close pot Or thermal flask.

 Thermodynamic Variables
12

State of System: They are the conditions of a system which is described

in terms of certain measurable properties such as Temperature (T),
Volume (V), Pressure (P) etc of the system

State Variables: The properties of system such as temperature,

pressure, volume when changed, the system also changes. These
properties are called state variables.

State Function: It is defined as the property whose value depends only

upon the state of the system and is independent of the path by which
state has been reached.
 States Variables
13 • S t a t e Variables (Definition).Quantitative d a t a that describe
the state of a system.

Pressure P Mass m

Force F

Length l
Example 2. Ball Attached to aSpring.
Volume V
Example 1. Ball.

Temperature T
 Thermodynamic Variables
14

Extensive variables depend on the size or quantity of matter present in the

system; e.g. mass, volume, entropy, magnetic moment, energy.

Intensive variables do not depend on the size of the system or quantity of

matter present in it. They are dependent on the nature of the substance
present in it. e.g. pressure, temperature, magnetic field.

An extensive variable may be changed to an intensive variable, known as a

specific value, by dividing it by a suitable extensive variable, such as mass,
no. of k moles, or no. of molecules.
• Example: the specific heat is normally (heat capacity)/(mass).
 S t a t e Variables (Cont’d)

15
• Our focus on A simple system which is defined by Gibbs as a homogeneous
system disregarding surface and gravitational effects and in the absence of
stress, electric, or magnetic fields.

• We define three categories of basic thermodynamic variables to describe a

system :

1. Total energy of the system.

1. The amounts of different types of matter inside the system.

1. The levels of potentials representing the intensities of the different forms of

energy and thus describing the corresponding thermodynamic stability of each
type of matter in the system.
 S t a t e Variables (Cont’d)
16
• We define three categories of basic thermodynamic variables to describe a
system:
1. Total energy of the system.
2. Matter inside the system.

3. Potential of the matter.

 S t a t e Variables (Cont’d)
17
 S t a t e Variables (Cont’d)
18
• Also, there exist state variables called Densities.
• There are mainly two types of density quantities:
1. amount of matter per mole, or molar quantities
2. amount of matter per unit volume, simply called the density of a
certain type of matter.
System Classifications
 Processes
20
When state of system changes then process is said to occur. Therefore,
a process refers to the change of a system from one equilibrium state to
another.
• An isobaric process is one in which the pressure is constant.
• An isochoric process is one in which the volume is constant.
• An isothermal process is one in which the temperature is constant.
• An adiabatic process is one in which no heat enters or leaves the system; i.e. Q = 0.
• An isentropic process is one in which the entropy is constant.
 Equilibrium States
21

• An equilibrium state is one in which the properties of the system do not

change with time.
• In many cases, an equilibrium state has intensive variables which are
uniform throughout the system.
• A non-equilibrium state may contain intensive variables which vary in
space and/or time.
• An equation of state is a functional relationship between the state
variables; e.g. if P,V and T are the state variables, then the equation of state
has the form f(P, V, T) =0.

Reversible, Irreversible, Spontaneous, Non-spontaneous processes

 Some Thermodynamics Quantities
22
❖Every system is associated with a definite amount of energy, which is
called its internal energy. It is denoted by E or U

❖Change in internal energy in a chemical reaction is the difference in

the internal energies of the products and the reactants
∆𝐸 = 𝐸𝑝 − 𝐸𝑟

❖ Enthalpy or heat content of a system may be defined as the sum of

the internal energy and the product of its pressure and volume.
H = E + PV

❑Entropy is the measure of randomness or disorder of the system. The

greater the randomness, higher the entropy.
 Some Thermodynamics Quantities
23
 Phase Equilibria
24

- Free energy: is function of the internal energy of a system and entropy.

𝐺 = 𝐻 − 𝑇𝑆

- Equilibrium: A system is at equilibrium (stable) if its free energy is at minimum under some specified
condition (temperature, pressure, composition).

- Phase equilibrium: Applies to systems in which more than one phase exists.

- Metastable state: In solid systems, the rate of approach to equilibrium is extremely slight and slow
(equilibrium not completely achieved), so they are in nonequilibrium or metastable state.
 ONE-COMPONENT (OR UNARY)
PHASE DIAGRAMS
25
 Solubility Limit
26
 Components and Phases
27

• Components:
The elements or compounds which are present in the alloy
(e.g., Al and Cu)
• Phases:
The physically and chemically distinct material regions
that form (e.g., α and β).

Aluminum- β (lighter
Copper
phase)
Alloy

α (darker
Adapted from chapter-
opening photograph,
phase)
Chapter 9, Callister,
Materials Science &
Engineering: An
Introduction, 3e.
 Metallic Crystal Structures
28

Simple Cubic (SC)

Face Centered Cubic (FCC)

Body Centered Cubic (BCC)

Hexagonal Closed Packed (HCP)

 Phase Equilibria
29

Simple solution system (e.g., Ni-Cu solution)

Crystal electroneg r (nm)

Structure
Ni FCC 1.9 0.1246
Cu FCC 1.8 0.1278

• Both have the same crystal structure (FCC) and have

similar electronegativities and atomic radii (W. Hume –
Rothery rules) suggesting high mutual solubility.
• Ni and Cu are totally miscible in all proportions.
 Phase Diagrams
30

T(°C)
1600 • 2 phases:
L (liquid)
1500 L (liquid) a (FCC solid solution)
• Phase
Diagram 1400 • 3 phase fields:
for Cu-Ni L
system 1300 L+ a
a
1200 a
Adapted from Fig. 9.3(a), Callister 7e.
(FCC solid (Fig. 9.3(a) is adapted from Phase
1100 Diagrams of Binary Nickel Alloys, P. Nash
solution) (Ed.), ASM International, Materials Park,
OH (1991).
1000
0 20 40 60 80 100 wt% Ni
 Binary-Eutectic Systems
31

has a special composition

2 components with a min. melting T.
Cu-Ag
T(°C) system
Ex.: Cu-Ag system 1200
• 3 single phase regions L (liquid)
(L, a, ) 1000
• Limited solubility: a L + a 779°C L+ 
800
a: mostly Cu TE 8.0 71.9 91.2
: mostly Ag 600
• TE : No liquid below TE a+
• CE : Min. melting TE 400

composition 200
0 20 40 60 CE 80 100
• Eutectic transition Co , wt% Ag
L(CE) a(CaE) + (CE) Adapted from Fig. 9.7,
Callister 7e.