Lecture 1

Engineering Thermodynamics

MIME 212

Prof. Jinhyuk Lee

Mining and Materials Engineering, McGill University
Winter 2024

1
 Instructor
Jinhyuk Lee
Assistant Professor, Materials Engineering

• B.S. in MSE, Seoul National University

• Ph.D. in MSE, MIT
• Postdoc at (a) UC Berkeley, and (b) MIT
• Energy-storage materials
• jinhyuk.lee@mcgill.ca
• Send me an email if you have any questions

2
Textbook & References

The main textbook ($75 in amazon)

“Introduction to the thermodynamics of
materials” ---- David R. Gaskell ----

3
Course Syllabus

4
 Lecture 1

INTRODUCTION AND DEFINITION OF TERMS

(CHAPTER 1 OF THE TEXTBOOK)
 Thermodynamics?
• Is the science of the flow of heat

• Macroscopic framework of energy flows and how this affects properties of a

system of interest.

(More specifically)

• Macroscopic viewpoint in “Classical thermodynamics”

No atomic coordinates (vs. microscopic perspective in statistical mechanics or
molecular biology)

• Energy flows: (a) heat (transfer of random internal kinetic energy), (b) work
(force x displacement), (c) introduction of matters

• A system moves from one macroscopic “equilibrium state” to another

“equilibrium state” due to the energy flows, which affects the properties of a
system

6
 Thermodynamics?

• Developed around 1800 at the time of industrial revolution (steam engine)

• Its original foundation is entirely based on experimentations yet is

“universal”.

“Thermodynamics is the only physical theory of universal content

concerning which I am convinced that, within the framework of the
applicability of its basic concepts, it will never be overthrown.”

Albert Einstein

7
 Relevance of Thermodynamics
• Is the science of the flow of energy (heat, work, and matter)
• Every phenomenon involves the exchange of energy (i) within a system, (ii)
between systems, and (iii) between the system and surrounding.
• Thermodynamics in physics, chemistry, biochemistry, mechanical
engineering, chemical engineering, materials engineering, etc.

8
Ref. Fundamentals of Engineering Thermodynamics by Michael J. Moran, Howard N. Shapiro, Daisie D. Boettner,
Margaret B. Bailey
 TD for Materials Scientists and Engineers
• Raw chemicals => material processing => structure => properties =>
performance (for a desired application)

a) Synthesis conditions for FCC-Fe vs. BCC-Fe (i.e., Phase diagram) (or Ni, NiO, NiO2)
b) Bulk engineering (Vacancies control, anti-site engineering, etc.)
c) Microstructure engineering (Preferred surface: rod / spherical / plate / nanotechnology)

“The materials paradigm”

• Understanding & controlling of material behaviors (under operation)

a) Thermodynamic stability (vs. degradation) of materials (e.g., Corrosion, oxidation)
b) Reaction mechanism of functional materials (e.g., battery materials)

9
 Laws of Thermodynamics

They are not proven but not wrong => “Statistical thermodynamics”
later helps you better understand why they appear to be never wrong.

Universally valid: they cannot be circumvented.

• 0th law: Defines Temperature (T)

• 1st law: Defines Internal energy (U)

• 2nd law: Defines Entropy (S)

• 3th law: Numerical value to the Entropy

10
 Introduction and definition of terms
“Thermodynamic system”

• It is that part of the universe that we are studying. Anything out of the
system is the surroundings. Between the system and the surroundings
is the boundary.

• A TD system is used to identify the subject of a thermodynamic

analysis.

• It is an amount of matter or a 3-D region of space, bounded by an

arbitrary surface.

• The boundary may be real or imaginary. 11

 Introduction and definition of terms
“Thermodynamic system”

• Interactions (transfer of heat, work, matter) across the boundary

between a system and its surroundings play an important role in
thermodynamics

• Proper definition of TD system and thus its boundaries can simplify a

TD analysis

• Again, the boundary may be real or imaginary. You define however

you want.

12
 Introduction and definition of terms
“Thermodynamic system”

When dealing with a TD system, you need to know:

ü Type of the system (i.e., boundaries)

ü Homogeneous / Heterogeneous (# of phases)

ü Number of components

ü TD Properties (Extrinsic / intrinsic properties)

ü Equilibrium (vs. non-equilibrium)

13
 Types of TD systems

a. Open: allows mass, heat, and work to flow freely through the
boundary (e.g., living organism, a boiling cup without a lid)

b. Closed: allows heat and work to flow through the boundary but
not the mass. (e.g., a cup with a tightly fitted cover)

c. Isolated: does not allow heat, work, and mass to flow through the
boundary. (e.g., universe)

14
 Homogeneous vs. Heterogeneous systems
Phase: a region of space, throughout which all physical properties
(e.g., density, index of refraction, crystal structure, chemical
composition) of a material are essentially uniform. A simple
description is that a phase is a region of material that is chemically
uniform, physically distinct, and (often) mechanically separable.

a. Homogeneous: only one phase in the system (it may be made of

many components, e.g., black coffee, salty water (NaCl, H2O)

b. Heterogeneous: multiple phases in the system.

Homogeneous Heterogeneous (e.g., ice + water)

15
 Number of components
Component: a component is one of a collection of chemically-
independent constituents of a system. The number of components
represents the minimum number of independent species necessary
to define the composition of all phases of the system.

Homogeneous Heterogeneous (e.g., ice + water)

Multiple components Single component

(H2O, 2–3% caffeine, 3–5% tannins, etc.) (H2O)

(another example) Salt water => H2O molecules exist in two different
=> A homogeneous system with two phases (solid, liquid)
components (H2O + NaCl) 16
 Thermodynamic properties
TD properties: a “macroscopic physical characteristic” of a system
(used to describe it and predict its behavior) which can be
quantitatively evaluated.

Macroscopic => visible to the naked eye; not microscopic.

Microscopic => so small as to be visible only with a microscope.

When you talk about macroscopic properties of matter, you don’t need
many variables to describe the system. You need few macroscopic
variables that are familiar to you:

• Pressure (P)
• Temperature (T)
• Volume (V)
• Number of moles (n)
• Mass (kg)

17
 Extensive vs. Intensive properties

• Extensive properties: Properties that depend on the size (extent) of the

system.

Examples: Volume, Mass, Surface area, Energy, Enthalpy, Entropy

• Intensive properties: Properties that are independent of the size (extent)

of the system.

Examples: Temperature, pressure, density

You can make intensive properties by dividing extensive properties by mass

(=> specific properties: e.g., specific volume) or number of moles (=> molar
properties: e.g., molar volume, molar heat capacity)
18
 State variables (State properties)
• The unchanged variables/properties at equilibrium are called state
variables. They describe the equilibrium state.

• They don’t care about the history of the state.

• Since there are relationships (e.g., ideal gas law, PV=nRT) between
properties (e.g., P, V, T) of a system, the state of the system can be
determined from a subset of all the properties of a system.

• For one component system all you need to describe the system is the
number of moles (ni) and 2 other variables from P, V, T.
Examples: Volume, Mass, Surface area, Energy, Enthalpy, Entropy

“State” of a system

It is the condition of a system as established by the values of its properties.

Chemical state is determined by the properties such as chemical composition, energy, entropy, etc.
Kinematic state is determined by the properties such as position, speed, acceleration, etc.
Hydrodynamic state is determined by the properties such as pressure, shearing, stress, strain rate,
etc.
19
 Thermodynamic “equilibrium”

• TD equilibrium is an axiomatic concept of TD. It is an internal state of a single TD

system, or a relation between several TD systems connected by more or less
permeable or impermeable walls.

• In TD equilibrium, there are no macroscopic change occurs (no macroscopic

flows of matter, energy, either within a system or between systems).

• Properties (e.g., P, V, T, n, chemical composition) of a system have definite,

unchanged values as long as external conditions are unchanged.

• A TD system is said to be in a TD equilibrium if it is in a chemical + mechanical

+ radiative + thermal equilibrium; so when the relevant parameters cease to
vary with time.

• In fact, properties themselves cannot be defined when a system is not in

equilibrium. So, in Thermodynamics, we only study systems at equilibrium.

We also define “Quasi-equilibrium”

=> It is the state of a system with an infinitesimal departure from thermodynamic
equilibrium.
20
 Equilibrium in simple words
• The properties (e.g., P, T, V, N) of a system don’t change with
time and space.
Þ Gas in a container has the same pressure at all the point at all the
time.

(Example)

• Thermal equilibrium: The temperature throughout a system is

uniform.
• Mechanical equilibrium: At every point within a system, there is
no change in pressure with time, and there is no movement of
material.
• Phase equilibrium: when the mass for each individual phase
reaches a value that does not change with time.
• Chemical equilibrium: the chemical composition of a system has
settled and does not change with time.

Your system is at thermodynamic equilibrium when all those

equilibriums are met. 21
 Compact chemical notation

• We can summarize all these definitions in compact

chemical notation.

Þ 5 mole of Hydrogen gas at 1 atmosphere pressure and

100oC:
5H2 (g, 1 atm, 100oC)

Þ A mixture of liquid water and methanol at 1 atm and 25oC:

3H2O (l, 1 atm, 25oC) + 3CH3CH2OH (l, 1 atm, 25oC)

• To write the notation for one equilibrium state that goes to

another, we just add “→” sign.

Þ 5H2 (g, 5 atm, 100oC) → 5H2 (g, 1 atm, 100oC)

22
 Thermodynamic “process” and “path”

• When a TD system undergoes a change of its state from one

equilibrium state to another [i.e., when its properties change,
e.g., (P, V, T) of (2 atm, 1 L, 298 K) => (1 atm, 2 L, 298 K)], the
system is said to have undergone a process.

• The sequence of states through which the system passes during

a process is defined to be the path of the process.

Sequential steps going from one equilibrium state to another.

Upon change, the system may or may not be in TD equilibrium during
the sequential steps. (reversible process vs. irreversible process)

23
 More about the “path”

To completely describe a process:

1. Define the initial state
2. Define the final state
3. Define the path
4. Define the interactions across sys
tem boundaries

And you basically solved the problem

24
 More about the “path”

• The prefix “iso” is used to designate process in which

one properties of a system is kept constant.

• Constant temperature process: isothermal process

• Constant pressure process: isobaric process

• Constant volume process: isochoric process

• No heat transfer through the boundaries of a system:

Adiabatic process (e.g., heat insulating boundary)

25
 Path function vs. State function
• Path functions: the functions that depend on the path taken to reach
that specific value.
Ui(Pi, Vi, Ti)
P initial
Heat (Q) and work (W=F∙l) W = ∫ pdV
Pa
Pa th
th A
B
Pat final
hC

Uf(Pf, Vf, Tf)

V

• State functions: the functions defined for a system relating several

state variables (e.g., P, V, T, n) or state quantities that depend only on
the current equilibrium TD state (a set of state variables define one
equilibrium TD state) of the system, not the path which the system took
to reach its present state.

Energy (E): U, H, G, F / Entropy (S) /

State variables (P, V, T, composition, N, etc.) can also be considered as state
functions. 26
 Reversible vs. Irreversible process
• A system is going through a • A system is going through a
reversible process: irreversible process:

Throughout the entire process, the The system is out of equilibrium

system is never out of TD equilibrium. during any point of process.
(“Quasistatic”, “Quasi-equilibrium”)
=> Irreversible path defines the
=> Having been reversed, it leaves no direction of time.
change in either the system or the
surroundings.

http://machineryequipmentonline.com/hvac-machinery/work-heat-reversible-
change/

27
 Dimensions and Units

Dimension Unit
• A name given to any • An arbitrary magnitude in which
measurable quantity: dimensions are measured:
– Mass – kg
– Time – s

Quantity SI Unit Symbol

Mass kg
Length m
Time s
Temperature K
Amount of substance mol
28
 Dimensions and Units

Physical Quantity Unit Symbol Definition

Force Newton N Kg m/s2
Pressure Pascal Pa N/m2=Kg /(m/s2)
Energy Joule J N.m=Kg m2/s2
Power Watt W J/s=Kg m2/s3

• In engineering application, it is common to work with the following multiples:

– kPa=103 Pa = 103 N/m2
– MPa=106 Pa
– bar= 105 Pa
• A common reference pressure is atmospheric pressure which, though it varies, is given the standard reference
value:
– 1 standard atmospheric (atm) = 101325 Pa
– = 1.01325 bar
– = 14.7 psi
• All the pressure we have discussed are absolute pressures, that is to say pressure above of a vacuum.
• Sometimes, pressure is measured relative to atmospheric pressure. This is called gauge pressure if p>p atm.
i.e., p gauge = p absolute - p atm
• If the pressure is less than atmospheric pressure (p<p atm). This is called vacuum pressure.

29