Advanced Thermodynamics

(M2794.007900)

Min Soo Kim

Seoul National University
Introduction

Professor Min Soo Kim

Homepage : [Link]

E-mail : minskim@[Link]

Tel) 880-8362

Assistant : Sung Bin Hong (301 – 218)

E-mail : honutbin@[Link]

Tel) 880-1648
Introduction

M2794.007900 Advanced Thermodynamics

Representative Instructor
Credits Department
Name Email
3 Mechanical Engineering Major Kim, Min Soo minskim@[Link]

This course is aiming at extending fundamental knowledge on the

laws of thermodynamics to various applications and at understanding
statistical approach to diverse problems. Starting from the classical
1. Goals
thermodynamics, basic principles and related topics will be dealt with.
Statistical modeling of gas, solid, and liquid phases will be made,
and behaviors of materials will be intensively studied.

Materials-Materials-Classical and Statistical Thermodynamics-Ashley H.

2. Texts Book
Carter-Prentice-Hall-2001
Attendance Task Midterm Final Attitude Others Total
3. Evaluation
0% 10% 40% 40% 0% 10% 100%
Introduction

[ 1 Week ] Introduction
[ 2 Week ] Nature of Thermodynamics, Equation of State
[ 3 Week ] The First Law of Thermodynamics, Applications
[ 4 Week ] The Second Law of Thermodynamics, Applications
[ 5 Week ] Chemical Potential, Kinetic Theory of Gases
[ 6 Week ] Classical and Quantum Statistics
[ 7 Week ] Classical Statistical Treatment of Ideal Gas
[Link]
[ 8 Week ] Mid-term Exam.
Plan
[ 9 Week ] Heat Capacity of Diatomic Gases
[ 10 Week ] Heat Capacity of Solid
[ 11 Week ] Bose-Einstein Gases (1)
[ 12 Week ] Bose-Einstein Gases (2)
[ 13 Week ] Fermi-Dirac Gases (1)
[ 14 Week ] Fermi-Dirac Gases (2)
[ 15 Week ] Final wrap-up
Advanced Thermodynamics (M2794.007900)

Chapter 1

The Nature of Thermodynamics

Min Soo Kim

Seoul National University
1.1 What is thermodynamics?

Thermodynamics? Effect of temperature change

Heat motion Transformations of energy

• The study of heat in the field of physics.

Thermodynamics Other mechanics

Mass
Heat
Length
Temperature
Time
…

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1.1 What is thermodynamics?

• The basis of thermodynamics is experimental observation (empirical).

• Zeroth, first, second and third laws of thermodynamics were founded
and formalized.

Laws of thermodynamics

 The 0th law of thermodynamics: Thermal equilibrium (Temperature define)

 The 1st law of thermodynamics: Energy conservation
 The 2nd law of thermodynamics: Increase in entropy
 The 3rd law of thermodynamics: Absolute value of entropy

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1.1 What is thermodynamics?

Thermodynamics

• Classical thermodynamics
• macroscopic
: matter is continuous (direct observation, measurement).

• Statistical thermodynamics
• microscopic
: matter is particulate (molecules and atoms).

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1.1 What is thermodynamics?

The scale of statistical thermodynamics

δ 𝑐ҧ

• Density of particles = 1mole / 22.4L = 6 x 1023 particles / 22.4L

• Mean velocity of particles 𝑐ҧ ≈ 450 m/s

• Size of a particle d → 1Ǻ = 10-10 m = 0.1 nm scale

• Mean particle separation δ ≈ 10d = 10-9 m = 1 nm scale

• Mean free path λ ≈ 10δ = 100d = 10-8 m = 10 nm scale

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1.2 Definitions

System – Some portion of the physical world, that could be a container of

gas, a piece of metal, a magnet, etc.

Surroundings – The surrounding systems of the given system.

The system can exchange energy or mass with them.

Universe – The system, together with its surroundings.

Universe

System

Surroundings

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1.2 Definitions

Boundary – The boundary between a system and its surroundings

through which changes may be imposed.

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1.2 Definitions

System (≠ control volume)

Open system
• The system that can exchange mass and energy with its
surrounding.

Closed system
• The system that cannot exchange mass, but can exchange
energy with its surrounding.

Isolated system
• The system that cannot exchange mass and energy with its
surrounding.

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1.2 Definitions

System

Heat Work
No energy exchange
Mass Flow

Control Control
Volume Control Volume
Volume

Work
Mass Flow No mass flow No mass flow
Heat

Open system Closed system Isolated system

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1.2 Definitions

Boundary (= system wall)

Adiabatic wall
• A boundary that permits no heat interaction with the surroundings.
• An isolated system is adiabatically contained, but a system with
adiabatic wall is not always isolated.
• Mechanical interactions, such as material exchange, volume
change, or magnetic field can be applied.

Diathermal wall
• A boundary that freely allows heat to be exchanged.

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1.2 Definitions

Properties – Observable characteristics of a system that describe the

macroscopic behavior of a system.

Property

Extensive property
• Properties that are proportional to the mass.
• Volume, internal energy, entropy, etc.

Intensive property
• Properties that are independent to the mass.
• Temperature, pressure, density, etc.

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1.2 Definitions

Property

• Usually, extensive properties (Volume (V), enthalpy (H), …) are

given by capital letter.

• Intensive properties Temperature (T), and pressure (P) are two

exceptions to distinguish it from time (t) and probability (p).

• An extensive property can be converted to an intensive property

by dividing by the mass. This is called a specific value.

Value of the extensive property

𝑆𝑝𝑒𝑐𝑖𝑓𝑖𝑐 𝑣𝑎𝑙𝑢𝑒 ≡
mass of the system

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1.2 Definitions

1 kilomole – unit of mass m in kilograms equal to the molecular weight.

ex) Molecular weight of oxygen gas (𝑂2 ) = 32

1 kilomole of oxygen gas (𝑂2 ) = 32 kg
1 mole of oxygen gas (𝑂2 ) = 32 g

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1.2 Definitions

State – A condition uniquely specified by a set of properties.

Two independent variables can specify the thermodynamic
state of a single component system.

Equilibrium state – One in which the properties of the system are uniform
throughout and do not change with time unless the system is
acted upon by external influences.

Non equilibrium state – A state that characterizes a system in which

gradient exist and whose properties vary with time.

State variable – Properties that describe equilibrium states.

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1.2 Definitions

Equation of state – A functional relationship among the state variables

for a system in equilibrium.

If the state variables are the pressure P, the volume V, and the
temperature T, the equation of state (EOS) takes the form

f (P, V, T) = 0

This relationship reduces the number of independent variables of

the system from three to two. The function f is assumed to be given
as part of the specification of the system.

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1.2 Definitions

The equation of state defines a surface in P-V-T space.

Any point lying on this surface represents a state in equilibrium.

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1.2 Definitions

Path – A series of states through which a system passes.

Process – A change of the state of a system.

‘change of state’ ≠ change of phase or phase transformation

Cyclical process – A process of which the initial and final states are the
same.

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1.2 Definitions

Process

Quasi-static process
• At each instant, the system departs only infinitesimally from
an equilibrium state.

Reversible process
• A quasi-static process without any dissipative forces.
Reversible process ≠ Quasi-static process

Irreversible process
• A process includes a finite change with dissipation

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1.2 Definitions

In many processes, some property of the system remains constant.

Isobaric process – The pressure of the system remains constant during

process.

Isochoric process – The volume of the system remains constant during

process.

Isothermal process – The temperature of the system remains constant

during process.

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1.2 Definitions

In case of figure 1.3, a piston enclosing a gas is immersed in a heat bath,

so that the gas is kept at constant temperature.
If the gas is very slowly compressed, the process is quasi-static, reversible,
and isothermal.

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1.2 Definitions

Instead of a gradual compression, if the piston is given a violent push,

sound or shock and turbulence will generated, accompanied by strong
temperature and pressure gradients. In this case, the process is an
irreversible, non-equilibrium process that cannot be represented by a path
in the P-V plane. Only the end points can be plotted

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1.4 Limits of the continuum

• We tacitly assume that classical thermodynamics is a continuum theory,

that properties vary smoothly from point to point in the system.
But if all system are made up of atoms and molecules, it is
reasonable to ask:
how small a volume can we be concerned with and still have
confidence that continuum theory is valid?

we can roughly obtain an approximate answer to this question by invoking

Avogadro’s law:
at standard temperature and pressure, one kilomole of gas occupies 22.4 m3
1 kilomole = NA = 6.02 X 1026 molecules

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1.4 Limits of the continuum

• Density of particles = 1mole / 22.4L = 6 x 1023 particles / 22.4L

1 nm
1 mm

1 nm
1 mm

# of particles in 1 mm3 ≈ 1016 # of particles in 1 nm3 ≈ 0.01

• Classical thermodynamics is applicable down to very small macroscopic

volumes, but ultimately a limit is reached where the theory will break down.

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1.4* Heat carriers

Heat carriers
• Heat transfer involves the motion of heat carriers generated by
temperature difference.

Gas molecule – A heat carrier is gas.

Electron – A heat carrier in metals.

Phonon – A heat carrier in solids (electrical insulators).

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1.4* Heat carriers

Phonon
The interatomic interactions in crystals can be represented by a mass-spring
system.
If one side of the solid is hotter, the atoms near the hot side will have larger
vibrational amplitudes, which will be felt by the atoms on the other side of the
system through the propagation and interaction of lattice wave.
A quantized lattice wave is called a phonon.

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1.7 Temperature and the zeroth law of thermodynamics

The zeroth law

: If two systems are separately in thermal equilibrium with a third

system, they are in equilibrium with each other.

A C B C

A and C in thermal B and C in thermal

equilibrium equilibrium

A B

A and B in thermal
equilibrium

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1.7 Temperature and the zeroth law of thermodynamics

Temperature

A C B C

Figure 1.3

The system C can be thought of as a thermometer. Its state is given by the

pair of variables (PC, VC). From observations, if we choose a particular
value for PA, then Va will be uniquely determined (only one variable is
independent).

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1.7 Temperature and the zeroth law of thermodynamics

The conditions under which A and C are in equilibrium may be expressed

by the equation

F1 (PA, VA, PC, VC) = 0, (1)

Where F1 is some function of the four variables.

We assume that this equation can be solved for PC

PC = f1 (PA, VA, VC). (2)

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1.7 Temperature and the zeroth law of thermodynamics

Next we place system B and C in thermal contact (Figure 1.x(b)).

For equilibrium,

F2 (PB, VB, PC, VC) = 0 (3)

or

PC = f2 (PB, VB, VC). (4)

Equating equations (2) and (4), we obtain the condition under which A and
B are separately in equilibrium with C

f1 (PA, VA, VC) = f2 (PB, VB, VC). (5)

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1.7 Temperature and the zeroth law of thermodynamics

But, according to the zeroth law, A and B are then in equilibrium with each
other, so that

F3 (PA, VA, PB, VB) = 0. (6)

Solving for PA, we obtain

PA = f3 (VA, PB, VB). (7)

Now, equation (5) can also be solved for PA, in principle

PA = g (VA, PB, VB, VC). (8)

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1.7 Temperature and the zeroth law of thermodynamics

Equation (8) states that PA is determined by four variables, whereas

equation (7) says that it is a function of only three.
This can only mean that the function f1 and f2 in equation 5 contain VC in
such a form that it cancels out on the two sides of the equation.

For example,

f1 = ϕ1 (PA, VA) ζ (VC) + η (VC),

f2 = ϕ1 (PB, VB) ζ (VC) + η (VC).

When the cancellation is performed, we have

ϕ1 (PA, VA) = ϕ2 (PB, VB). (9)

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1.7 Temperature and the zeroth law of thermodynamics

Extending the argument to additional systems, we get

ϕ1 (PA, VA) = ϕ2 (PB, VB) = ϕ3 (PC, VC) = ∙∙∙ . (10)

For any system in thermal equilibrium with a given system, we can choose
to write

ϕ1 (PA, VA) = T, (11)

Where we define T as the empirical temperature and equation 11 is the

equation of state (EOS) of the system.
Equation 10 then says that systems in thermal equilibrium with one another
have the same temperature. Thus temperature is a property of a system
that determines if thermal equilibrium exists some other system.

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1.7* The laws of thermodynamics

The first law

Law of conservation of energy.

Q12 – W12 = E2 – E1
Transferred Work Internal
heat energy
(temperature related)

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1.7* The laws of thermodynamics

The first law

q w

hi

u1 → u2
ho
ws
q

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1.7* The laws of thermodynamics

The second law

For isothermal, quasi–static, irreversible process,

𝛿𝑄 𝛿𝑄
𝑑𝑠 ≥ , or 𝑑𝑠 = + 𝛿𝜃, 𝛿𝜃 ≥ 0
𝑇 𝑇
entropy generation
(disorder production)

𝛿𝑄
∆𝑆 = 1, =1
𝑇
S = 11
2

0
S = 10
.1 𝛿𝑄
∆𝑆 = 1, = 0.5, 𝛿𝜃 = 0.5
𝑇

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1.7* The laws of thermodynamics

The second law

q/T

si

+θ
+θ
s1 → s2
so

q/T

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1.7* The laws of thermodynamics

The third law

Behavior of S as T → 0

lim ∆𝑆 = 0
𝑇→0

It is possible to assign S(T=0) = 0

This normalized entropy is called ‘absolute entropy’

lim 𝑆 = 0
𝑇→0

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