PHY 503: Statistical Mechanics

Dr. Yugandhar Bitla

Department of Physics
Central University of Rajasthan

Brief review of thermal Physics

Extensive and intensive variables, laws of thermodynamics, entropy and Gibbs paradox,
Legendre transformation, thermodynamic potentials, chemical potential, Jacobian determinant,
Maxwell’s relations and their applications.
 A few quotes on the history of the subject
But although, as a matter of history, statistical mechanics owes
its origins to investigations in thermodynamics, it seems
eminently worthy of an independent development, both on
account of the elegance and simplicity of its principles, and
because it yields new results and places old truths in a new light
in departments quite outside of thermodynamics.(J.W. Gibbs).

I am conscious of being only an individual struggling weakly against the

stream of time. But still remains in my power to contribute in such a way
that, when the theory of gases is again revived, not too much will have to
be rediscovered. (L. Boltzmann).
 Thermodynamics = Therme + Dynamis
(Heat) (Power)
Study of motion of Heat

William Thomson (Lord Kelvin), first to use “thermodynamic” word in his work (1849)

Thermodynamics deals with heat and work - two processes by which a system transacts
energy with its surroundings or with another system.

Thermodynamics is the study of the effects of work, heat, and energy on a system
Thermodynamics is only concerned with macroscopic (large-scale) changes and observations

As with science in general, thermodynamics is based on empirical observation.

Moreover, it is important that those observations be repeatable.

Study of Thermodynamics
a) Macroscopic Approach = Classical Thermodynamics (does not require
knowledge of the behavior of individual particles)
b) Microscopical Approach = Statistical thermodynamics
Thermodynamics:
• Describes macroscopic properties of equilibrium systems
• Empirical observation.
• Built on four laws
 System and surroundings
boundary System: The small part (Quantity of mass or
region in space) of the universe under
consideration.
e.g. a piece of iron, a glass of water, an engine

The rest of the universe (in which we stand and

make observations and measurements on the
system) is called the surroundings
Boundary: real/imaginary surface that
separates system from its surroundings. Can
be fixed/movable, shared by both(system &
surrounding), no thickness, no mass/volume

universe
The system and the surroundings together is called the universe

Ex: A glass of water is the system and the room

in which the glass is placed is called the
surrounding.
 Different types of system
Nature of boundary

Permeable and dia-thermic Adiabatic

dia-thermic but not permeable (impassable)

closed vacuum
bucket of water sealed bottle flask holding hot cup of
coffee
Control Volume Control mass
 State of the system
A set of properties that completely describe the condition of the system is known as its
STATE.
At a given state all of the properties are known; changing one property changes the state.

A system at two
different state

states & state variables

fluid (pressure, volume, temperature)
surface (tension, area)
black-body radiation (energy density, radiation pressure)
electrical contact (potential, current)
 Macroscopic vs Microscopic states

Microstate
Position, velocity, momentum, force, etc for N
particles.
N is of the order of 1024 (Say N is infinite!!)

Macrostate
Pressure (P), Volume (V), Temperature (T) and
mass (m), Energy, etc
• Macroscopic Point of View
- concerned with the Gross or Average
Effects of many molecules
• Continuum
• Microscopic Point of View
- Classical and Statistical approach
Most microscopic properties cannot be measured with common instruments nor can be
perceived by human senses
 Extensive and intensive Thermodynamic Variables
Any measurable or observable characteristics of the substance when the system remains in
equilibrium is called a PROPERTY or Variable. Ex: Pressure (P), Volume (V), Temperature (T) and
mass (m), Magnetization (M), Electric Resistance, (R), Thermal Conductivity (k), etc.

Thermodynamic Variables

Extensive Intensive
no. of Particles (N)
mass (m) temperature (T)
volume (V) pressure (P)
energy (E) density (ρ = N/V)
entropy (S) chemical potential (μ)
free energy

Extensive property: Depends on the quantity of matter present in the system

Intensive property : Independent of the quantity of matter present in the system
We often construct an intensive variable by extensive variable /extensive variable
e.g. density: mass/volume ;
specific heat: heat capacity / mass
specific volume: volume / number of molecules;

Mathematically,

x is extensive when it is first-order homogeneous in y and z extensive variables

x is intensive when it is zero-order homogeneous in y and z extensive variables

In general, for a given system, we can express one thermodynamic property as a function of
other thermodynamic properties.

PV = N kB T

P = (N/V) kB T
Example
 Thermodynamic Equilibrium
EQUILIBRIUM : State of Balance A state where system parameters no longer evolve,
no fluxes of matter or energy through the system
Thermal Equilibrium :
- NO Temperature Gradient throughout the system.
(uniform temperature)

Mechanical Equilibrium :
- NO Pressure Gradient throughout the system.
(uniform pressure).

Phase Equilibrium :
- System having more than 1 phase.
- Mass of each phase is in equilibrium.

Chemical Equilibrium :
- Chemical composition is constant
- NO reaction occurs.
Diffusional equilibrium = equality of chemical potential

Thermodynamic Equilibrium: All macroscopic average values are time-independent.

 Path and Process
Any change a system undergoes from one equilibrium state to another
is known PROCESS.
Series of states through which system passes during the process is
known as its PATH

(A2,B2)

(State 2)
Property B

(A1,B1)

Path
(State 1) State 1 State 2

Property A
State: Energy (Point Function)
Path: Work or Heat (Path Functions) 16
 • Quasi means ‘almost’.
• During a quasi-equilibrium/static process the system remains
practically in equilibrium at all times.
• We study quasi-equilibrium processes because they are easy to
analyze (equations of state apply) and work-producing devices
deliver the most work when they operate on the quasi-equilibrium
process.

State 1 State 2 State 1 State 2

Slow expansion Very fast expansion

(Quasi-static) (nonquasi-static/nonequi)
Process proceeds in such a manner that system
remains infinitesimally close to equilibrium
17
conditions at all times.
In most of the processes, one thermodynamic property is
held constant.

Types of Processes
Process (Constant Property)

•Isothermal (T)
•Isobaric (p)
•Isochoric/Isovolumetric (v)
•Isentropic (s)
•Isenthalpic (h)
•Isosteric (concentration)
•Adiabatic (no heat addition or removal)

18
In most of the processes, one thermodynamic property is held constant. Some of
these processes are

A system at two different states

(Process??)

PVn = constant

Isobaric (P = const)
Isothermal (T = const)
Isothermal (T = const)

P Adiabatic T

Isovolumetric/isochoric (V = const) Isoentropic (S = const)

V S
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 Cycle

(A2,B2)

Property B State 2
(A1,B1)

Path
State 1

Property A

CYCLE: A system is said to have undergone a cycle if it returns to its

ORIGINAL state at the end of the process.
Hence, for a CYCLE, the INITIAL and the FINAL states are identical.
20
Zeroth Law of Thermodynamics
and
Concept of Temperature
Zeroth Law of Thermodynamics and Concept of Temperature
Formulated and labeled by R.H. Fowler in 1931

• If two blocks (one warmer than the other) are brought into
contact and isolated from their surroundings, they would
interact thermally with changes in observable properties.
• When all changes in observable properties cease, the two
blocks are in thermal equilibrium.
• Temperature is a physical property that determines whether
the two objects are in thermal equilibrium.

Zeroth Law
If A is in thermal equilibrium with B and B is in thermal equilibrium with C
then C will be in thermal equilibrium with A.
In other words, all three systems have the same ‘temperature’.
Zeroth law of thermodynamics: If two bodies are in thermal equilibrium with a
third body, they are also in thermal equilibrium with each other.

By replacing the third body with a thermometer, the zeroth

law can be restated as two bodies are in thermal
equilibrium if both have the same temperature reading
even if they are not in contact

Temperature

• No EXACT Definition. But “Degree of Hotness / Cold” based on our physiological

sensation.
• Misleading. e.g. Metallic knob may feel colder than Wooden door; even at same
temperature!!
• Properties of materials change with temperature.
• We can make use of this phenomenon to deduce EXACT level of temperature.
Common Temperature scales: Fahrenheit, Celsius and Kelvin.

1. Celsius scale :
• Also Known as Centigrade scale.
• It is divided into 100 parts
• The freezing point of water is 0°C
• Boiling point is 100 °C
2. Fahrenheit scale
• The freezing point of water is 32°F
• The boiling point is 212°F
3. Kelvin scale
• The freezing point of water is 273K
• The boiling point of water is 373K
• This temperature scale is often uses when gases are involved.
• Its zero point(0K) corresponding to -273 °C and referred to as
Absolute zero.
 Temperature scales: Fahrenheit, Celsius, Kelvin and Rankine.

Kelvin scale (K): An absolute thermodynamic temperature scale whose

unit of temperature is the kelvin (K); the SI base unit for temperature.

Rankine scale (R): An absolute thermodynamic temperature scale with

absolute zero that coincides with the absolute zero of the Kelvin scale;
the English base unit for temperature. T(oR) = 1.8T(K)

Celsius scale (oC):

T(oC) = T(K) – 273.15

Fahrenheit scale (oF):

T(oF) = T(oR) – 459.67 25
26
First Law of Thermodynamics
When two bodies at different temperatures are brought in contact with each other,
heat transfers from the body at higher temperature to that with lower one until both
attain a Thermal Equilibrium.

HOT cup of coffee cools off w.r.t. time.

COLD Drink warms up w.r.t. time.

Energy can cross the Boundary of the System in two forms : 1. Heat
Heat 2. Work
system
Work
 Concept of Work & Heat

Thermodynamics deals with heat and work - two processes by which a system
transacts energy with its surroundings or with another system.

Heat: Energy of ‘random’ molecular motion

heat is energy in transit, when the transit is caused by temperature gradient

work is energy in transit, when the transit is caused by pressure difference

Path Functions have Inexact Differentials, designated by symbol δ or đ.

Thus, a differential amount of Heat or Work is represented as δQ or δW; in stead of dQ or dW.

Properties, on the other hand, are Point Functions, and have Exact Differentials,
designated by symbol d.
Path Function : Magnitude depends on the Path followed during the Process, as
well as the End States.
Point Function : Magnitude depends on State only, and not on how the System
approaches that State.
Similarities between HEAT & WORK :
1. Both are recognized at the Boundary of the System, as they cross the Boundary.
Hence both are Boundary Phenomena.
2. System possesses Energy, but neither Heat nor Work.
3. Both are associated with Process, not State. Heat and Work have NO meaning at
a State.
4. Both are Path Functions.

Sign Convention :
Heat Transfer TO a System : + ve
Heat Transfer FROM a System : - ve
Work done BY a System : + ve
Work done ON a System : - ve
 Heat
Energy Transfer in from of Heat by 3 ways :

CONDUCTION : Transfer of Energy from a more energetic particle of a substance

to the adjacent less energetic one, as a result of interaction
between them.

CONVECTION : Transfer of Energy between a solid surface and the adjacent fluid
that is in motion. It involved both, the combined effect of
conduction and fluid motion.

RADIATION : Transfer of Energy due to the emission of electromagnetic waves.

 Work
WORK : Work is the Energy transfer associated with a Force acting through a distance.
Denoted by J or kJ.

Field/Intensive variables: P, T, stress, electric field, magnetic field,…,

Fi(generalized force)

State/Extensive variables: V, S, strain, electric polarization, magnetization,…,

Xi(generalized flux)
Integrating factor

δW = P dV dV = δW (1/ P)
δW = ΣFidXi Conjugate variables
 Comment: Exact and inexact differentials

e.g. Small change in Volume, is represented as dV, and is given by;

2

 dV = V
1
2 − V1 = V

Thus, Volume change during Process 1 – 2 is always =

(Volume at State 2) minus (Volume at State 1). State 2
Regardless of path followed.

Pressure
HOWEVER, total Work done during Process 1 – 2 is;
2
State 1

 dW = W
1
12 ( NOT W )

i.e. Total Work is obtained by following the Process V1 Volume V2

Path and adding the differential amounts of Wok (δW)
done along it.

Integral of δW is ≠ ( W2 – W1 ).
 PdV Work
Area A Let the Piston be moving from
Thermodynamic Equilibrium State 1 (P1, V1)
P 2 V2
P1 V1 to State 2 (P2, V2).
Let the values at any intermediate
Equilibrium State is given by P and V.
State 1 State 2

For an Infinitesimal displacement, dL, the Infinitesimal Work done is:

dW = F * dL = P*A*dL = PdV P1
Quasi-Static

Pressure
Similarly, for Process 1 – 2; we can say that Process Path

P2
V2

W1− 2 =  PdV
V1 V1 Volume V
2
 Work
P=Const State 1
Isobaric P1
V=Const

Pressure (P)
State 1 State 2 Isochoric
Pressure (P)

W1-2

P2 State 2

Volume (V)
V1 Volume (V) V2

V2 V2
W1− 2 =  PdV = P (V2 − V1 ) W1− 2 =  PdV = 0
V1
V1
 Work in polytropic process

n
PV
PV = P1V1 = P2V2 = C  P = 1 n1
n n n

P1
1 PVn = C V
V2

W1− 2 =  PdV
Pressure

V1
V2
 V − n +1 
V2
n dV
=  P1V1 n = P1V1
n
n =∞ n =1 W1− 2  
2 V1
V  − n + 1 V1
P2
( )
1− n 1− n
P V X V2 − P1V1 X V1
n n n
n =3 n =2 PV 1− n 1− n
= 1 1 V2 − V1 = 2 2
1− n 1− n
P1V1   P2  
Volume n −1 / n
P1V1 − P2V2
= = 1 −   
n −1 n − 1   P1  

 Work: Ideal gas

PdV Work in Different Quasi-Static Processes :

V2
State 1
P1 W1− 2 =  PdV
PV = C
Pressure

V1
Quasi-Static
P1V1
PV = P1V1 = C  P =
n =1 V
State 2 V2
dV V P
W1− 2 = P1V1 
P2
= P1V1 ln 2 = P1V1 ln 1
V1
V V1 P2
V1 V2
Volume
38
41
First Law of Thermodynamics and its differential form

δQ – δW = dU
δQ and δW are Inexact differentials
dU is an exact differential

δQ – δW is same for all process

Internal Energy

43
 Isochoric
or V = Const. T = Const.
isovolumetric
Isothermal

Isobaric
44
P = Const.
 First law of Thermodynamics
Process and path

P1, V1, T1 Initial state

• Initial state(T1,P1,V1)
• Final state (T2,P2,T2)
1 2 3
( )T ( )V ( )P
δQ – δW = dU

P2, Va, T1 P2, V1, Tb P1, Vc, T2

Path 1: T1,P1,V1→T1,P2,Va (Constant-

temperature) →T2,P2,V2 (Constant-pressure) ( )P 2 ( )P ( )T
1
3

Path2: T1,P1,V1→Tb,P2,V1 (Constant-volume)

→T2,P2,V2 (Constant-pressure)
P2, V2, T2 Final state
Path3:T1,P1,V1→T2,P1,Vc (Constant-presure)
→T2,P2,V2 (Constant-temperature)

δQ – δW is same for all process

 The First Law of Thermodynamics
Q = Ē + W
Ē = Change in the internal energy of the system.
Q = NET heat transferred to the system.
W = Work done BY the system.
• The 1st Law is deceptively simple looking. It’s
obviously a form of the general
Law of Conservation of Total Energy.
• But Be careful about the sign conventions!
Positive Q is heat transferred to the system.
Positive W is work done by the system.
The First Law of Thermodynamics
In words:
The change in the internal
energy OF a system depends only
on the NET heat transferred TO
the system & the net work done
BY the system, & is independent
of the processes involved.
Energy is a property and is possessed by the system, whereas heat and work are
boundary phenomena.

δQ – δW is same for all process

Change in energy of the system between its two states is the same, irrespective
of how this change in state is brought out, but the amount of work and heat transfer will
depend on how the change is made.

First law of đQ = δQ = dU + δW = dU + đW
Thermodynamics
dU = δQ – δW = đQ – đW

48
 đW, đQ, dU: a microscopic view

Work: transfer of energy that makes use of the uniform motion of atoms in
the surroundings.
Heat: transfer of energy that makes use of random motion of atoms in the
surroundings.
Internal energy: kinetic energy + potential energy of the system’s
constituent atoms.
 Application of First law of thermodynamics to different systems

System Intensive property Extensive Property δW dU = δQ- δW

(Generalized Force) (Generalized
Displacement)

Mechanical Force (F) Displacement (dx) -Fdx dU = δQ +Fdx

Solid rod Stress (σ) Strain (dℇ) -σdℇ dU = δQ +σdℇ

(elastic)
Wire stretching Tension (σ) Extension (dL) -σdL dU = δQ +σdL
Compression/ex Pressure (P) Volume change (dV) PdV dU = δQ -PdV
pansion
Liquid film Surface tension (σ) Area change (dA) -σdA dU = δQ +σdA

Torsion Moment (Mr) Angle change (dω) -Mrdω dU = δQ +Mrdω

Electric Electric field (E) Electric displacement (dD) -E.dD dU = δQ +E.dD

Magnetic Magnetic field (H) Magnetization change (dM) -H.dM dU = δQ +H.dM

 Application of First law of thermodynamics to different processes

System Constant dU = δQ- δW Remarks

Quantity

Isothermal T dU = 0 as dT = 0; Heat supplied is used up in doing

δQ = δW work

Isobaric P dU = δQ -PdV

Isochoric V δW = 0 as dV = 0; Heat added to the system increases

dU = δQ its internal energy

Adiabatic Q=0 δQ = 0; dU = -δW Work done on the system increases

its internal energy

Isolated system W= Q = 0 dU = 0 No change in systems internal

energy
 Second Law of Thermodynamics
Reversible and Irreversible process. Conversion of Work into Heat and
vice versa. Heat Engines. Carnot’s Cycle, Carnot engine & efficiency.
Refrigerator & coefficient of performance, 2nd Law of
Thermodynamics. Carnot’s Theorem. Applications of Second Law of
Thermodynamics. Entropy: Concept of Entropy, Clausius Theorem.
Clausius Inequality, Entropy of a perfect gas, Entropy Changes in
Reversible and Irreversible processes.

52
 Reversible and Irreversible process
A reversible process for a system
-- a process that once having taken place can be reversed and in so doing
leave no change in either system or surroundings.
For transformation/process to be reversible, it is necessary to control
step-by-step evolution of the system. i.e., all the state variables must
be permanently constrained by the operator (they do not vary without
control operator). For such a situation not only system follow a
quasistatic transformation but also it is permanently in equilibrium
with its surroundings.

Quasi-static process ↔ succession of equilibrium states of the system.

Reversible process ↔ succession of equilibrium states of the universe (sys. +
surroundings).

Any reversible process is quasi-static, however, converse need not be true

always.
 Effects/Factors that render processes Irreversible: irreversibilities
They include friction, unrestrained expansion, mixing of two fluids, heat transfer across
a finite temperature difference, electric resistance, inelastic deformation of solids, and
chemical reactions.
Irreversible compression and
expansion processes
Friction

Unrestrained Expansion
Heat Transfer through a Finite Temperature Difference

(a) Heat transfer through a temperature

difference is irreversible, and
(b) the reverse process is impossible.

Mixing of Two Different Substances

Other Factors
– hysteresis effects
– i 2 R loss encountered in
electrical circuits
– ordinary combustion
 Reversible and Irreversible process
Reversible process: A process that can be reversed without leaving any trace on
the surroundings.
Irreversible process: A process that is not reversible.

• All the processes occurring in nature are irreversible.

• Why interested in reversible processes?
• (1) they are easy to analyze and (2) they serve as
idealized models (theoretical limits) to which actual
processes can be compared.
• Some processes are more irreversible than others.
• We try to approximate reversible processes. Why?

56
Reversible processes deliver the most and consume the least work.
 Internally and Externally Reversible Processes
• Internally reversible process: If no irreversibilities occur within the boundaries of
the system during the process.
• Externally reversible: If no irreversibilities occur outside the system boundaries.
• Totally reversible process: It involves no irreversibilities within the system or its
surroundings.
• A totally reversible process involves no heat transfer through a finite temperature
difference, no nonquasi-equilibrium changes, and no friction or other dissipative
effects.

57
57
 Recap

Energy is a property and is possessed by the system, whereas heat and work are
boundary phenomena.

Change in energy of the system between its two states is the same, irrespective
of how this change in state is brought out, but the amount of work and heat transfer will
depend on how the change is made.
δQ – δW is same for all process

đQ = δQ = dU + δW = dU + đW
First law of Thermodynamics
dU = δQ – δW = đQ – đW

58
 Few examples
Hot cup of coffee cools off when exposed to surrounding.
Heat Energy lost by coffee = Energy gained by Surroundings.

Here, First Law of Thermodynamics is satisfied.

HOWEVER, converse is NOT true.

i.e. Taking out Heat from Surroundings ≠ Coffee getting hot.

Still, First Law of Thermodynamics is satisfied !

Hot cup of coffee

Electric Energy supplied to the heater = Energy transferred to the

Heat
I Surroundings ( room air ).

Here, First Law of Thermodynamics is satisfied.

HOWEVER, converse is NOT true.

Transferring Heat to the wire ≠ Equivalent amount of Electric Energy

generated in wire.
Room Heater: Heating of a room
by passing Electric Current through
Still, First Law of Thermodynamics is satisfied !

the Resistor.

59
 Paddle Wheel mechanism operated by falling mass.
Paddle wheel rotates as mass falls down and stirs the fluid inside the
container.
Decrease in Potential Energy of the mass = Increase in Internal Energy of
the fluid.
Here, First Law of Thermodynamics is satisfied.

Heat HOWEVER, converse is NOT true.

Transferring Heat to the Paddle Wheel ≠ Raising the mass.
Paddle Wheel Still, First Law of Thermodynamics is satisfied !

Petrol is used as a car drives up a hill, but the fuel level in the gasoline tank cannot be
restored to its original level when the car coasts down the hill.

From these examples, it can be clearly understood that satisfying the First Law of

Thermodynamics does not ensure for a Process to occur actually.

Processes proceed only in certain direction; but may not in Reverse direction.
60
First Law of Thermodynamics has no restriction on the DIRECTION of a Process to occur.

This inadequacy of the First Law of Thermodynamics; to predict whether the Process

can occur is solved by introduction of the Second Law of Thermodynamics.

Significance of second law of thermodynamics:

1. It identifies the direction of the Process.

2. It also asserts that Energy has quantity as well as Quality.

3. It helps to determine the Degree of Degradation of Energy during the Process.

4. It is also used to determine the Theoretical Limits for the performance of the

commonly used engineering systems, such as Heat Engines and Refrigerators.

61
Thermal Energy Reservoir: Hypothetical body with relatively very large Thermal

Energy Capacity ( mass x Sp. Heat ) that can supply or absorb finite amount of Heat

without undergoing change in Temperature.

e.g. ocean, lake, atmosphere, two-phase system, industrial furnace, etc.

Source
Reservoir that supplies Energy in form of Heat is known as SOURCE.
Heat

Heat
Reservoir that absorbs Energy in form of Heat is known as SINK.
Sink

62
 Heat Engines
1. Work can be converted to Heat.
2. However, Converting Heat to Work requires special devices.
These devices are known as Heat Engines. e.g. Gas Turbines, I.C. Engines, Steam Power
Plants, etc.
Characteristics of Heat Engines:
High Temp
Source • They receive the Heat from High-Temp
Reservoir ( i.e. Source ) (e.g. Solar
Qin
Energy, Oil Furnace, Nuclear Reactor,
etc.).
Heat Engine Wnet
• They convert part of this Heat to Work
( Usually in form of rotating shaft ).
Qout
• They reject the remaining Heat to Low-
Temp Reservoir ( i.e. Sink ) (e.g.

Low Temp Atmosphere, River, etc.)

Sink • They operate on a CYCLE. 63
A steam engine is one type of heat engine.

© 2014 Pearson Education, Inc.

 Steam Power Plant : ANS : NO.
Can Qout be eliminated ?
Without a Heat Rejection
Process, the Cycle can not
Source
(Furnace) be completed.
Qin
Net Work Output: Worknet,out = Wout - Win
Boiler
Each component is an Open system
However, as a complete set of
Win Wout components, no mass flows
Pump Turbine in/out of the system

Hence, it can be treated as a

CLOSED SYSTEM ∆U = 0
Condenser
Worknet,out = Qout - Qin
Qout Sink
(Atm. )

65
Part of Heat output that is converted to net Work output, is a measure of performance of
the Heat Engine; and is known as the Thermal efficiency of the Heat Engine.

Net Work Output

Thermal Efficiency =
Total Heat Input

Wnet ,out Qout

th = =1−
Qin Qin

QH = Magnitude of Heat Transfer between cyclic device and Source at temperature TH

QL = Magnitude of Heat Transfer between cyclic device and Sink at temperature TL

Worknet,out = QH - QL

Wnet ,out QL
 th = =1−
QH QH 66
• Heat Engine must give away some heat to the Low Temperature Reservoir ( i.e. Sink ) to

complete the Cycle.

• Thus, a Heat Engine must exchange Heat with at least TWO Reservoirs for continuous

operation. This forms the basis for the Kelvin – Planck

expression of the Second Law of

Thermodynamics: It is impossible for any

Thermal Energy
Reservoir
device that operates on a Cycle to receive
QH = 100 kW
Heat from a single Reservoir and produce
Heat Wnet = 100 kW
net amount of Work.
Engine

QL = 0 (or)

No Heat Engine can have 𝜼𝒕𝒉 = 𝟏𝟎𝟎%

67
 Refrigerator / heat pump :

Heat is always transferred from High Temperature to Low Temperature region.

High Temp
Source

QH The reverse Process can not occur on itself.

Refrigerator
Wnet, in
Transfer of Heat from Low Temperature
region to High Temperature one requires
special devices, known as Refrigerators.
QL

Low Temp
Sink
 Surrounding Air Efficiency of a Refrigerator is expressed in
QH terms of Coefficient of Performance (COP)R.
Condenser Desired Output QL
COPR = =
Re quired Input Wnet ,in
Wnet, in
Expansion First Law of Thermodynamics gives;
Valve Worknet,in = QH - QL
Compressor
QL 1
Evaporator COPR = =
QH − QL  QH 
QL  Q  −1
 L
Refrigerated Space
Thus, COPR can be > 1

For a Heat Pump, COP is expressed as (COP)HP.

Desired Output QH QH 1
COPHP = = COPHP = =
Re quired Input Wnet ,in QH − QL 1 −  QL 
 Q 
 H 
69
Thus; COPHP = COPR + 1
Second Law of Thermodynamics

Clausius Statement :

It is impossible to construct a device that

operates in a Cycle, and produces no effect
High Temp
other than the transfer of Heat from a Source
Lower Temperature Body to a Higher
QH = 10 kJ
Temperature body. Refrigerator
(or) Wnet, in = 0
No Refrigerator can operate unless its
compressor is supplied with external Power
source. QL= 10 kJ

Low Temp
Sink
70
Second Law of Thermodynamics

(Kelvin): ‘No cyclic process is possible in which heat is

taken from a hot source and converted completely into
work.’ (e.g. engine)

(Clausius): ‘Heat cannot pass from a body at low

temperature to one at higher temperature
without work being done.’ (e.g. refrigerator)

71
 Second Law of Thermodynamics

TH TH
QH
Wnet = Q H + QL QL
QH
Wnet = 0
Heat
Engine =
Refrigerator
QL = 0 QL QL Refrigerator

TL TL

This Proves that;

Violation of Kelvin – Planck Statement results in violation of Clausius Statement.
Converse is also True.

72
73
 Carnot’s Cycle, Carnot engine & efficiency

Sadi Carnot
• 1796 – 1832
• French Engineer
• Founder of the science of thermodynamics
• First to recognize the relationship between work
and heat

Carnot Engine
• A theoretical engine developed by Sadi Carnot

• A heat engine operating in an ideal, reversible cycle (now called a Carnot

Cycle) between two reservoirs is the most efficient engine possible

• Carnot’s Theorem: No real engine operating between two energy

reservoirs can be more efficient than a Carnot engine operating between
the same two reservoirs.
 Carnot Engine
The Carnot engine was created to examine the efficiency of a heat engine. It is
idealized, as it has no friction. Each leg of its cycle is reversible.
The Carnot cycle consists of:
1. Isothermal expansion
2. Adiabatic expansion
3. Isothermal compression
4. Adiabatic compression

Wnet ,out QL
 th = =1−
QH QH

Carnot Cycle
© 2014 Pearson Education, Inc.
The Reversed Carnot Cycle
The Carnot heat-engine cycle is a totally reversible cycle.
Therefore, all the processes that comprise it can be reversed,
76
in which case it becomes the Carnot refrigeration cycle.
 Thermodynamics: An Engineering Approach
Carnot cycle Yunus A. Çengel, Michael A. Boles, McGraw-Hill, 2015

Execution of the Carnot cycle in a closed system.

Reversible Isothermal Expansion (process 1-2, TH = constant)
Reversible Adiabatic Expansion (process 2-3, temperature drops from TH to TL)
Reversible Isothermal Compression (process 3-4, TL = constant)
Reversible Adiabatic Compression (process 4-1, temperature rises from TL to TH77)
 The carnot principles

1. The efficiency of an irreversible heat engine is always less than the

efficiency of a reversible one operating between the same two
reservoirs.
2. The efficiencies of all reversible heat engines operating between the
same two reservoirs are the same.

Carnot’s Theorem: No real engine operating between two energy reservoirs

can be more efficient than a Carnot engine operating between the same two
reservoirs.

78
 Concept of Entropy: Thermodynamic approach

First law of Thermodynamics đQ = δQ = dU + δW = dU + đW

For quasi-static reversible process (ideal gas)

𝒏𝑹𝑻
𝜹𝑾 = 𝑷 𝒅𝑽 = 𝑷 𝒅
𝑷
−𝒏𝑹𝑻 𝒏𝑹
=𝑷 𝒅𝑷 + 𝒅𝑻
𝑷𝟐 𝑷
𝒏𝑹𝑻
= 𝒏𝑹𝒅𝑻 − 𝒅𝑷
𝑷

For an ideal gas, internal energy U depends only on T. Hence, 𝒅𝑼 = 𝑪𝑽 𝒅𝑻.

𝒏𝑹𝑻
𝜹𝑸 = 𝑪𝑽 𝒅𝑻 + 𝒏𝑹 𝒅𝑻 − 𝒅𝑷
𝑷
𝒏𝑹𝑻
= (𝑪𝑽 +𝒏𝑹) 𝒅𝑻 + − 𝑷 𝒅𝑷
= 𝒇(𝑻, 𝑷) 𝒅𝑻 + 𝒈 𝑻, 𝑷 𝒅𝑷

𝒏𝑹𝑻
𝒇 𝑻, 𝑷 = 𝑪𝑽 + 𝒏𝑹 𝐚𝐧𝐝 𝒈 𝑻, 𝑷 = − 𝑷

Lets check if 𝜹𝑸 is exact or inexact differential.

 𝜕2𝑄 𝜕2𝑄 𝜕𝑓 𝜕𝑔
= 𝑜𝑟 ≠ or = 𝑜𝑟 ≠
𝜕𝑃𝜕𝑇 𝜕𝑇𝜕𝑃 𝜕𝑃 𝜕𝑇

𝜕𝑓 𝜕𝑔 𝒏𝑹
=0 and =−
𝜕𝑃 𝜕𝑇 𝑷

𝜕𝑓 𝜕𝑔
∴ ≠
𝜕𝑃 𝜕𝑇

Hence, 𝑸 is not exact differential and is therefore not a state function of the state
variables P and T.
i.e., Q is not a property of the system.

Clausius Invents Entropy

𝒏𝑹𝑻
𝜹𝑸 = (𝑪𝑽 +𝒏𝑹) 𝒅𝑻 + − 𝒅𝑷
𝑷
Divide above equation by T
𝜹𝑸 𝑪𝑽 + 𝒏𝑹 𝒏𝑹
= 𝒅𝑻 + − 𝒅𝑷
𝑻 𝑻 𝑷
= 𝒇(𝑻, 𝑷) 𝒅𝑻 + 𝒈 𝑻, 𝑷 𝒅𝑷
𝑪𝑽 +𝒏𝑹 𝒏𝑹
𝒇 𝑻, 𝑷 = 𝐚𝐧𝐝 𝒈 𝑻, 𝑷 = −
𝑻 𝑷
 Lets check if 𝜹𝑸/𝑻 is exact or inexact differential.

𝜕𝑓 𝜕𝑔
=0 and = 0
𝜕𝑃 𝜕𝑇

𝜕𝑓 𝜕𝑔
∴ =
𝜕𝑃 𝜕𝑇

Hence, 𝜹𝑸/𝑻 is exact differential. Let 𝒅𝐒 = 𝜹𝑸/𝑻. Therefore, S is a state function

of the state variables P and T.
i.e., S is a property of the system or a state variable.
82
 Carnot engine & the second law
Wnet ,out QL
 th = =1− Carnot efficiency
QH QH

the second law

But for an ideal engine

Reversible heat engine

 Any heat engine

Carnot heat engine

• 100% efficiency can be achieved only if the cold reservoir is at absolute zero, which is
impossible.
• Real engines have some frictional losses. at best they achieve 60-80% of the Carnot value of
efficiency. 84
Entropy: Statistical Mechanics view
 Heaviside step function
0 𝑓𝑜𝑟 𝑥 < 0
𝜃 𝑥 =
1 𝑓𝑜𝑟 𝑥 > 0
Discontinuous at x = 0

−𝜃 −𝑥 𝑓𝑜𝑟𝜆 < 0
𝜃 𝜆𝑥 =
𝜃 𝑥 𝑓𝑜𝑟𝜆 > 0
using
 Connecting both entropies

J/K

For an isolated system of N ideal gas molecules with energy E and confined to
volume V, the number of microstates is given by
Earlier case
 using

We expect ∆S to be zero, because there is no distinction between the

system with and without the shutter.

Let us say we start with the shutter out. First insert the shutter; next
remove the shutter. We get back to the initial state. We have reversibility.
Hence entropy of mixing should be zero. This is called Gibbs paradox.

To resolve the Gibbs’ paradox, Boltzmann introduced the notion of

indistinguishability of particles to correct for over counting of the micro
states.
 In terms of number density

Clausius entropy is deeply rooted in thermal phenomenon : entropy is heat divided by temperature.
Boltzmann entropy is based on counting of the micro states of a system, thermal or otherwise.
 We will see later

Notice
 Clausius Inequality

In general,

wherein equality obtains when the process is (quasi - static and) reversible.
Consider a system that undergoes a cyclic process. Since S is property of the system
and since the system returns to its initial state after a cycle, dS = 0. This statement is
true irrespective of whether the cycle is reversible or has one or more segments that are
irreversible.

If the different segments that constitute the cyclic process are all reversible then

where the integral is taken over the cycle. However if the cyclic process contains
one or more irreversible segments, then, the Clausius inequality reads as,

In general, for a cyclic process,

wherein equality obtains if the cyclic process is (quasi static and) reversible.
101
 Second Law of Thermodynamics: few remarks

Another statement of the second law of thermodynamics:

The total entropy of an isolated system never decreases.

Entropy is a measure of the disorder of a system.

This gives us yet another statement of the second law:
Natural processes tend to move toward a state of
greater disorder.

Thermal equilibrium is a similar process—the uniform final state has more disorder than the
separate temperatures in the initial state

Perpetual-motion machine: Any device that violates the first or the second law.
A device that violates the first law (by creating energy) is called a PMM1.
A device that violates the second law is called a PMM2.
First Law of Thermodynamics in terms of S dU = δQ – δW

δQ = TdS (reversible process)

H = U + PV
δW = PdV
dH = dU + PdV + VdP
dU = TdS – PdV
dH = TdS + VdP
TdS = dU + PdV Gibbs equation
TdS = dH - VdP

𝒅𝐔 𝒅𝐕 𝒅𝐇 𝒅𝐏
𝐝𝐒 = +𝐏 𝐝𝐒 = −𝐕
𝐓 𝐓 𝐓 𝐓

Differential changes in entropy in terms of other properties

Isoentropic process: constant entropy process (𝐝𝐒 =0)

103
 Carnot cycle Thermodynamics: An Engineering
Approach
Yunus A. Çengel, Michael A. Boles, McGraw-Hill,
2015

P-V diagram T-S diagram

Reversible Isothermal Expansion (process 1-2, TH = constant)
Reversible Adiabatic Expansion (process 2-3, temperature drops from TH to TL)
Reversible Isothermal Compression (process 3-4, TL = constant)
104
Reversible Adiabatic Compression (process 4-1, temperature rises from TL to TH)
 Applications of Second Law of Thermodynamics.
Entropy change of liquids and solids
Liquids and solids can be approximated as incompressible substances since their
specific volumes remain nearly constant during a process.

𝒅𝐔 𝒅𝐕
𝐝𝐒 = +𝐏
𝐓 𝐓
𝒅𝐔 𝒅𝐓
Since 𝒅𝐕 = 0 for liquids and solids 𝐝𝐒 = =𝐂
𝐓 𝐓

𝐬𝐢𝐧𝐜𝐞 𝑪𝑷 = 𝑪𝑽 = 𝑪 𝐚𝐧𝐝 𝒅𝐔 = 𝑪𝒅𝐓

𝒅𝐓 𝑻𝟐
𝑺𝟐 − 𝑺𝟏 = න 𝐂(𝐓) ≅ 𝑪𝑨𝒗𝒈 𝒍𝒏
𝐓 𝑻𝟏

For and isentropic process of an incompressible substance

𝑻𝟐 105
𝑺𝟐 − 𝑺𝟏 ≅ 𝑪𝑨𝒗𝒈 𝒍𝒏 𝑻𝟏
= 0 ⟹ 𝑻𝟐 = 𝑻𝟏
 Applications of Second Law of Thermodynamics.
Entropy change of ideal gas (PV = RT)

From the first T ds relation From the second T ds relation

𝒅𝐔 𝒅𝐕 𝒅𝐇 𝒅𝐏
𝐝𝐒 = +𝐏 𝐝𝐒 = −𝐕
𝐓 𝐓 𝐓 𝐓

𝒅𝐔 = 𝑪𝑽 𝒅𝐓 𝒅𝐇 = 𝑪𝑷 𝒅𝐓

P = RT/V V = RT/P

𝒅𝐓 𝒅𝐕 𝒅𝐓 𝒅𝐏
𝐝𝐒 = 𝐂𝐕 +𝐑 𝐝𝐒 = 𝐂𝐏 −𝐑
𝐓 𝐕 𝐓 𝐏

𝟐
𝒅𝐓 𝑽𝟐 𝟐
𝒅𝐓 𝑷𝟐
𝑺𝟐 − 𝑺𝟏 = න 𝐂𝐕 𝐓 + 𝑹 𝒍𝒏 𝑺𝟐 − 𝑺𝟏 = න 𝐂𝐏 𝐓 − 𝑹 𝒍𝒏
𝟏 𝐓 𝑽𝟏 𝐓 𝑷𝟏
𝟏

Exercise Problem: Derive the expression for dS = S2-S1 in terms of P and V 106
 CHANGE IN ENTROPY FOR VARIOUS PROCESSES

Constant Volume Process

𝟐
𝒅𝐓 𝑽𝟐
𝑺𝟐 − 𝑺𝟏 = න 𝐂𝐕 𝐓 + 𝑹 𝒍𝒏
𝟏 𝐓 𝑽𝟏

V1=V2, i.e., ln(V2/V1)=0

𝟐
𝒅𝐓 𝑻𝟐 𝑷𝟐
𝑺𝟐 − 𝑺𝟏 = න 𝐂𝐕 𝐓 = 𝑪𝒍𝒏 or 𝑺𝟐 − 𝑺𝟏 = 𝑪𝒍𝒏
𝟏 𝐓 𝑻𝟏 𝑷𝟏

107
Constant Pressure Process

𝟐
𝒅𝐓 𝑷𝟐
𝑺𝟐 − 𝑺𝟏 = න 𝐂𝐏 𝐓 − 𝑹 𝒍𝒏
𝟏 𝐓 𝑷𝟏

P1 = P2, i.e., ln(P2/P1)=0

𝟐
𝒅𝐓 𝑻𝟐 𝑽𝟐
𝑺𝟐 − 𝑺𝟏 = න 𝐂𝐏 𝐓 = 𝑪𝒍𝒏 or 𝑺𝟐 − 𝑺𝟏 = 𝑪𝒍𝒏
𝟏 𝐓 𝑻𝟏 𝑽𝟏

108
Constant Temperature Process

𝟐 𝟐
𝒅𝐓 𝑽𝟐 𝒅𝐓 𝑷𝟐
𝑺𝟐 − 𝑺𝟏 = න 𝐂𝐕 𝐓 + 𝑹 𝒍𝒏 or 𝑺𝟐 − 𝑺𝟏 = න 𝐂𝐏 𝐓 − 𝑹 𝒍𝒏
𝟏 𝐓 𝑽𝟏 𝟏 𝐓 𝑷𝟏

T1 = T2, i.e., dT=0

𝑽𝟐
𝒅𝑺 = 𝑺𝟐 − 𝑺𝟏 = 𝑹 𝒍𝒏
𝑽𝟏

𝑽
𝑹𝑻 𝒍𝒏 𝑽𝟐 𝑸
𝟏
𝒅𝑺 = = 109
𝑻 𝑻
 Adiabatic Process
Adiabatic process of a system is one in which there is no heat transfer.

Reversible adiabatic
or
isoentropic Process

There is no area under the T-s diagram

because there is no heat transfer during the
process dS = δQ/dT and δQ = 0.
Therefore, change in entropy is zero. dS = 0.

Irreversible adiabatic Process

But δQ = 0 (for adiabatic process)

Therefore, S2 – S1 > 0 or S2 > S1110

 Polytropic Process

Heat transfer during

polytropic process is
given by,
𝛾−𝑛
𝛿𝑄 = 𝛿𝑊
𝛾−1
𝛾 = CP/CV
𝛾−𝑛
𝛿𝑄 = 𝑃𝑑𝑉
𝛾−1

𝛾 is adiabatic index and n is polytropic index

𝛿𝑄 (𝛾 − 𝑛) 𝑃
dS = = 𝑑𝑉
𝑇 (𝛾 − 1) 𝑇

𝛾 − 𝑛 2𝑃 (𝛾 − 𝑛) 2 𝑅
S2 − S1 = න 𝑑𝑉 = න 𝑑𝑉
𝛾−1 1 𝑇 (𝛾 − 1) 1 𝑉

𝜸−𝒏 𝑽𝟐
𝐒𝟐 − 𝐒𝟏 = 𝑹𝒍𝒏
𝜸−𝟏 𝑽𝟏
111
 APPLICATIONS OF ENTROPY PRINCIPLE

• Transfer of Heat through a Finite Temperature Difference

(i) If ΔS> 0 (or) T1 > T2 the process is irreversible and possible.

(ii) If ΔS= 0 (or) T1 = T2 the process is reversible.
(iii) If ΔS< 0 (or) T1 < T2 the process is impossible. 112
 • Mixing of Two Fluids Consider a system with two subsystems as shown.
Subsystem 1 contains fluid of mass m1, specific heat at constant
pressure, c1 and temperature, T1, where T1 > T2.
Subsystem2, mass m2 has a specific heat at constant pressure,
c2 and temperature, T2.

T1 T2 Let us assume that these two subsystems are separated by a

partition in an adiabatic enclosure.

When the partition is removed, the two fluids start mixing with each
other. After mixing, it will attain the thermal equilibrium with some final
temperature, Tf .
Note that Tf will be lesser than T1 but greater than T2 (T2 < Tf < T1).

By energy balance,

Subsystem 1 Subsystem 2

Total entropy of the System

113
 To simplify, assume m1 = m2 = m and c1 = c2 = C,

This is always positive because the arithmetic mean of any two numbers is always greater
that the geometric mean.

114
• Maximum Work from Two Finite Bodies at Temperatures TH and TL

Consider two identical finite bodies having same constant heat

capacity. Let them be at temperatures TH and TL, respectively, TH
> TL.
If the two bodies are merely brought together
into thermal contact, delivering no work, the final
temperature, Tf , reached would be maximum and is given by
Tf = (TH + TL)/2

Heat supplied to heat engine, QS = CP(TH-Tf )

Heat rejected to heat engine, QR = CP(Tf-TL)

Work delivered, W = QS - QR

W = CP(TH-Tf )-CP(Tf-TL)=CP(TH+TL-2Tf)

115
116
Third Law of Thermodynamics
 • ABSOLUTE ENTROPY

By now it should be clear that entropy is defined only in terms of entropy change in a
system from initial to final state. It is not measured in terms of absolute entropy. To
provide an absolute value for entropy, a zero value of entropy of the system should be
chosen arbitrarily as a standard state. Then, the entropy change is calculated with respect
to this standard state.

For example, consider a system being at state 1. The absolute entropy, ΔS = S1−S0
So, where S1 is entropy of the system at state 1 and S0 is entropy of the system at
standard state denoted by 0.

In this connection, the entropy of a pure crystalline substance is taken as zero at absolute
temperature of zero. This statement is called the third law of thermodynamics. This law
provides an absolute reference point is called as absolute entropy. It is more useful in
thermodynamic analysis of chemical reactions.

118
Third Law of Thermodynamics

Nernst Heat Theorem (1926)

Adapted from Prof. Graeme Ackland’s notes

Third Law of Thermodynamics Nernst Heat Theorem (1926):
based on Experimental Observation
 Planck’s Statement
of the Third law

Simon’s Statement of the Third law (1937)

 Third Law of Thermodynamics: Consequences
1. Unattainability of absolute Zero
Alternate
statement of the
Third law

2. Vanishing (𝜷)
Thermal expansion coefficient
3. Vanishing Heat Capacity
4. Magnetic cooling: Adiabatic demagnetization
Maxwell’s Demon: breaks second law of thermodynamics
Entropy: Other definitions
 Laws of Thermodynamics: Overview
• 0th Law: Defines Temperature (T)
Allows the use of Thermometers!
• 1st Law: Defines Energy & says total Energy is Conserved.
Also Defines
Internal Energy U, Heat Q, and Mechanical Work W
• 2nd Law: Defines Entropy (S)
• 3rd Law: Gives Entropy a
Numerical Value (as T → 0!)
• NOTE! These laws are UNIVERSALLY VALID
for systems at equilibrium &
They can not EVER be circumvented for such systems!
 The “Calculus” of Thermodynamics
Overview
• The main focus is
The development of functional property
relationships for simple systems
The relationships developed will be completely
general.
• These relationships are not physical property
models. Instead, they represent practical
constitutive equations specific for each pure
substance or mixture.
• Another major objective is to introduce
techniques for recasting derived
properties and their derivatives into
forms that can be directly evaluated in
terms of primitive properties which are
measurable.
• This objective will be accomplished by
manipulating the
Combined 1st & 2 nd Laws
through various differential calculus techniques
 Some Thermodynamic Variables:
Internal Energy = U, Entropy = S
Temperature = T
• Mostly for Gases: (also true for any substance):
External Parameter = V
Generalized Force = p
(V = volume, p = pressure)
• For a General System:
External Parameter = x
Generalized Force = X
Assume that the External Parameter = Volume V in order
to have a specific case to discuss. For systems with another
external parameter x, the infinitesimal work done is đW =
Xdx. In this case, in what follows, replace p by X & dV by
dx.
• For infinitesimal, quasi-static processes:
1st & 2nd Laws of Thermodynamics
1st Law: đQ = dU + pdV
2nd Law: đQ = TdS
 The Combined 1st & 2nd Laws
TdS = dU + pdV
• In above relation, there are 5 Variables: T, S, U, p, V
• It can be shown that: Any 3 of these can always be
expressed as functions of any 2 others.
• That is, there are always
2 independent variables & 3 dependent variables.
Which 2 are chosen as independent is arbitrary.
• The number N of possible choices of the 2 independent
variables out of the 5 is N = (5!)/[(2!)(3!)] = 10
• In what follows, we discuss the 4 most common (& useful!)
choices of the 2 independent variables.
A Brief, Pure Math Discussion!!
• Consider 3 variables: x, y, z. Suppose that
we know that x & y are Independent
Variables. Then, It Must Be Possible to
express z as a function of x & y. That is,
There Must Exist a Function:
z  z(x,y).
• Calculus Result:
 The total differential of z(x,y) is:
dz  (∂z/∂x)ydx + (∂z/∂y)xdy (a)
• Suppose that, for these 3 variables: x, y, z,
we take y & z as independent variables
instead of x & y. Then,
There Must be a Function x = x(y,z).
• From calculus, the total differential of x(y,z) is:
dx  (∂x/∂y)zdy + (∂x/∂z)ydz (b)
• (a) from the previous slide is:
dz  (∂z/∂x)ydx + (∂z/∂y)xdy (a)
• Using (a) & (b) together, the partial derivatives
in (a) & those in (b) can be related to each
other as follows:
• The total differential of x(y,z) is:
dx  (∂x/∂y)zdy + (∂x/∂z)ydz (b)
• The total differential of z(x,y) is:
dz  (∂z/∂x)ydx + (∂z/∂y)xdy (a)
• Using (a) & (b) together, the partial derivatives in (a)
& those in (b) can be related to each other as follows:
• Suppose we are in a situation where z is constant. In
that case, (a) becomes:
0  (∂z/∂x)ydx + (∂z/∂y)xdy (a')
• Solve (a') for the ratio (dx/dy):
(dx/dy) = - (∂z/∂y)x/(∂z/∂x)y (c)
• The left side of (c) is just (∂x/∂y)z so
(∂x/∂y)z = - (∂z/∂y)x/(∂z/∂x)y
• Consider again the 3 variables: x, y, z, & take x
& y as independent variables.
Then there Must be a Function z = z(x,y)
• The total differential of z is given by:
dz  (∂z/∂x)ydx + (∂z/∂y)xdy
• In what follows, we always assume that all
functions are analytic.
So, the 2nd cross derivatives
are equal, such as:
(∂2z/∂x∂y)  (∂2z/∂y∂x), etc.
• In what follows we’ll repeatedly use this property.
 Mathematics Summary
• Consider a function of 2 independent variables:
f = f(x1,x2).
• It’s exact differential is
df  y1dx1 + y2dx2
& by definition:

• Because f(x1,x2) is an analytic  y2   y1 

  = 
function, it is always true that: x 
 1  x2  2  x1
x

Or: [∂ (y
2
2)/∂x1∂x2)]  [∂ (y
2
1)/∂x2∂x1)]
 Some Methods & Useful Math Tools for
Transforming Derivatives
Derivative Inversion
 F   1   S  =  1 
  =     
 y  x  y F  x  P T  P S T
Triple Product (xyz–1 rule)
 F   x   y  = −1  H   T   P 
            = −1
 x  y  y  F  F  x  T  P  P  H  H T
Chain Rule Expansion to Add Another Variable
 F   F    
  =
 S  =  S   T  = C P 1 = 1
        
 y  x    x  y  x  H 
P  P 
T H  P T CP T
Maxwell Reciprocity Relationship
  (F x ) y    (F y )x 

 y
 = 
x  x

y
Fxy = Fyx
Pure Math: Jacobian Transformations
• A Jacobian Transformation is often used to
transform from one set of independent
variables to another.
• For functions of 2 variables f(x,y) & g(x,y) it is:
 f   f 
   
 ( f , g )  x  y  y  x =  f   g  −  f   g 
        
 ( x, y )  g   g   x  y  y  x  y  x  x  y
   
 x  y  y  x
Determinant!
 Jacobian Transformations
Have Several Useful Properties
( f , g ) ( g , f )
Transposition =−
 ( x, y )  ( x, y )
( f , g ) 1
=
Inversion  ( x, y )  ( x, y )
( f , g )

Chain Rule  ( f , g )  ( f , g )  ( z , w)
=
Expansion  ( x, y )  ( z , w )  ( x, y )
• Suppose that we are only interested in the
first partial derivative of a function f(z,g)
with respect to z at constant g:
 f  ( f , g )
  =
 z  g ( z , g )
• This expression can be simplified using the chain
rule expansion & the inversion property
( f , g )
 f  = ( x, y )
 
 z  g ( z , g )
 ( x, y )
 Properties of the Internal Energy E
dU = TdS – pdV (1)
• First, choose S, V as independent variables:
U  U(S,V), so
U 
 ∂U U 
 ∂U
dE = 
dU  dS +   dV (2)
 S V  V  S
• Comparison of (1) & (2) clearly shows that
U 
 ∂U U 
 ∂U
  = T and   = −p
 S V  V  S
 Internal Energy E(S,V)
S, V are independent variables:
• We just showed that
 ∂U
U  ∂U
U
  =T   = −p (3)
 S V  V  S
• The general result for analytic functions is that
the 2nd cross derivatives are equal:
So: (∂2U/∂S∂V)  (∂2U/∂V∂S) (4)
• Putting (3) in (4) gives:
 T   p  Maxwell Relation I!
  = − 
 V  S  S V
• Instead of (S,V), if (S,p) are taken as
independent variables, its useful to define the
following energy:
H  H(S,p)  U + pV  Enthalpy
• Use the combined 1st & 2nd Laws. Rewrite
them in terms of dH:
dU = TdS – pdV = TdS – [d(pV) – Vdp] or
dH = TdS + Vdp (1)

• But, also:
(2)
• From the previous slide, the combined 1st & 2nd
Laws in terms of differential enthalpy dH are:
dH = TdS + Vdp (1)

• But, also: (2)

• Comparison of (1) & (2) clearly shows that

and
• Applying the general result for the 2nd cross derivatives:
 T   V 
  =   Maxwell Relation II!
 p  S  S  p
• Instead of (S,V), or (S,p), if (T,V) are taken as
independent variables, its useful to define the
energy:
F  F(T,V)  U – TS
 Helmholtz Free Energy
• Use the combined 1st & 2nd Laws. Rewrite
them in terms of dF:
dU = TdS – pdV = [d(TS) – SdT] – pdV or
dF = -SdT – pdV (1)
• But, also:
dF ≡ (F/T)VdT + (F/V)TdV (2)
• From the previous slide, the combined 1st &
2nd Laws in terms of differential Helmholtz
free energy dF are:
dF = -SdT – pdV (1)
• But, also:
dF ≡ (F/T)VdT + (F/V)TdV (2)
• Comparison of (1) & (2) clearly shows that
(F/T)V ≡ -S and (F/V)T ≡ -p
• Applying the general result for the 2nd cross derivatives:

Maxwell Relation III!

• If T & p are chosen as independent variables,
it is convenient to define the energy:
G  G(T,p)  U –TS + pV
 Gibbs Free Energy
• Use the combined 1st & 2nd Laws. Rewrite
them in terms of dG:
dE = TdS – pdV = d(TS) - SdT – [d(pV) – Vdp]
or dG = -SdT + Vdp (1)
• But, also:
dG ≡ (G/T)pdT + (G/p)Tdp (2)
• From the previous slide, the combined 1st &
2nd Laws in terms of differential Gibbs free
energy dG are:
dG = -SdT + Vdp (1)
• But, also:
dG ≡ (G/T)pdT + (G/p)Tdp (2)
• Comparison of (1) & (2) clearly shows that
(G/T)p ≡ -S and (G/p)T ≡ V
• Applying the general result for the 2nd cross derivatives:

Maxwell Relation IV!

 Summary: Energy Functions
1. Internal Energy: U  U(S,V)
2. Enthalpy: H = H(S,p)  U + pV
3. Helmholtz Free Energy: F = F (T,V)  U – TS
4. Gibbs Free Energy: G = G(T,p)  U – TS + pV

1. dU = TdS – pdV
Combined 1 st 2. dH = TdS + Vdp
& 2nd Laws 3. dF = - SdT – pdV
4. dG = - SdT + Vdp
Another Summary: Maxwell’s Relations
(a) ΔU = Q + W 1. 2.
(b) ΔS = (Qres/T)  T   p   T   V 
  = −    =  
 V  S  S V  p  S  S  p
(c) H = U + pV
(d) F = U – TS 3. 4.
 S   p   S   V 
  =    = − 
(e) G = H - TS  V T  T V  p T  T  p

1. dU = TdS – pdV  z   z 
Mdx + Ndy = dz =   dx +   dy
2. dH = TdS + Vdp  x  y  y  x
3. dF = -SdT - pdV  M   N 
4. dG = -SdT + Vdp   =  
 y  x  x  y
 Summary
The 4 Most Common Maxwell Relations:

 T   P   S   P 
  = −    = 
 V  S  S V  V T  T V

 T   V   S   V 
  =  −  =  
 P  S  S  P  P T  T  P
Maxwell Relations
 Maxwell Relations
Maxwell Relations from dU, dF, dH, & dG
Internal  T   P 
  = − 
Energy  V  S , N   S V , N

Helmholtz  S   P 
  = 
Free Energy  V T , N  T V , N

 T   V 
Enthalpy   = 
 P  S , N   S  P , N

Gibbs Free  S   V 
  = − 
Energy  P T , N  T  P , N
Mathematical Preliminaries and Legendre transforms

Delta function ≡ Derivative of a Heaviside function

න 𝑓(𝑥)𝛿(𝑥 − 𝑥0) 𝑑𝑥 = 𝑓(𝑥0)

154
Theorem 1:
If a relation exists among the variables say, x, y and z, then z may be expressed as a function
of x and y.
z = f (x,
y)

Note that M and N are the functions of x and y, respectively.

and

This means

This is the condition for exact or perfect differential.

Theorem 2: If a quantity f is a function of the variables say, x, y and z and a relation exists
among the variables say, x, y and z, then f is a function of any two of x, y and z. Similarly, x, y
and z may be regarded as a function of f .
Thus, if

Similarly, if

Substituting the expression of dy in the preceding equation:

Again,
Theorem 3:
Among the variables say, x, y and z any one variable may be considered as a function of the other
two.
Thus, if

Similarly,

Cancelling dx on both sides and as dy ≠ 0, we have

 Taking inverse on both sides,

By rearranging

In the case of the three thermodynamic variables p, V and T , the following relations holds good
 U(S, V, N) and its partial derivatives

First Law of thermodynamics

S(U, V, N) and its partial derivatives

I Law of thermodynamics
Chemical Potential
The partial derivative of U with respect to N is called the chemical potential, and is
usually denoted by the symbol µ.

In the entropic picture,

Closed System and Helmholtz Free Energy

Consider a closed system - a system which is in thermal contact with the surroundings. It
exchanges energy but is closed to exchange of matter.
The system is in thermal equilibrium with its surroundings whence the system and its
surroundings are at the same temperature.
Thus temperature is a natural variable for describing the system.

Since the temperature remains constant

For a process that takes the system reversibly from an equilibrium state 1 to an equilibrium
state 2, at constant temperature T , we can write,

where W is the work done during the isothermal reversible process 1 → 2

U - TS (= F) as a thermodynamic property of the system.

F: Helmholtz free energy and is employed for studying closed systems

It is readily seen that the principle of minimum energy and maximum entropy can be
combined into a single principle of minimum free energy.
Spontaneously a system would go to a state with minimum free energy.
We also see that work done on the system is minimum for a reversible process.

Free Energy and the Second Law

Clausius inequality 𝜹𝑸 𝜹𝑸 ≤ 𝑻𝒅𝑺

≤ 𝒅𝑺
𝑻
First law of thermodynamics δQ = dU + δW dU + δW ≤ 𝑻𝒅𝑺
dU − 𝑻𝒅𝑺 ≤ δW
dU − 𝑻𝒅𝑺 ≤ δW
δW ≥ dU − 𝑻𝒅𝑺
 δW ≥ d(U − 𝑻𝑺)
δW ≥ dF

The above is a statement of the Second law of thermodynamics in terms of free energy and
energy transacted by work in an isothermal process, not necessarily reversible; equality obtains
when the isothermal process is reversible.

Legendre Transform : General

Consider f , a quantity that varies when x is
varied

Take a point (x, y = f(x)) on the graph.

Draw a line tangent to the curve at this point.

Let the slope of this tangent be denoted by m.
Note that m depends of x. Principle of Legendre Transform : Intercept C
is expressed as a function of slope
From figure,
provides an alternate description of
In other words,
Legendre transformation of

Legendre transform contains all information in the original

fundamental relation.
Free energy provides an alternate formulation of thermodynamics suitable for describing closed
system.
In what follows we shall see of general alternate formulations of thermodynamics based on
Legendre transform.

Consider passage from internal energy picture suitable for studying isolated systems to free
energy picture, suitable for closed systems, as a transform :

The basic idea is to view the curve U(S), as an envelop of a set of tangents; each tangent is
specified by its slope and the intercept. The slope is temperature, T and the intercept is Free
energy, F . Thus we go from U versus S picture to F versus T picture
Legendre Transform : S → T and U(S, V, N) → F (T, V,
N)
Take f as U and x as S. We see that the slope m corresponds to temperature,
T . Denote the intercept by F and we have the Legendre transform : S → T and U → F
.
Procedure
• Start with U ≡ U(S, V, N).
• Derive an expression for the partial derivative of U with respect
to S. This partial derivative is a function of S, V and N .
• Equate it to T and invert it to express S ≡ S(T, V, N).
• Replace S by this function in the expression : U(S, V, N) - TS.
• You will get an expression involving only T , V , and N . This is
the desired expression for the free energy F (T, V.N).
Example
Let the fundamental equation of substance be given by
where Θ is a constant.
In the first step, we derive an expression for temperature as a function of S, V and N . We have

In the second step, we invert the above expression and get S as a function of T, V and N

In the third step, we carry out the Legendre transform:

The independent variables of F are T , V and N .

By taking the partial derivatives of F with respect to T , V , and N we obtain expressions for
entropy, pressure and chemical potential respectively. We have
Enthalpy/Heat of reaction 𝒅𝐇 = d(U +PV) = δQ Constant Pressure

Change in H when the system undergoes a reversible process, equals energy transacted by
heat, or what the chemists call as heat of reaction.

Enthalpy increases when the chemical reaction is endothermic, i.e. when energy enters the
system by heat.

Enthalpy is negative if the process is exothermic, whence energy exits the system by heat.

Legendre Transform : V → P and U(S, V, N) → H(S, P, N)

 Example

Consider the fundamental equation,

An expression for pressure in terms of S, V, N can be derived as

Now take P as an independent variable and express V as a function of P :

Enthalpy is formally given by

Eliminating V from the above we get

By taking the partial derivatives of H with respect to S, P and N , we can derive expressions for
T, V and µ. We have,

We see immediately that,

 Gibbs Free Energy Gibbs free energy is a function of T, P, and N

Legendre Transform : S → T , V → P , and U(S, V, N) → G(T, P, N)

Legendre Transform : S → T and H(S, P, N) → G(T, P, N)

Example

We have

Now consider T as an independent variable and express S as a function of T, P, and N . We get,

By taking partial derivatives of G with respect to the variables T, P, and N , we can derive
expressions for S, V , and µ. We have

Euler Theorem for Homogeneous Functions

Let f(x1, x2, · · · xN) be an n-th order homogeneous function of x1, x2, · · · xN. We can express
this formally as,

Differentiate both sides of the equation with respect to λ. We get

The above is valid for any value of λ; take λ = 1; we get the theorem for homogeneous functions
discovered by Euler and is given by
• Helmholtz free energy F is a function of T , V and N. Itis an important property of a closed
system; it is an extensive property; F is a first order homogeneous function of V and N .
• Enthalpy is an extensive property of a thermodynamic system; it is a function of S, P and N; it
is a first order homogeneous function of S and N.
• Gibbs’ free energy is a function of T , P , and N ; it is a first order homogeneous function of N;

Euler Relation: (a) Internal Energy

Let us differentiate both sides of the above equation with respect to λ, We get,

The above is valid for any number λ. Let us set λ = 1. We get,

(b) Helmholtz Free Energy

(c) Enthalpy

(b) Gibbs Free Energy

 Gibbs-Duhem Relation
Start with the Euler relation, for the internal energy,

Take the derivatives on both sides and get,

The first law of thermodynamics tells us that

Hence,

Let s = S/N denote entropy per particle and v = V/N denote the volume per particle. s and v are
now intensive properties. We can now write the above equation as,

The above is called Gibbs-Duhem relation. It tells us that the three intensive properties T,
P, and µ are not all independent. If you know any two, the third can be obtained.
 Maxwell Relations Follow 7th chapter of Callen’s book

Maxwell relations involve partial derivatives of intensive variables taken with respect
to extensive variables.

Maxwell relations are based on the observation that the order with which we take the partial
derivatives does not matter.

Either way we should get the same result.

Internal Energy and First Maxwell Relation

The partial derivative of U(S, V ) with respect to S is T (S, V ) while the negative of
partial derivative of U(S, V ) with respect to V is P (S, V ).

First Maxwell Relation

 Helmholtz Free Energy and Second Maxwell
Relation
Helmholtz Free Energy

or

The partial derivative of F with respect to T is S and the partial derivative of F with respect to
V is P.

Second Maxwell Relation

Enthalpy and Third Maxwell Relation

Enthalpy H (S,P) or

The partial derivative of H with respect to S as T and the partial derivative of H with respect
to P is V
Third Maxwell Relation
Gibbs Free Energy and Fourth Maxwell Relation
Gibbs Free Energy G(T,P)

or

The partial derivative of G with respect to T is S and the partial derivative of G with respect
to P is V .

Fourth Maxwell Relation

Mnemonic for Maxwell Relations From: C B P Finn, Thermal Physics, Second

Edition, Chapman and Hall (1993)pp.121-
Society for Prevention of Teaching Vectors 122
Scheme
• Start at any of the above four letters.
• Go round clock-wise or anti-clock wise to the third alphabet. Mark it
as an outer arc.
• The outer arc gives the partial derivative of the first letter with respect
to the second letter keeping the third letter constant.
• Proceed one letter further along the same direction and stop.
 Internal Energy and First Maxwell Relation

Helmholtz Free Energy and

Second Maxwell Relation

Enthalpy and Third Maxwell Relation

Gibbs Free Energy and

Fourth Maxwell Relation
These Maxwell relations are limited to simple
compressible systems.
 Thermodynamics relations in a nutshell

H = H (S, P)

F = F (T, V)
U = Internal energy
F = Helmholtz free energy
E = H enthalpy
G =Gibbs free energy

dH

dF

H
I. Isothermal Compression coefficient of thermal volume expansion at
constant pressure

Isothermal
Taking into account the change of V during the
compression process
First Maxwell Relation
 II. Adiabatic Compression

For an adiabatic process the change of S at constant

P is zero, since there is no heat transaction between
the system and the surroundings.

using

Fourth Maxwell Relation

 III. Energy Equations
Each thermodynamic law gives rise to the definition of a thermodynamic variable
• Zeroth law → temperature
• First law → internal energy and
• Second law → entropy

First Second

First Energy Equation

Consider a thermodynamic system; let us investigate how does the internal energy (U) of the
system changes with its V, P and T.
First law of thermodynamics
dT coeff. dV coeff.

Second Maxwell Relation

The above is called the first energy equation. Note that the right hand side can be calculated
from the equation of state.
It would enable us to gain information about the internal energy.
Applications of First Energy Equation
1. Ideal gas
The internal energy does not depend on
volume. It depends only on temperature.

2. van der Waals gas

We find that internal energy depends on volume.

For a non-ideal gas, internal energy shall depend upon both temperature and volume.
3. First energy equation in terms of isothermal compressibility (γ) and
coefficient of thermal expansion (κT)
Second Energy Equation

Equating the coefficients of dT

Equating the coefficients of dP

 Fourth Maxwell Relation

In terms of isothermal compressibility κT and coefficient thermal expansion γ

 IV. TdS Equations
S as a function of (i) T and V , (ii) T and P , and (iii) P and V

First TdS equation

Second Maxwell Relation

Second TdS equation

Fourth Maxwell Relation

Third TdS equation

Using the identities

V. Clausius-Clapeyron Equation
𝑆 ≡ 𝑆(𝑇, 𝑉)

𝜕𝑆 𝜕𝑆
𝑑𝑆 = 𝑑𝑇 + 𝑑𝑉
𝜕𝑇 𝑉
𝜕𝑉 𝑇

When a phase-change takes place from saturated liquid to saturated vapor, the temperature
remains constant. Therefore,

𝜕𝑆 𝑑𝑆 𝜕𝑆
𝑑𝑆 = 𝑑𝑉 =
𝜕𝑉 𝑇 𝑑𝑉 𝜕𝑉 𝑇

𝜕𝑆 𝜕𝑃
Second Maxwell Relation: =
𝜕𝑉 𝑇 𝜕𝑇 𝑉

𝜕𝑃
𝑑𝑆 = 𝑑𝑉
𝜕𝑇 𝑉

𝜕𝑃
is the slope of the of the saturation curve. Integrating the above equation
𝜕𝑇 𝑉

𝑆𝑔𝑎𝑠 𝑉𝑔𝑎𝑠
𝜕𝑃
න 𝑑𝑆 = න 𝑑𝑉
𝑆𝑙𝑖𝑞𝑢𝑖𝑑 𝜕𝑇 𝑉 𝑉𝑙𝑖𝑞𝑢𝑖𝑑
 𝜕𝑃 𝜕𝑃 (𝑆𝑔𝑎𝑠 − 𝑆𝑙𝑖𝑞𝑢𝑖𝑑)
𝑆𝑔𝑎𝑠 − 𝑆𝑙𝑖𝑞𝑢𝑖𝑑 = (𝑉𝑔𝑎𝑠 − 𝑉𝑙𝑖𝑞𝑢𝑖𝑑) =
𝜕𝑇 𝜕𝑇 (𝑉𝑔𝑎𝑠 − 𝑉𝑙𝑖𝑞𝑢𝑖𝑑)

𝜕𝑃 (𝑆𝑔𝑎𝑠 − 𝑆𝑙𝑖𝑞𝑢𝑖𝑑) 𝜕𝑃 𝑑𝑆
= or =
𝜕𝑇 (𝑉𝑔𝑎𝑠 − 𝑉𝑙𝑖𝑞𝑢𝑖𝑑) 𝜕𝑇 𝑑𝑉

𝛿𝑄 𝑑𝐻 𝜕𝑃 𝑆𝑔𝑎𝑠, 𝑙𝑖𝑞𝑢𝑖𝑑 1 𝐻𝑔𝑎𝑠, 𝑙𝑖𝑞𝑢𝑖𝑑

𝑑𝑆 = 𝑑𝑆 = = =
𝑇 𝑇 𝜕𝑇 𝑉𝑔𝑎𝑠, 𝑙𝑖𝑞𝑢𝑖𝑑 𝑇 𝑉𝑔𝑎𝑠, 𝑙𝑖𝑞𝑢𝑖𝑑

Clausius-Clapeyron Equation
VI. CP-CV 𝜕𝑈 𝜕𝑈 𝜕𝑆 𝜕𝑆
𝐶𝑉 = = =𝑇
𝜕𝑇 𝑉
𝜕𝑆 𝑉
𝜕𝑇 𝑉
𝜕𝑇 𝑉

𝜕𝐻 𝜕𝐻 𝜕𝑆 𝜕𝑆
𝐶𝑃 = = =𝑇
𝜕𝑇 𝑃
𝜕𝑆 𝑃
𝜕𝑇 𝑃
𝜕𝑇 𝑃

𝜕𝑆
𝑇
𝜕𝑆 𝜕𝑆 𝐶𝑃 𝜕𝑇 𝑃 𝜕𝑆 𝜕𝑇
𝐶𝑃 − 𝐶𝑉 = 𝑇 − 𝛾= = =
𝜕𝑇 𝜕𝑇 𝐶𝑉 𝑇 𝜕𝑆 𝜕𝑇 𝑃
𝜕𝑆 𝑉
𝑃 𝑉
𝜕𝑇 𝑉

𝜕𝑆 𝜕𝑆 𝜕𝑆 𝜕𝑆 𝜕𝑆 𝜕𝑉
𝑆 ≡ 𝑆(𝑇, 𝑉) 𝑑𝑆 = 𝑑𝑇 + 𝑑𝑉 − =
𝜕𝑇 𝑉
𝜕𝑉 𝑇
𝜕𝑇 𝑃
𝜕𝑇 𝑉
𝜕𝑉 𝑇
𝜕𝑇 𝑃

𝜕𝑆 𝜕𝑃 𝜕𝑆 𝜕𝑆 𝜕𝑃 𝜕𝑉
Second Maxwell Relation: = − =
𝜕𝑉 𝑇 𝜕𝑇 𝑉
𝜕𝑇 𝑃
𝜕𝑇 𝑉
𝜕𝑇 𝑉
𝜕𝑇 𝑃
𝜕𝑃 𝜕𝑉
𝐶𝑃 − 𝐶𝑉 = 𝑇
𝜕𝑇 𝑉
𝜕𝑇 𝑃

𝜕𝑉 𝜕𝑃 𝜕𝑇 𝜕𝑉 𝜕𝑃 𝜕𝑉
= −1 =−
𝜕𝑃 𝑇
𝜕𝑇 𝑉
𝜕𝑉 𝑃 𝜕𝑃 𝜕𝑇 𝜕𝑇
𝑇 𝑉 𝑃
 𝜕𝑃 𝜕𝑉 2
𝐶𝑃 − 𝐶𝑉 = 𝑇 𝜕𝑉 𝜕𝑃
𝜕𝑇 𝜕𝑇 𝐶𝑃 − 𝐶𝑉 = −𝑇
𝑉 𝑃 𝜕𝑇 𝑃
𝜕𝑉 𝑇

𝜕𝑉 2 𝜕𝑃
• Since > 0 and < 0, 𝐶𝑃 − 𝐶𝑉 > 0 → 𝑪𝑷 > 𝑪𝑽
𝜕𝑇 𝑃 𝜕𝑉 𝑇
• As 𝑇 → 0, 𝑪𝑷 → 𝑪𝑽 or 𝑪𝑷 = 𝑪𝑽 at absolute zero
𝜕𝑉
• When 𝜕𝑇 = 0, for example, for water at 4 oC when density is maximum or
specific volume is minimum 𝑪𝑷 = 𝑪𝑽

1 𝜕𝑉 Coefficient of volume expansion 𝜕𝑉

𝛽= or = 𝛽𝑉
𝑉 𝜕𝑇 𝑃
𝜕𝑇 𝑃
volume expansivity

1 𝜕𝑉
𝜅𝑇 = − Isothermal compressibility
𝑉 𝜕𝑃 𝑇 𝜕𝑉
𝜕𝑃 𝜕𝑇 𝑃 𝛽
𝜕𝑉 𝜕𝑃 𝜕𝑇 =− =
= −1 𝜕𝑇 𝜕𝑉 𝜅𝑇
𝜕𝑃 𝜕𝑇 𝜕𝑉 𝑉
𝑇 𝑉 𝑃 𝜕𝑃 𝑇

𝑉𝑇𝛽 2
𝐶𝑃 − 𝐶𝑉 = Mayer relation
𝜅𝑇