Phys 253 Thermal Physics

Physics 253: Thermal Physics
Lecture 1: Introduction
Prof: Walter Reisner

Time: 2:35-3:25
Place: BURN 1B39
Office Hours: 2-3 MW
Rutherford 411
What is Thermodynamics?
Thermodynamics distinct from other areas of physics. . .
Concerned with macroscopic system behavior
(e.g. systems containing a very large number of particles, ~1023 atoms in 1 mole)
Concerned with inter-conversion of different forms of energy (e.g.
mechanical work, heat, chemical energy, 1st of thermodynamics )
Concerned with irreversibility: 2nd law of thermodynamics provides a
directionality to time (arrow-of-time, certain processes only go one way)
Proscriptive: 2nd law places fundamental limitations on processes that
can occur in nature (perpetual motion not likely!)
Extremely general but empirical in character: thermodynamics provides

a framework for understanding/extending/processing experimental data from
a vast range of systems
Thermodynamics has fundamental laws but no fundamental underlying equations!
It is a fact of everyday life that certain systems can be
characterized in a simple way. . .
(e.g. gas at rest in a piston, a liter of ethyl alcohol at rest, a pitcher of
water left to sit on a table. . )
(1) These systems eventually reach states of equilibrium (uniform
composition, no flows, no pressure gradients/temperature gradients)
(2) In equilibrium they require only a few numbers for their description
(e.g. volume, density, temperature, pressure)
This is so despite the fact that these systems have at the microscopic
level an enormous number of degrees of freedom (e.g. are made up of
atoms in constant rapid motion) !
Thermodynamics applies to systems large enoughand studied over time
scales long enoughso that the details of atomic scale motion are
averaged out and in equilibrium the system can be characterized by a limited
set of macroscopic coordinates
What is large enough?
(Macroscale~1023 atoms, e.g. one moles worth)
What is long enough?
Much greater than characteristic time scale of atomic motions
(~10-15 s=1fs)
Equilibrium Thermodynamics: restricted to studying systems in equilibrium
(classical theory: our focus in this course)
Non-Equilibrium Thermodynamics: systems that are far from
equilibrium, characterized by dynamic energy flows/transport/diffusion,
chemical reactions, irreversible
(Note: non-equilibrium systems need more than just a few numbers for their
characterization, e.g. a spatially varying pressure or temperature distribution,
but are still coarse-grained with respect to the atomic scale)
Thermodynamics applies to systems large enoughand studied over time
scales long enoughso that the details of atomic scale motion are
averaged out and in equilibrium the system can be characterized by a limited
set of macroscopic coordinates
In equilibrium
P, V, T, N
1 mole of a gas (say Ar) ~ 1023 atoms
(Avagadros number NA=6.0221023)
Can be characterized by just four numbers:

Temperature (T), pressure (P), volume (V),
particle number (N)
Disordered highly rapid particle motions are blurred-out

Only large-scale, collective properties of particles survive averaging
(e.g. particle momentum transfer/unit time per unit area creates a net pressure pushing
against the walls that I could measure, say with a piston)
The First Law

As a consequence of thermodynamic averaging we necessarily loose
information regarding microscopic degrees of freedom of our system
Do these missing degrees of freedom (DOF) have physical consequences?
YES!!!
The missing DOF act as an additional repository for energy
We can transfer energy by performing mechanical work. . .
(e.g. by letting our gas expand and push a piston)
Energy can also be transferred via hidden DOF. . . this is HEAT!

Flow of heat energy and mechanical work both lead interchangeably to
increases in a systems internal energy: this is the heart of the 1st law of
thermodynamics
The Second Law

The laws of mechanics are time-reversible!
A particle traces out a certain trajectory, reverse the sign of the
force, the particle will go backwards along the same path!
If you change the direction at which you stir, can you make the cream
stirred into your coffee spontaneously go back to the center of your cup?
Use the heat dissipated by friction into the street by your cars wheels to
power your car?
Can you transport heat from an object at low temperature to high
temperature?
Well, no. . .
The Second Law

Nothing in life is certain except death, taxes
and the second law of thermodynamics. . . .
Seth Lloyd (2004)
The Second Law

Thermodynamics allows us to quantify what type of
processes can and cannot go backwards
This is the heart of the second law of thermodynamics
For an isolated system (fixed energy, volume, particle number):
Processes that increase the entropy: are irreversible
Processes that lead to no change in entropy: can go
backwards (are reversible)
Processes that decrease the entropy: not allowed!
Thermodynamics has no fundamental underlying equation
Basic Problem of Classical Mechanics:
Q: Given force F(x,t) how do I deduce the particles motion?

A: Use Newtons 2nd Law!
x(t)
F(x,t)
m
d 2x
F(x,t) = m 2
dt
Particle trajectory determined uniquely given initial conditions x=xo and v=vo
Solve fundamental
underlying equation(s) to determine system
behavior for all time!
(e.g. for varying system specification/initial/boundary conditions, etc.)
Same idea also applies to: classical electrodynamics, quantum

mechanics, relativistic field theories, general relativity etc.
. . .but NOT to thermodynamics!
Use Newtons law to model the dynamics of
all 1023 particles in a mole of gas? No Way!
Thermodynamics does NOT allow us to predict the time-course of

all system degrees of freedom given initial conditions
Thermodynamics does allow us to predict what process are
physically possible for the system/make future predictions on the
basis of certain empirical information (e.g. equation of state)
Thermodynamics does NOT require a detailed microscopic model,

hence its conclusions are unusually general and powerful
Thermodynamics vs Statistical Mechanics

Statistical
Mechanics
PV=NkBT
P, V, T, N
(PHYS 362)
Model System
(e.g. non-interacting pointparticles)
Thermodynamics
(system described in terms of a limited
number of macroscopic coordinates, linked
by equation of state, e.g. ideal gas law)
Statistical Mechanics: Directly calculate thermodynamic

properties of system from a physical model (e.g. by finding average
values of system properties over a statistical ensemble,)
Very few systems exactly solvable!
For many real-world systems

equation-of-state only known
empirically!
Prerequisites
Preresquisites: CEGEP physics or Phys 131 &
CEGEP Chemistry or Chem 120
Corequisite: Math 222
Math Background: Multivariable calculus
Know how to minimize/maximize functions of many variables
Know the difference between ordinary and partial derivatives
Know the difference between inexact/exact differentials
Timeline
I. Foundational Concepts and Eq-of-State: Concept of equilibrium,
isotherms, empirical temperature scales, equation-of-state of different
substances, ideal gas law, real gases, black-bodies.
II. Heat, Work and the first law of thermodynamics (Week 3-4): Work, heat,
heat capacities, quasi-static/isothermal/adiabatic processes and the first law.
III. Heat Engines and The Second Law (Weeks 4-5): Engines
types, Otto-cycle, Carnot cycle, Kelvin/Clausius statements of the
second law, absolute temperature scale
IV. Entropy (week 6-7): Entropy, entropic formulation of second law
(for cyclic processes and isolated systems), entropy and heat, entropy
changes in irreversible/reversible processes, statistical concept of
entropy, entropy of ideal gasses and rubber bands. Nernst Postulate
(third law).
Timeline
V. Thermodynamic Formalism (week 8): Postulates of
thermodynamics, Gibbs-Duhem relation, thermodynamic potentials.
VI. Application of Thermodynamic Potentials (week 9): Enthalpy
(Gibbs-Thomson Processes), Gibbs Free Energy (Chemical
Equilibrium)
VII. Phase Equilibra (weeks 10): Vapor-liquid coexistance,
magnetic systems, critical point, order parameter, first and second
order phase transitions.
VIII. Non-equilibrium thermodynamics (week 11): Chemical kinetics,
fluctuations, diffusion
IX Introduction to Statistical Mechanics (week 12).
Why Study Thermodynamics?

Thermodynamics is fundamental to your physics education:
Atheoryisthemoreimpressivethegreaterthesimplicityofits
premises,themoredierentkindsofthingsitrelates,andthe
moreextendeditsareaofapplicability.Thereforethedeep
impressionthatclassicalthermodynamicsmadeuponme.Itis
theonlyphysicaltheoryofuniversalcontentwhichIam
convincedwillneverbeoverthrown,withintheframeworkof
applicabilityofitsbasicconcepts.
-Albert Einstein
Why Study Thermodynamics?

Thermodynamics is THE most generally applied area of physics
Astrophysics (solar/planetary models)
Chemistry (physical/biochemistry)
Earth Science (geology/soil science/atmospheric science/glaciology)
Engineering (chemical/mechanical/electrical)
Life Science (bioenergetics/metabolism/nutrition)
Condensed Matter Physics (soft/hard, biophysics)
Textbook (Required)
Required Textbook: Thermal Physics by CBP Finn (2nd Edition)
Pros: Concise, reasonably clear, focus on essential concepts
Cons: Too concise, not enough examples?
Basic Problem: in my view there does not exist a genuinely
excellent thermodynamics text at this level
Other thermodynamics texts:
Heat and Thermodynamics, M. Zemansky and R. Dittman
(I use this text in lecture preparation: used by P. Grutter last year)
Thermodynamics and an Introduction to Thermostatistics, HB Callen
(a beautiful and inspiring text, but too advanced)
An Introduction to Thermal Physics, D, Schroeder
(too much stat mech for this level, but pedagogically excellent)
Grading Policy
Problem Sets (30%): One problem set will be assigned
about every week. (Three sets per month)
In-class tests (30%): There will be two closed-book inclass tests. You are allowed to bring an index-card size
physics formulary. Your grade will be determined by
highest score (i.e. exam with lowest score will be
dropped)
Final (40%): A closed-book cumulative final (with lettersize physics formulary)
Homework Policy
Full Credit (100%): Turn in sets at the beginning of Friday
lecture
Partial Credit (70%): Turn in sets by 10am Monday (to my
office, under door)
Partial Credit (50%): Turn in sets one week from due date
(office or mail-box)
Problem sets will not be accepted more than a week
from the due-date!
I am open to special circumstances if you email me more
than two days before due-date. . .
Office Hours and TAs

My office hours are: 2-3 MW (I will talk to you at other times if I can)
Class TAs:
Adriel Arsenault
Office hours: wed 3:30-4:30, thurs 11-12,
Office Location: ERP207
Email: adriel.arsenault@mail.mcgill.ca)
Sangwook Ryu
Office hours: wed/thurs 1-2pm
Office Location: ERP314
Email: sangwook.ryu@mail.mcgill.ca
TAs will handle all grading of problem sets (they will alternate sets)
You need to first speak to TAs if you have a question regarding grading
Policy on Group Work

You are encouraged to work together, but
(1) please indicate on your problem set the names
of other students who have contributed to your
solution
(2) make explicit that you have worked/thought
through each step of the problem on your own.
Solutions from Online Research

Use of the group-mind aka Google is inevitable. . .
(although not always pedagogically desirable)
Online sources are fine as background reading
(there are many excellent note series available online, of
course use at your own risk. . .)
Directly copying down solutions from wikipedia or any other
online source is NOT PERMITTED.
If you are caught copying an online solution for your HW,
you will receive zero credit and will be referred to the
Deans office.
Error Treasure Hunt/Contest

I will give between 0.1-1% extra-credit if you find credible
physics mistakes/typos on any class material!
The extra-credit goes to the first person to email me the
corrections (email date will be used to assign priority)
I will give >0.5% only for major typos
Spelling/grammar mistakes will not receive credit
In-Class Problem Tutorials

Many lectures will include mini problem tutorials. . .
(about 5-15 min to solve a problem
followed by discussion of solution)

Lecture 2: Thermal Equilibrium
Time: 2:35-3:25
Place: BURN 1B39
Rutherford 411
Accompanying Reading: Finn p. 1-15
I use WebCT (My Courses)!

Please check WebCT for assignments every Friday
ALL slides available on WebCT
Problem Set I: due Friday Sept 21
The System, Surrounding and Walls

We restrict our investigation to a particular part of the universe: our
system separated from the surrounding environment by boundary walls
Surroundings
System
Surroundings
(e.g. confined volume

of fluid or gas, block of
solid material, etc.)
Walls
Our system can interact in various way with the surrounding environment:
matter and energy can be exchanged, energy in the
form of mechanical work and/or heat
Permitted interactions between system and surroundings
are controlled by the type of system walls present

Different types of walls allow different types of physical exchanges
Open System: walls allow exchange of matter and energy
(system completely open to surroundings)
Surroundings
Matter
Energy
Open
System
Surroundings

Examples of open thermodynamic systems. . .
Liquid in open pot on the stove
Living organisms like yourself. . .
Cities. . .
Economies. . .

Different types of walls allow different types of physical exchanges. . .
Closed system: walls allow exchange of energy but NOT matter
(walls impermeable to particle flow)
Surroundings
Surroundings
Closed
System
Energy
Isolated System: walls prohibit exchange of matter and energy

(system completely isolated from surroundings)
Surroundings
Surroundings
Isolated
System

We can further classify walls that restrict/allow specific types of
energy flows. . .
Movable vs Rigid Walls: Movable walls allow volume exchange with
surroundings; rigid walls prohibit volume exchange.
System
Surroundings
Surroundings
Movable Walls
In practice I can accomplish volume-exchange via the below piston arrangement:
movable piston
Surroundings
System
Surroundings

Question: what kind of energyand how much of it! is exchanged during a
process where the system volume is decreased by V by pushing on the piston
with a constant force F over a distance L? (express answer in terms of V)
movable piston
System
volume decreased by
V=AL
Surroundings
Answer: Mechanical energy is transferred to system from

surroundings by performing a work:
W = F L =
F
A
AL= Pext V
with
Pext
F
=
A
Process that involve volume exchange

transfer energy in the form of mechanical work
Pressure: Units
Pressure: force per unit area
SI Unit of pressure: pascal (Pa)=1 N/m2
Many alternative units for pressure. . .

torr: pressure due to 1 mm column of mercury
bar: 1 bar=105 Pa
atmosphere (atm): pressure due to earths atmosphere
Useful to remember: 1 atm=760 torr=101325 Pa105 Pa=1 bar

Heat transfer: form of energy transfer that does not
involve performing mechanical work!
Diathermal vs Adiabatic Walls: Diathermal walls allow exchange of heat
with surroundings; adiabatic walls prohibit heat exchange.
System
Surroundings
Heat
Examples: Good thermal

conductors (e.g. metals)
Diathermal walls
Examples: good thermal

insulators, e.g. styrofoam,
dewars (double-walled flaks
with evacuated space
between walls)
System
Heat
Adiabatic walls
Surroundings

Examples of closed thermodynamic systems. . .
Helium Ballon
Liquid in sealed flasks
The planet earth
Of course, these systems are open on

long enough time scales. . .

All this fuss over walls may seem a little strange and rather belabored. . .
Walls are actually very important in thermodynamics!
Much of the formalism of thermodynamicsand HW problems you will encounter
will depend in detail on the type of walls present
(e.g. in exactly what ways the system is allowed to interact with its surroundings)
Alert! A common student confusion in thermodynamics is to

confuse the properties of closed and isolated systems. . .
IMPORTANT: Always be aware of whether the system

under consideration is open, closed or isolated
Equilibrium
The concept of equilibrium is foundational to the subject of thermodynamics
An equilibrium state is one in which the bulk physical
properties of the system are uniform throughout the system
and do not change with time (Finn, p. 2)
Key properties of equilibrium states:

Properties of equilibrium states are generally determined by
intrinsic factors
Past external influences are forgotten: equilibrium
states lack memory of their past history
Equilibrium states are characterized by a limited
number of macroscopic parameters
Equilibrium states depend on nature of boundary wall
Equilibrium
Different types of equilibrium states are possible,
depending on what boundary walls are in place
Mechanical Equilibrium: arises between systems
separated by movable walls that allow volume exchange
Thermal Equilibrium: arises between systems
separated by diathermal walls that allow heat exchange
Chemical Equilibrium: arises between systems separated by
permeable walls* allowing particle exchange and after any
chemical reactions are complete
*We will not discuss chemical equilibrium further until much later in the class
PV-Systems
For simplicity, we will restrict ourselves to PV-systems*:
PV System: an isotropic system of constant mass and constant
composition that exerts a uniform pressure on its surroundings
(in the absence of gravitational, electric/magnetic effects)
The mechanical properties of a PV system can be uniquely
characterized by a defined volume and pressure
Examples:
(1) A pure chemical substance in the form of solid, liquid or gas, a mixture of any
two, or a mixture of any three
(2) A homogeneous mixture of different compounds (mixture of inert gases,
liquids or a solution)
*This is my terminology. Zemansky and Dittman call PV-systems hydrostatic systems; their
terminology does not appear to be universal however and I feel that the term hydrostatic is a
little misleading as solid-phase materials are included
The
thermodynamics of PV-systems can be extended without loss of generality to XYsystems with XY generalized thermodynamic coordinates
Mechanical Equilibrium
Two PV-systems are brought into contact via an
impermeable, adiabatic movable wall
System 1
V1,i, P1.i
System 1
V1, P1
System 2
V2, P2
System 2
V2,i, P2,i
System 1
P2,i>P1,i
System 2
V1,f P1,f
V2,f P2,f
movable partition
P2,f=P1,f
volume of system 2 increases. . .
until mechanical equilibrium is reached

(with the system pressures balanced)
P2>P1
Mechanical Equilibrium
If two systems (A and B) are in mechanical equilibrium with each other
System A
System B
PA=PB
and if systems B and C are also in mechanical equilibrium. . .
System B
System C
PB=PC
Then systems A and C will be in mechanical equilibrium!

(e.g. volumes will not
change when they
are connected)
System A
System C
PA=PC
Pressures are equal
Thermal Equilibrium
Let systems A and B be connected by an
adiabatic, rigid wall (e.g. are isolated)
System A
System B
Let systems A and B be connected by a

diathermal rigid wall (allowing heat exchange)
System A
System B
VA=VB; NA=NB; PA=PB
VA=VB; NA=NB; PA=PB
I push piston in:
I push piston in:

Pisto
P n =P
Ppiston=PB
VA>VB; NA=NB; PA<PB
piston
VA>VB; NA=NB; PA<PB
Nothing happens!
Ppiston=PB
System A
pressure will
change!
Ppiston=PB
System A and B have come to thermal equilibrium!
Thermal Equilibrium
If two systems (A and B) are in thermal equilibrium with each other
System A
System B
and if systems B and C are also in thermal equilibrium. . .
System B
System C
Then systems A and C will be in thermal equilibrium!

(e.g. volumes/pressure
will not change when
they are placed in
diathermal contact)
System A
System C
Thermal Equilibrium
The 0th law of Thermodynamics:
If each of two systems is in thermal equilibrium with a third
system, they are in thermal equilibrium with another
When systems are in mechanical equilibrium recall they share
common values of a certain scalar quantity: pressure
(why scalar? equilibrium does not depend on the contact orientation
if it did a tensorial, e.g. matrix, quantity would be needed*)
What scalar quantity is shared by systems in thermal equilibrium?

Answer: Temperature (by definition!)
Temperature is the property that determines whether or not a
given system is in thermal equilibrium with other systems
*a 0th law type property does not exist for equilibrium of elastic crystalline solids for this reason
Isotherms
PV-space: each point represents a possible equilibrium state of the system
P
P
System A
System B
(P1A,V1A)
(P1B,V1B)
V
System A in thermal equilibrium with
system B
V
System A
(P1A,V1A)
System B
(P1B,V1B)
Isotherms
P
P
System A
System B
(P1A,V1A)
(P1B,V1B)
(P2A,V2A)
Remove system A and change its state

New state (PA2,VA2) found that is also in
thermal equilibrium with state (P1B,V1B)
of system B
System A
(P2A,V2A)
System B
(P1B,V1B)
Isotherms
P
P
System A
System B
(P1A,V1A)
(P1B,V1B)
(P2A,V2A)
(P3A,V3A)
V
Remove system A and change state

Third state (PA3,VA3) found that is also in
thermal equilibrium with (P1B,V1B). . .
System A
(P3A,V3A)
System B
(P1B,V1B)
Isotherms
P
P
System A
System B
(P1A,V1A)
(P1B,V1B)
(P2A,V2A)
(P2B,V2B)
(P3A,V3A)
(P3B,V3B)
V
Continuing this procedure, a continuous

set of states can be formed in thermal
equilibrium with (P1B,V1B)
V
The same procedure can be applied
to system B, finding states of B in
thermal equilibrium with (P1A,V1A)
Isotherms
P
TI
TIII
TII
System A
(P1A,V1A)
TI
TII
TIII
System B
(P1B,V1B)
(P2A,V2A)
(P2B,V2B)
(P3A,V3A)
(P3B,V3B)
V
By changing starting conditions, we can generate additional curves
These curves are called isotherms

Each isotherm represents equilibrium states sharing a particular
fixed value of temperature T
Equation of State
The isotherms are characterized mathematically by
some functional relationship linking P, V and T:
f (P,V,T) = 0
This relationship is known as an equation-of-state
Note that there are only two independent parameters:
(P, V),(P, T) or (V, T)
Thermometers
How do we measure temperature?
By measuring a physical property of the system
that varies with temperature!
Temperature dependent physical parameter is called
the thermometric property or variable
Thermometric variable: X
Define temperature: TX=X/c
The quantity c is a numerical constant
Measure X at experimental conditions that lead to a reproducible temperature
value: this is called a fixed-point (e.g. vapor point, freezing point of liquid)
Scale values of X at this fixed point by c to obtain a particular empirical
temperature scale
Fixed Points from Early in History of

Thermometry. . .
Source: Inventing
Temperature by Hasok
Chang. . .
Liquid/vapor/solid phases
coexist at triple point
Water triple point most reproducible,
experimentally accurate fixed point
available (T and P uniquely fixed at
one point)
Well for
thermometer
Water vapor
Pressure
Water Triple-Point as Fixed Point

Solid
Phase
Triple
Point
Liquid
Phase
1am
Gaseous
Phase
(TTP ,PTP )
TriplePoint Cell
Vapor
Ice sheath
Thermal contact
liquid
X
TX = a
X TP
Liquid water
a 273.16
Temperature
(Kelvin-scale)
7 The last international comparison of water triple point cells

The national standards for the water triple point temperature, maintained at 20 National Metrology
Institutes worldwide, were compared in a recent international key comparison of water triple point
cells, coordinated by the International Bureau of Weights and Measures (BIPM, Sevres, Paris).
The results (see fig. 4) showed significant discrepancies between the water triple point temperatures
realized by different countries. For example, it is clear that the triple point temperatures of South
Africa, New Zealand and Canada are hotter than the rest of the countries.

100
50
0
-50
-100
Russia
Turkey
Singapore
Slovakia
Germany
Canada
United Kingdom
Netherlands
Japan
USA
China
New Zealand
Korea
Portugal
Italy
Australia
South Africa
Mexico
Spain
France
-150
BIPM
Temperature difference /microkelvin
150
Water triple-point measurements around the world

(differences due to isotopic composition of water!)
Figure 4: Temperature differences observed between the water triple point realized by different countries during the recent
international comparison coordinated by the International Bureau of Weight and Measures (BIPM), Paris. Uncertainties are K=1.

SMOW: standard mean ocean water
(mixture of ocean water from different points around the globe!)
(from http://www.isotech.co.uk/files/document_library_file-50.pdf)
Thermometer Choices
Mercury Column Thermometer
Fluid expands when heated: X=h
Platinum Wire Thermometer

Wire electrical resistance changes as
function of temperature: X=R
(Pt-wire most accurate)
Thermocouple Thermometer
Voltage difference V develops across
junction of disimilar metals
(small, versatile, imprecise)
X= V
thermocouple
See www.omega.com for best selection!
Gas Thermometer
Gas-filled
capiliary
Pressure
Head
Bulb
sensor
Gas pressure: P=gL
Hg
reservoir
Ideal Gas Thermometer

Steam Point
(pressure of gas in ideal gas
PTP (torr) thermometer at triple-point)
P
TIG = 273.16 lim
N 0 P
TP
(N number of gas molecules in bulb)
Plot from
Finn p. 10

OK, but different choices of thermometric
variables give different temperature values away
from the triple point. . .
Comparison of Thermometer Values
Table from Zemansky/Dittman, Heat and Thermodynamics, p. 16

The ideal gas temperature has more fundamental meaning than
other thermometric variables introduced, but it still depends on the
properties of gases in general
Later in the class we will show that it is possible to introduce an
absolute thermodynamic temperature T. . .
This absolute scale is equivalent to the ideal gas scale
(and is known as the Kelvin scale)
So we will let T=TIG on a provisional basis. . .
Define Celsius scale: t(oC)=T(K)-273.15
tsteam
tice
(oC)=99.97
(oC)=0
From experiment!
(the ~100o difference between the vaporization
and ice points is an empirical fact!)
Temperature
point of water. The International Temperature Scale (ITS) is a temperature scale which is designed to be consistent with thermodynamic
Luminous Intensity
temperatures measured on the basis of this definition. ITS is calibrated by using temperature fixed-points (defining fixed-points), which are
Amount of Substance
obtained when specific substances are in phase equilibrium, and several stable thermometers. The first International Temperature Scale was
R & D of Measurement
Standards
established in 1927. After a series of subsequent extensions of temperature range and precision improvements, the International Temperature
Public Services
Scale of 1990 (ITS-1990) was adopted and is still in use today. Numerical values in the unit of Celsius temperature, symbol C (degree
Topics
Celsius), are produced by those in kelvins minus 273.15.
International Temperature Scale

Events & Publications
About Metrology
Links
Access Maps
Ideal-gas thermometers
Job Opportunities impractical
Inquiry
for routine calibrations/measurement
Pt-resistance thermometers are
calibrated against ideal gas
thermometry at a set of fixedpoints chosen by an international
committee (ITS-90)
Complex schemes are
devised to accurately
interpolate between obtained
Pt-resistance values
Defining fixed points of the International Temperature Scale of 1990 (ITS-90) and interpolating thermometers

Lecture 3: Simple Thermodynamic
Models--Ideal Gas I
Time: T/Th/F 2:35-3:25
Place: BURN 1B39
Office Hours: 2-3 M,W
Rutherford 411
Class Roadmap:
Properties of Simple Model Systems

In the next few lectures we will overview properties of key thermodynamic
model systems:
Ideal gases (today and Monday)
Fluid systems and real gases (Van-der-Walls fluid)
Black body (photon gas)
PV systems of reduced dimensionality (polymers, Langmuir films)
More general two-coordinate systems (paramagnet)
These systems are of importance in their own right and will serve as training
grounds throughout the class for applying the principles of thermodynamics
In addition, these model systems will provide a demonstration of the
general applicability of thermodynamics in a variety of fields
The systems will be presented via a mix of history, experimental background
and simple molecular models (where appropriate)
Review: Equilibrium
The concept of equilibrium is foundational to the subject of thermodynamics
An equilibrium state is one in which the bulk physical
properties of the system are uniform throughout the system
and do not change with time (Finn, p. 2)
Key properties of equilibrium states:

Properties of equilibrium states are generally determined by
intrinsic factors
Past external influences are forgotten: equilibrium
states lack memory of their past history
Equilibrium states are characterized by a limited
number of macroscopic parameters
Equilibrium states depend on nature of boundary wall
Review: Equilibrium
Different types of equilibrium states are possible,
depending on what boundary walls are in place
Mechanical Equilibrium: arises between systems
separated by movable walls that allow volume exchange
Thermal Equilibrium: arises between systems
separated by diathermal walls that allow heat exchange
Chemical Equilibrium: arises between systems separated by
permeable walls* allowing particle exchange and after any
chemical reactions are complete
*We will not discuss chemical equilibrium further until much later in the class
Review: Thermal Equilibrium

If two systems (A and B) are in thermal equilibrium with each other
System A
System B
and if systems B and C are also in thermal equilibrium. . .
System B
System C
Then systems A and C will be in thermal equilibrium!

(e.g. volumes/pressure
will not change when
they are placed in
diathermal contact)
System A
System C
Review: Thermal Equilibrium

The 0th law of Thermodynamics:
If each of two systems is in thermal equilibrium with a third
system, they are in thermal equilibrium with another
When systems are in mechanical equilibrium recall they share
common values of a certain scalar quantity: pressure
What scalar quantity is shared by systems in thermal equilibrium?
Answer: Temperature (by definition!)
Temperature is the property that determines whether or not a

given system is in thermal equilibrium with other systems
Equation-of-State
P
TI
TII
TIII
(P1A,V1A)
PV-space: each point in space represents a

possible equilibrium state
Isotherm : set of equilibrium states sharing a
particular fixed value of temperature T
(P2A,V2A)
Equation-of-State: functional relationship

that links the thermodynamic coordinates
of a system (P,V,T):
(P3A,V3A)
f (P,V,T) = 0
How do we obtain an equation-of-state?

(1) Directly from experiment:
(i) In the form of tables of empirical data .
(ii) or empirical/semiempirical formulas

obtained from curve-fitting to data
(2) From statistical mechanical calculations based on underlying models

for system behavior formulated at molecular level
Equation-of-State: Ideal Gas Law

V ~ 1/ P
Robert Boyle: Anglo-Irish aristocrat,

scientist, theologian
Boyles Law (1663): PV=constant
trapped
air
Hg
column

Jacques Charles:
French inventor, scientist;
developed and flew in the first
manned hydrogen balloon!
First manned hydrogen

balloon (1783)
Charles observed hydrogen-filled balloons expand when heated in proportion

to the temperature rise (1787): V is proportional to T (at constant pressure)

Amedeo Avogadro (1811): V is proportional to n (number of moles of gas)
at constant pressure/temperature
To summarize:
Boyles law:
V 1/ P
Charles law:
V T
Avagadros law:
V n
(constant temperature)
(constant pressure)
(constant pressure/temperature)
PV nT
Constant of proportionality known as the universal gas constant:
R = 8.31441 JK 1 mol1

PV = nRT
Ideal gas law
The ideal gas law is a very good approximation to the
behavior of most gases for sufficiently low pressure/density
Chemists
like to write the ideal gas law
in molar units
Physicists like to use molecule number:

N=n NA (NA=6.0231023)
TI
TII
TIII
TI<TII<TIII
PV = Nk B T
k B = R / N A = 1.3807 10 23
(Boltzmanns constant)
PV/nkBT
Well, how good an approximation is the ideal

gas law really?
PV = Nk B T
Pressure (atm)
Recall lecture 2:
Pressure (atm)
P
P>0 P
TP
TIG 273.16 lim

Point of view of theory. . .classical
microscopic model for ideal gas:
Ideal Gas Model
1. Consider box filled with N particles, N~NA,

each with mass m
2. Particles are so small they can be
considered point-like
3. Particles are in constant random motion
4. Motion is on average isotropic (e.g. no
preferred direction)
5. Particles interact only via elastic collisions
with themselves and the walls (i.e. no longrange interactions present)
statistical
mechanics
PV = Nk B T
Pressure results from net momentum transfer of particles colliding with wall
Ideal Gas: Kinetic Theory I

Consider a single
particle ideal gas
(assume particle travels

at fixed velocity v)
Piston area: A
Volume: V=LA
Average pressure on piston:
2
F
1
1 p 1 2mv x
mv x
2
mv
=
=
=
P=
x =
A A t A (2L /v x ) AL
V
F:
P V = constant
Time-average force on walls
i
f
mv
p : Momentum transfer
p =
per collision
x mv x = 2mv x
i
2L
=
v
t : Time between collisions t = v

x
x
Ideal Gas: Kinetic Theory II

BUT. . .
There is more than one particle in the gas!

Particles travel at different speeds. . .
Particles strike surface over a range of incident
velocity vectors (collision trajectories). . .
dA
Particles striking
patch of area dA
We have (considerably) more work to do:

N(v) dv: number of particles with speed between v and v+dv
f(,) d d: fraction of particles that
strike the surface with a
trajectory in the angular
range to +d and
to +d
=0
Example: =0 (head-on collision)

=/2 (glancing collision)
=/2

The distribution N(v)dv does not change in time
(if it did, the gas could not be in equilibrium!)
How do we deduce f(,)dd ?
Distribution of collision angles must be isotropic by assumption
(there can be no preferred direction)
What does isotropic mean mathematically?
It absolutely does NOT mean that the distribution of
collision angles is independent of and !
Instead, we expect a patches of equal area on the unit
sphere to contain an equal number of collision velocity
orientations.
The different element of area on the unit sphere, d is
known as solid angle
Concept of Solid Angle

z
r=1
Imagine inspecting the
trajectory of each molecule
in a sample of gas. . .
First, normalize each trajectory

(e.g. divide out by speed)
Second, place the resulting unit

vectors at the center of a coordinate The number of unit velocity vectors lying
system: the tips of each vector will in a patch of differential area d will be
proportional to the area of the patch
lie on the unit sphere

z
d(,)
r=1
Fraction of particles that strike

the surface with a trajectory in the
angular range to +d and
to +d:
f (, )dd d(, )
unit sphere = 4
, )
f (, )dd = 41 d(
The number of unit velocity vectors

lying in a patch of differential area d
will be proportional to the area of the
patch

How to calculate element
of solid angle d as a
z function of and ?
Recall spherical coordinates:

Position of vector r=(x,y,z)
designated by r, and
Varying and by d and
d sweeps out area d
r=1
( fig just shows d variation)
Need to calculate area d at

vector position r, and .

Total solid angle, i.e.
integrated over the entire
unit sphere, is just 4:
2
Introduce local coordinate

system at vector position:
dx
d(, )dd = 4
0 0
dx
z
dx = rd
dx = r sin d
(r = 1)
= dx dx = d (sin d )
Element of solid angle d: d
= sin dd
d(, ) = sin dd

Question #2: what fraction of particles with a given speed and collision
trajectory in a certain solid angle range actually strike the surface?
Consider a group of such particles approaching the surface in time dt
(dt is such a short time no collisions can be made)
The particles will fill a tilted cylinder
impinging on the surface
The cylinder will have a volume:
dV = (vdt) (dA cos )

Total fraction of such particles
hitting surface in time dt:
dV v cos
=
dtdA
V
V
dA

Question #3: what is the momentum transfer per collision?
v cos
-v cos
dA
p = mv cos (mv cos ) = 2mv cos

We are now ready to complete the calculation. . .
Total change of momentum over time dt

due to particles with speed between v and
v+dv striking surface with collision angle
between to +d and to +d
Fraction of particles with speed between v

and v+dv in the solid angle d(, )
Fraction of these particles striking a
surface dA in time dt
(Change in momentum per collision)

We are now ready to complete the calculation. . .
Total change of momentum over time dt

due to particles with speed between v and
v+dv striking surface with collision angle
between to +d and to +d
Number of particles
1 with speed between v
and v+dv in the 4
solid
angle d(, )
N (v) dv
d(, )
= sin dd
v cosparticles
Fraction of these
striking a
dtdA
surface dA in time dt
(Change in
momentum per collision)
2mv
cos
1
2
1 sin cos 2 d d dA dt dv
= mv N (v) 2
V

From previous slide, the change in momentum due to all colliding particles in dt
(with particular speed and collision trajectory):
dp = 1 mv 2 N (v) 21 sin cos 2 d d dA dt dv

V
1 dp
dP =
dA dt
(the contribution to the pressure arising from

speed and solid angle range)
collisions in a specific
1
= mv 2 N (v) 1 sin cos 2 d d dv
2
V
One final step: integration over all speeds and

collision trajectories!

2 / 2
(total pressure from collisions occurring over

all speeds and solid angle)
P = dP
0
m
=
V
1
2
v N (v)dv
2
m
=
3V
mN
=
3V
d d sin
0
N (v)dv mN
v N = 3V
0
Probability particle has speed
cos 2
= 1/ 3
N: total number
of particles
/2
v N (v)dv
0
between v and v+dv
2
v
P(v)dv
0

OK: almost finished!
P=
:
mN
3V
mN 2
v P(v)dv = 3V v
0
2
Denotes average over velocity distribution
v 2 v 2 P(v)dv
Average energy of gas: U = KE = N Particle KE
PV
=
= N 1 m v2
2
2
U
3
OK,
but how to calculate U ?
(the average energy of the gas)

Answer: we cant directly calculate
PV =
(Until we know statistical mechanics!)
BUT. . .
2
U
3
If we assume the ideal gas law, deduced from experiment, is correct:
PV = Nk B T
U =
3
Nk B T
2
=3N
1
2
k BT
This is just the equipartition theorem

(three translational
degrees of freedom per particle)
Kinetic theory tells us that the

temperature is basically a measure of average KE

Lecture 4: Ideal Gas II

Time: T/Th/F 2:35-3:25
Place: BURN 1B39
Rutherford 411

PV = nRT
Ideal gas law
Chemists
in molar units

N=n NA (NA=6.0231023)
TI
TII
TIII
TI<TII<TIII
PV = Nk B T
k B = R / N A = 1.3807 10 23
Ideal Gas Law: Example Problem

A hot air balloon, approximately spherical in shape, floats in a state of neutral
buoyancy (i.e. not moving up nor down) when the supported weight is Fb=3000N
and the density of the surrounding air is =1.2kgm-3. Assume the gas within the
balloon is at Tb=40oC having the same pressure and composition of the
surrounding air. The temperature of the surrounding air is Ta=20oC.
What is the diameter of the balloon?
P N /V b
Ta
Ta
N
=
b =
=
PV = Nk B T
k BT
Tb
Tb
V
Neutral Bouyancy: Fb + b Vb g ="Displaced weight" = Vb g
Ta 4 3
Fb = ( - b ) Vb g = 1 - r g

Tb 3
1/ 3
1/ 3
3000N
Fb
d = 2
= 2
= 19.7 m
3
2
293
4
T
4
)(1 313 )( 3 )
(1.2kgm )(9.81ms
g(1
T)( 3 )
a
b

Point of view of theory. . . classical
Ideal Gas Model

each with mass m
. vi

6. Walls are smooth: particles are
specularly reflected upon collision
(e.g. vi=-vf with designating particle velocity
component perpendicular to the wall)
vi
vf
Pressure results from net momentum

transfer of many particles colliding
with wall
Review Kinetic Theory

Key result from kinetic theory
(derived last lecture):
PV =
2
U
3
If we assume the ideal gas law, deduced from experiment, is correct:
PV = Nk B T
U =
3
Nk B T
2
=3N
1
2
k BT
This is just the equipartition

theorem
(three translational degrees of freedom per particle)
Kinetic theory tells us that the temperature

is basically a measure of average KE
Ideal Gas: Velocity Distribution

Particles in gas have a fixed speed distribution
P(v)dv: Probability particle has speed between v and v+dv
(Note: P(v) probability density: probability per unit velocity interval)
What is a speed `probability distribution? Imagine if you could

measure the instantaneous velocity of individual gas particles.
If you made many such measurements, and histogramed the
resulting speed values, you would obtain a particular estimate of P(v)
Ncounts
P(v)dv
N counts (v)
N total counts
bin size : v

Probability distributions have some important general properties
First consider a discrete distribution Pi for measuring x-values xi

Probability of measuring xi:
Ni
Pi =
N tot
Examples of discrete distributions:

Coin flipping:
Is it heads (P1=1/2)
or
tails (P2=1/2)?
Grade Distribution
What is the probability of getting an A,
A-, a B+, B, B- a C in this class?
Total number of times particular

value xi returned
Total number of
measurements

The probabilities of all outcomes

must sum to 1:
Pi = 1
i=1
probability
distribution is
normalized
The average of x over the distribution is defined:
Ni =
Pi xi
= xi
i=1 N
i=1

For continuous distribution replace sums by integrals:

must sum to 1:
P(x) dx = 1
The average of x over P(x) is defined:
In general . . .
f (x) =
x2 =
f (x) P(x) dx
x P(x) dx
The average of x2 over P(x) is defined:
x =
2
x
P(x) dx

It is possible to deduce the form of P(v) on very general grounds
First consider the particle velocity distribution
Particle velocity vector
v = (v x ,v y ,v z )
Pvel (v)
with speed:
v = v 2x + v 2y + v 2z
The velocity distribution is a function of all three velocity components
Pvel (v) dv x dvy dvz :

(probability per unit velocity3)
vz
Pvel(v) lives
in 3D space!
Probability particle has velocity vector with vx

between vx and vx+dvx, vy between vy and vy+dvy
and vz between vz and vz+dvz
vy
dvz
dv x
dvy
vx
Probability of finding velocity vector lying in

differential cubic volume at position v

The probability of measuring any given values
vx, vy and vz should be independent:
Pvel (v) = P(v x )P(v y ) P(v z )
The velocity distribution must be isotropic:
P vel (v) Pvel (v)
= v2
guess
( v 2x + v 2y
The Gaussian distribution satisfies
B
+ v 2z )
Pvel (v) = A e 2
these two requirements:
2
vz
= Ae e
vy
Bv x Bv y Bv 2z
vx
all velocity vectors v lying on

sphere of radius v are of equal
probability
= Ae
Bv 2
(calculate from
normalization
requirement)
P(vx, vy)
vy
vx
(Probability distribution for velocity components in 2D gas)

One final step: how do we convert our velocity
distribution into a distribution over particle speeds?
Fixed speed v corresponds to a range of different vector orientations
These velocity vectors lie in a spherical shell of
radius v and differential thickness dv
vz
Probability of measuring particle with speed v:

v
P(v)dv= (volume of shell at speed v) x
vx
dv
vy
(probability particle has velocity

consistent with speed v)
= 4 v 2 dv Pvel ( v = v)
= A e
Bv 2 2
v dv

The fixed speed distribution then has the form:
2
P(v) = A v e
A :
Bv 2
obtain from normalization
B: obtain
from equipartition
3 ( 12 k B T)
=average particle KE
P(v) is known as the Maxwell-Boltzmann speed distribution
(You will calculate A and B for HW!)

P(v)
Maxwell-Boltzmann and
Nanofabrication
How many of you might want
to work in McGills Nanotools
cleanroom facility some day?
Or does a sad and

desperate future as
theorists await you
all. . )-: ?
Maxwell-Boltzmann and
Nanofabrication
OK: what do they have to do with each other?
Concepts from kinetic theory is critical to
understanding a wide-range of fabrication
technology. . .
Example: evaporative coating
Evaporation
Belljar
Vacuum
Chamber
(belljar)
Wafers
Material
Crucible
Ventgas
Coldtrap
diusionpump
RealworldEvaporator
Metalisheated,evaporatesandcoats
sample
TypicalEvaporatorDesign
Lowpressure(~2x106torr)essenNalto
preventredeposiNonofcontaminaNng
airmoleculesonsamples
Evaporation: Thermal vs Ebeam

Electron
Beam
Filament
Filamenttypes
Accelera.ng
Grid
Deec.on
Plates
Heatedlament
ResisNve(thermal)
Thermal: Resistive heating of filament
No radiation, but source contamination
Electron-beam: Heating via focused ebeam
(3-20kev). Low source contamination, high
deposition rates, but X-rays generated
ElectronBeam
Bending
Magnet
Kinetic Theory: Impingement Rate

Q: What is the net flux of particles impinging on a surface?
Jx
Net molecule flux through unit area
per unit time. . . or . . .number of
molecules striking surface of unit area
per unit time (from one side!)
Total number of particles dNv with velocity in range vx to vx+dvx that

will strike surface in time dt:
vxdt
dN v=
dA
(number of particles per

unit volume with velocity
in the range vx to vx+dvx)
(Volume of cylinder of length vxdt and

area dA)

Jx

vxdt
dN v=
dA
1
N P(v x )dv x
V
(Volume of cylinder of length vxdt and

area dA)

Jx

vxdt
dN v=
dA
(v x dt) dA
1
N P(v x )dv x
V
dN v N
= v x P(v x )dv x
dtdA V
(number density)
=c

Jx

Total rate of particle impingement per unit area of surface:

(i.e. due to particles in all velocity ranges)
R=
cv
P(v x )dv x
=c
v x P(v x )dv x

Problem: Calculate the net impingnement rate R in terms of the
gas pressure!
R = c v x P(v x )dv x
0
N
c =
P(v x ) =
m
B=
2k B T
(you will show

this for HW)
xe
Bx 2
Bv x
1
dx =
2B

Problem: Calculate the net impingnement rate R in terms of the
gas pressure!
R =c
v x P(v x )dv x
B
=c
v e
Bv x
Ideal gas law:
1
=
2
dv x
c 2 k BT =
m
P
c=
k BT
B 1 =c 1
=c
2B
2 B
R = c v x P(v x )dv x
P(v
x) =
P2
2 m k B T
B=
2k B T
xe
N
c =
V
Bv x
(you will show

this for HW)
Bx 2
1
dx =
2B
Kinetic Theory: Mean Free Path

Q: What is the mean distance between particle-particle collisions?
(mean free path)
Effective collision area swept

out by moving particle:
A = d
Collisions can occur when centers of target particles are within a

circle of radius d from the incoming particle
n
Mean-free path
=
=
Mean distance traveled by particle per collision

Distance traveled by particle
Number of collisions in traversed volume
= 1/ 2
v
vt
1
1
= 2
=
= 2
2 d 2 c
d vrel tc d c vrel
1 k BT
Number of collisions
=
In target volume
2 d 2 P

Distance traveled
Ideal gas
law:
c=
P
k BT
Kinetic Theory Numbers

Mean-free path:
1
1 k BT
=
=
2
2
2 d c
2 d P
Impingement Rate:
Presssure
(Torr)
P2
R=
2 k B Tm
20
5x103 airat25oC
~
P(torr) (incm)
~ 3.5x10 P(torr)
airat25oC
(inparNcles/cm2s)
Pressure
(bar)
Number
impingement
rate(s1cm2)
Monolayer
MeanFree
Impingement Path(cm)
(s1)
104
107
1016
10
50
105
108
1015
500
106
109
1014
0.1
5x103
107
1010
1013
0.01
5x104
Atoms per monolayer:~1015
Evaporation: Step Coverage
Mean free path larger than source-to-sample distance:

Evaporation extremely directional process.
Geometric shadowing and poor step coverage
Evaporation: Lift-off
Poorstep
coverage
anadvantage
forliHo!
spincoatresist
pa^ernresist
evaporatemetal
removeresist
(acetone)

Lecture 5: Real Gases and Fluids
Time: T/Th/F 2:35-3:25
Place: BURN 1B39
Rutherford 411

PV = nRT
Ideal gas law
Chemists
in molar units

N=n NA (NA=6.0231023)
TI
TII
TIII
TI<TII<TIII
PV = Nk B T
k B = R / N A = 1.3807 10 23

Remember (unlike your prof!) to use
Kelvin units when using the ideal gas law
PV\NkBT
How good an approximation is the ideal gas

law really?
PV = Nk B T
Pressure (atm)
Recall lecture 2:
Pressure (atm)
P
P>0 P
TP
TIG 273.16 lim
Equation-of-State: Fluids
Real substances exist in multiple phases (e.g. gas, liquid solid)
Consider fixed amount (n moles) of fluid in a container of volume V
PV diagram for H20
Showing fluid phase
transition (gas to liquid)
Pressure rises rapidly

as compression
continues
saturated
liquid
A
vapor
phase
liquid/vapor phases in
equilibrium at fixed
pressure and temperature
(coexistance line)
vapor
liquid
Isothermal compression
B
liquid condensation
progresses
saturated
vapor
(figure from Zemansky and Dittman, Heat and Thermodynamics, 7th Ed)
Question: at particular position along coexistance line how much
of substance is in vapor versus liquid phase?
x: fraction of substance in
vapor phase (x=Nv/N)
Vx: total system volume when
vapor phase is at fraction x
VB: system volume at point B
(system saturated vapor)
VC: system volume at point C
(system saturated liquid)
Density of liquid and vapor
phases remain constant along a
given coexistance curve:
(and equal to their respective saturated values)
N
cL =
;
VC
N
cV =
VB
Vc
Vx
VB
Comment on Density
In thermodynamics, two quantities related to density:
N
c=V
N
m
V
molecular mass
(Number density: molecules/unit volume)
(Mass density: mass per unit volume)
x: fraction of substance in vapor phase.
VC: volume of liquid phase at point C
VB: volume of vapor phase at point B
Vx: total system volume when vapor
phase is at fraction x
Densities of liquid and vapor phases
remain constant along a given
coexistance curve:
cL =
N
;
VC
cV =
1
1
+(1 x)N
Vx = xN
cL
c

V
Number of molecules in
Number of molecules in
vapor phase
liquid phase
= xVB +(1 x)VC
x=
N
VB
Vx VC
VB VC
x
C
B
Vc
Vx
VB
Vapor-Liquid Density Near

Critical Point
Density (kg/m3)
No distinction between liquid and

gas phase above critical point!
Saturated
liquid density
Critical
point
saturated
vapor density
Temperature (K)
Density curves for liquid/vapor
phase H2O near critical point
Consider fixed amount (n moles) of fluid in a container of volume V: we
adjust n so that density is equal to the density at the critical point
gas
vapor
liquid
vapor
vapor
meniscus disappears!
Above critical point no
distinction between
liquid and gas phase!
liquid
vapor
liquid
Heat substance at liquid-vapor coexistance

By taking system above critical point you can continuously transition from
vapor to liquid phase!
compress
gas
cool
liquid
heat
vapor
Equation-of-State: PT Diagram
PT Diagram for H20
No coexistence
regions on a PT
surface: these
collapse to a line
(Note slope negative: very

special property of water)
Ice-skating!
Liquid/vapor
coexistance occurs at
fixed pressure and
temperature of liquid/
vapor phases
boiling
1atm
(Increased pressure
liquefies ice under skate,
creating lubricating layer)
(e.g. phases are

in thermal and
mechanical
equilibrium during
coexistance)
T
Super-Critical Fluids and All-Natural

Skin Care Products
Are any of you consumers of all-natural bath/body products?
100% Canadian-grown Sea Buckthorn

(from Mount Echo Naturals, Quebec based natural product company)
Mount Echo tells me that sea Buckthorn oil has key medicinal/nutritional uses and
makes great skin-care products
Well, we cant extract buckthorn oils with nasty organic solvents can
we? That would sort of defeat the point. Methods that require heating
may damage the oils. . .
Super-Critical Fluid Technology

Supercritical CO2 to the rescue!
Supercritical CO2 will expand to fill
container but has a density
comparable to a liquid: makes a very
effective solvent!
Pump CO2 at P>Pc with T>TC
through buckthorn; CO2 will extract
key oils from plant material
Lower pressure and CO2 will
vaporize leaving behind oil extract
Environmentally friendly/no
hazardous biproduct/emissions
PT Diagram for CO2:

TC=31.1oC; Pc=72.9 atm
Equation-of-State: Full PVT Surface
f (P,V,T) = 0
P = g(T,V
)
V
(figure from Finn p. 166)
Equation-of-State:
Substance expands upon
Freezing (e.g. H2O)
(negative
slope)
(figure from C. Borgnakke, R.

Sonntag, Fundamentals of
thermodynamics, 7th Ed)
Equation-of-State:
Substance contracts upon
Freezing
(most other substances)
(positive
slope)

Review: Ideal Gas Model

Point of view of theory. . .classical
Ideal Gas Model

each with mass m
We need to relax this

assumption for a real
substance!
Pressure results from net momentum transfer of particles colliding with wall
Model for Real Gas

Real gases have long range intermolecular interactions
(attractive/repulsive)
Molecules have finite size. . .
Modify ideal-gas law as follows (Van der Waals 1873):
V Veff = V Nb
=Volume per particle
P Pideal +Peff
Nk B T
+Peff
=
Veff
effective reduction/increase of
pressure due to
intermolecular interactions
Equation-of-State: Real Gas

Modify ideal-gas law as follows:
V Veff = V Nb
P Pideal + Peff =
How to calculate Peff?
Nk B T
+ Peff
Veff
Find potential energy associated with interaction of one particle with neighbors:
Interaction probability for single particle pair:
Pint =
interaction volume per pair

total volume
Interaction energy:
V
= int
V
Vint
(>0: assume interactions attractive)
Total interaction energy for one particle:
N
=
P
N
U 1 int = Vint
V
Total interaction energy for all particles:
U N = N U 1 = Vint
N2
V
Equation-of-State: Real Gas

Modify ideal-gas law as follows:
V Veff = V Nb
P Pideal + Peff = Nk B T + Peff

Veff
How to calculate Peff?
Finally, find pressure associated with total interaction energy:
Total interaction energy for

N particles (from previous slide):
U N = Vint
N2
V
Pressure associated with total interaction energy:
Peff
2
dU N
N2
N
=
= Vint 2 a 2
dV
V
V
a
Van-der-walls
Equation of State:
Substance cannot be
compressed below a
volume V=Nb!
Nk B T
N2
P = V Nb a 2
V
Van der Walls Equation-of-State

2
Nk B T
N
P=
a 2
V Nb
V
Example of a semi-empirical equation of state:

Obtain parameters a and b from comparison to experimental data
Define the number density or particle concentration:
N
c
V
c
ac 2 ck B T (when concentration is low)
P = k BT
1 bc
Eq of state for ideal gas

Pressure
What do isotherms
of VdW Eq. of state
look like?
Toy model for
system with phase
transition!
T1<T2<T3<T4<T5<T6
T6
T5
gas
T4: critical isotherm

T3
liquid
vapor
T2
T1
coexistence region
Volume
Internal Energy Van der Walls Fluid

Recall that for an ideal gas (monotonic) the internal energy is:
U ideal =
3
2
Nk B T
(equipartition)
What is the internal energy of a VdW Fluid?

Recall that interaction energy between the gas particles is:
N2
int = Vint
V
a
2
N
U VdW = U ideal +U int = 32 Nk B T a
V
2
N
U VdW = 32 Nk B T a
V

Lecture 6

Time: 2:35-3:25
Place: BURN 1B39
Office Hours: MW, 2-3
Outline
I. Concept of Probability Distribution
II. Review of Maxwell-Boltzmann statistics for
speed distribution of particles in an Ideal Gas
III. Equation of State for Radiation in Thermal
Equilibrium (Photon-Gas)
Discrete Probability Distribution

First consider a discrete distribution Pi for measuring x-values xi
Probability of measuring xi:
Ni
Pi =
N tot
Examples of discrete distributions:

Coin flipping:
Is it heads (P1=1/2) or
tails (P2=1/2)?
Grade Distribution
What is the probability of getting an A,
A-, a B+, B, B- a C in this class?
Total number of times particular

value xi returned
Total number of
measurements


must sum to 1:
Pi = 1
i=1
probability
distribution is
normalized
The average of x over the distribution is defined:
x =
P
1
xi N i =
i
N i=1
i=1
xi

Example: Age Distribution
Imagine a room filled with

people. . .
Ages of people in the room:

One person aged 14: N(14)=1
One person aged 15: N(15)=1
histogram
Three people aged 16: N(16)=3

Two people aged 22: N(22)=2
Two people aged 24: N(24)=2
Five people aged 25: N(25)=5
What is the probability, if I select an individual

at random, that their age will be 14?
Answer: P(14)=1/14
(There are 14 possible choices, each equally likely, and only one person is aged 14)

Example: Age Distribution
Imagine a room filled with

people. . .
Most probable value
Average
value
Histogram of peoples ages in a room

What is the most probable age? Answer: 25
What is the average age? Average Age: 14+ 15+ 3(16)+ 2(22)+ 2(24)+ 5(25)
14
The average and most probable value are not necessarily the same!
=21
Continuous Probability Distribution

Continuously defined variables can also have probability distributions. . .
the probability someone is aged exactly 14 years, 3 months, 5 days, 3
hours, 24 min, 16 seconds. . .
the probability that your romantic interest will be standing at a
particular position in a room. . .
the probability that you will have to wait a certain time t for the
metro to arrive. . .

Continuously defined variables can also have probability distributions. . .
What is the probability I wait a

time t, if the trains arrive every
t min?
Waiting time distribution is uniform:
PMetro (t) = constant
Answer:
dt
PMetro (t)dt =
PMetro (t)
1=
How
do I determine ?
PMetro (t)dt
0
= dt = t
0
= 1/t

Continuous probability distributions are probability densities. . .
They give a probability per unit interval. . .
I multiply by some small interval dx to give the probability of
making a measurement in a certain differential range
P(x)dx: Probability quantity has value x between x and x+dx

The probability of making a measurement in a finite range is an integral:
x2
P(x) dx
x1
= probability of measuring x between x1 and x2

Properties of continuous probability distributions
must sum to 1:
P(x) dx = 1
The average of x over P(x) is defined:
2
x
P(x) dx
f (x) P(x) dx
x P(x) dx
f (x) =
x =
The average of x2 over P(x) is defined:

In general . . .
Ideal Gas: Speed Distribution

Particles in gas at thermal equilibrium have a
fixed (time-independent) speed distribution
The speed distribution is an example of a
continuous probability distribution!
P(v)dv: Probability particle has speed between v and v+dv
(P(v): probability per unit velocity interval)
N: total number of particles

NP(v)dv:
Number of particles (on average) with speed

between v and v+dv

What is a speed `probability distribution? Imagine if you could
measure the instantaneous speed of individual gas particles.
If you made many such measurements, and histogramed the
resulting speed values, you would obtain a particular estimate of P(v)
Ncounts
P(v)dv
N total counts
bin size : v
N counts (v)
Animations from http://www.chm.davidson.edu/vce/kineticmoleculartheory/Maxwell.html

How to calculate P(v)?
First deduce the form of the velocity distribution!

Pvel (v) :
The particle velocity distribution
Particle velocity vector
v = (v x ,v y ,v z )
v = v 2x + v 2y + v 2z
The velocity distribution is a function of all three velocity components
Pvel (v x ,v
y ,v z ) dv x dv y dv z :
(probability per unit velocity3)
with speed:
vz
Pvel(v) lives
space!
dvz
in 3D
vy
dv x
dvy
vx
Probability particle has velocity vector with
x-component
between vx and vx+dvx, ycomponent between vy and vy+dvy and zcomponent between vz and vz+dvz
Gives probability of finding velocity vector lying

in differential cubic volume at position v

The probability of measuring any given values
vx, vy and vz should be independent:
The velocity distribution must be isotropic:
The Gaussian distribution satisfies

these two requirements:
vz
v
vy
vx
P vel (v) Pvel (v)

( Px = Py = Pz )
= v 2
Pvel (v) = Px (v x )Py (v y )Pz (v z )
guess
B ( v 2x + v 2y + v 2z )
e
Pvel (v)
= A Bv
Bv Bv
Bv
= Ae
e e
=
Ae
2
x
all velocity vectors v of equal

magnitude are of equal
probability
2
y
2
z
(calculate from
normalization
requirement)

v x = vy = 0
P(vx, vy)
vy
vx
(Probability distribution for velocity components in 2D gas)

One final step: how do we convert our velocity
distribution into a distribution over particle speeds?
Fixed speed v corresponds to a range of different vector orientations
These velocity vectors lie in a spherical shell of
radius v and differential thickness dv
vz
Probability of measuring particle with speed v:

v
P(v)dv= (volume of shell at speed v) x
vx
dv
vy
(probability particle has velocity

consistent with speed v)
= 4 v 2 dv Pvel ( v = v)
= A e
Bv 2 2
v dv

The fixed speed distribution then has the form:
2
P(v) = A v e
A :
Bv 2
obtain from normalization
B: obtain
from equipartition
3 ( 12 k B T)
=average particle KE
= K
P(v) is known as the Maxwell-Boltzmann speed distribution
(You will calculate A and B for HW!)

most probable
speed
P(v)
average speed v
root-mean
square speed
v
2
P(v) = A v e
Bv 2
v2
Thermodynamics of Radiation?
You may be under the impression that thermodynamics is only
concerned with everyday systems like gases and liquids
We can describe radiation in thermodynamic terms!
or
Photons in a box!
Electromagnetic standing waves

(like modes of a violin string)
Remarkably, we can consider radiation in thermal equilibrium with its

surroundings as a PVT system satisfying an equation-of-state!
Thermodynamics of Radiation
Fact 1: Photons all travel at the speed of light, c!
Fact 2: Photons have a certain frequency distribution
n(,T)d : Average number of photons per unit volume with

frequency in the range to +d at temperature T
(technical comment: photons are NOT conserved, there

is no such thing at the total number of photons N)
p = h/
Fact 3: Photons have a momentum:
(h: Plancks constant)
Fact 4: Photons have an energy:
E = h
(c = )
(you will learn this content formally in a class on quantum mechanics,

but it is ALL you need to know for the HW!)
Thermodynamics of Radiation
Spectral energy density of photon gas: u(,T)d
(Energy density per unit volume in a differential range of frequency)
Average number of photons with

frequency in the range to +d:
u(,T)d = h n(,T)d
Energy of photon
with
frequency
Total energy of photon gas:
U=V
u(,T)d
0
Integral over all frequencies!
How to Measure Energy Density of Radiation in

Thermal Equilibrium?
Metal surface
Radiation entering hole will be

trapped and thermalized in cavity
Hole emits thermalized radiation
Experimental realization:
metal cavity with entrapped EM radiation
Walls at temperature T will radiate energy into the cavity
How to Measure Energy Density of Radiation in

Thermal Equilibrium?
We can relate theoretically the energy emitted by the cavity
to the energy density inside the cavity
energy density
( ,T)
u(T,T)
T
(energy per unit

volume)
How to do this?
Energy emitted:
(units of energy per unit area, per unit

time, per unit frequency interval)
Use similar arguments to what we used to model
classical particles impinging on a surface!
Thermalized Radiation: Internal Energy

Imagine photons escaping through a hole of area dA
First find dNescape:
Average number of photons, of frequency ,
arriving at surface in solid angle range
d(,), escaping through area dA in time dt
dNescape= Number of photons in tilted cylinder =

(Average number of photons per
unit volume with frequency in the
range to +d, arriving at surface
in solid angle range d(,)
dA
X
(Volume of tilted cylinder)
Energy leaving cavity

through area dA in time dt =
h X dNescape
Thermalized Radiation: Internal Energy

Imagine photons escaping through a hole of area dA
We want to find dNescape:
Average number of photons, of frequency ,
arriving at surface in solid angle range
d(,), escaping through area dA in time dt
dNescape= Number of photons in tilted cylinder

1
d(, )
4
= sin dd
= n( ,T)d
X (dA
cos ) (cdt)
dN escape
= c n( ,T)d
dtdA
Energy
Emitted
(
,T)d
= u( ,T)
= h
dN escape
dtdA
Energy of a photon of
frequency
dA
1
cos sin dd
4
= h n( ,T)d
1
4
/2
d cos sin =
d
0
= 2
= 1/2
c
u( ,T) d
4
Stefan-Boltzmann Law (1879)

Total Power per unit area radiated by cavity:
P = SB T
SB: Stefan-Boltzmann constant (5.67x10-8 W m-2K-4)
(determined experimentally in late 1870s)
(J\m2)
Spectrum of Thermalized Radiation
Planck Distribution Law

(,T ) = A
Empirical guess!
a T
(parameters A and a obtained from fitting to experimental data)
Total power radiated:
P=
(,T )d ~ T 4
(You will derive this law

on fundamental
grounds
in later classes on
mechanics, we wont discuss it further)

quantum mechanics/statistical
Thermal Radiation Internal Energy

Spectral energy density of thermalized
radiation:
u( ,T) =
(previous slide)
U(T,V ) = V u( ,T)d
4V
=
c
Ideal Gas:
4
4
T
=
V
( ,T)d c SB
3
2
U = Nk B T
N
3
VdW Fluid: U = 2 Nk B T a
V
Thermal Radiation: U = AVT
4
c ( ,T)
Thermal Radiation Eq. of State

You will show (for HW)!
PV
4
A
1
= 3 U= 3 VT
(important in astrophysics, for example photon pressure tends to

destabilize massive stars)

Lecture 7: Simple Models V
Time: T/Th/F 2:35-3:25
Place: BURN 1B39
Rutherford 411
Finn: p. 19-22
Finn: Appendix B (p. 210-211)
Equation-of-State
P
TI
TII
TIII
(P1A,V1A)
PV-space: each point in space represents a

possible equilibrium state
Isotherm : set of equilibrium states sharing a
particular fixed value of temperature T
(P2A,V2A)
Equation-of-State: functional relationship

that links the thermodynamic coordinates
of a system (P,V,T):
(P3A,V3A)
f (P,V,T) = 0
How do we obtain an equation-of-state?

(1) Directly from experiment:
(i) In the form of tables of empirical data .
(ii) or empirical/semiempirical formulas

obtained from curve-fitting to data
(2) From statistical mechanical calculations based on underlying models

for system behavior formulated at molecular level
Overview: Simple Model Systems

Ideal Gas:
VdW Fluid:
PV = Nk B T
N2
Nk B T
P=
a 2
V Nb
V
Thermal Radiation:
U=
P=
A 4
T
3
3
2
Nk B T
2
N
= 32 Nk B T a
V
U = AVT 4
(Equation of state treasure hunt. . .)

A few more examples in this lecture!
PV diagram for H20
Showing fluid phase

as compression
continues
saturated
liquid
A
vapor
phase
(coexistance line)
vapor
liquid
B
liquid condensation
progresses
saturated
vapor
gas
vapor
liquid
vapor
vapor
distinction between
liquid
vapor
liquid

Equation-of-State Continued. . .
We can also consider systems of reduced dimensionality (2D, 1D)
Imagine life in molecular flatland: a liquid surface!
Molecules at
interface have a
higher energy than
those in bulk
(experience fewer
attractive
interactions)
Surface tension : energy per

unit area associated with creating
an interface between two phases
L (fixed)
Energy cost to increase surface area:
x (variable)
interfacial
por
area
dx
dU = Ldx
Resulting in a tension (force per unit length)
tending to contract surface:
dU
= L
dx
/ L =
Equation-of-State in 2D: Langmuir Films

Deposit amphiphilic molecules on a water interface:
Hydrocarbon tail
(hydrophobic)
Polar or
charged
head group
(hydrophillic)
Air
Water
Think of molecular monolayer as

a 2D thermodynamic system!
Amphiphiles will spread on water

interface forming a monolayer
Equation-of-State in 2D: Langmuir Films

adjustible
barrier
amphipilic
monolayer
water
Use floating barrier to
compress monolayer
A 2D piston for 2D
thermodynamic system!
Measure surface
pressure as a
function of film area A!
= water film
Equation-of-State in 2D
Measure surface pressure as a function of monolayer area at
constant temperature
Surface pressure
Obtain isotherms for 2D system!
solid
liquid
gas
Area per molecule (nm2)
In gas regime monolayer obeys effective 2D ideal gas law!
A = nRT
Equation-of-State in 1D?
Why not? This is just polymer thermodynamics!
A polymer is a long chain made of repetitive chemical units
We can the model the polymer as series of beads connected by flexible hinges
r
For small stretching, we find that polymers obey an equation of state
r
= ak B T
L
r:
:
polymer extension
L:
tension
(e.g. length of polymer string

measured end-to-end)
polymer contour length
Equation-of-State in 1D?
Think of a polymer system as a molecular-rubber band!
r
= ak B T
L
Rubber band composed of chemically
cross-linked polymer chains. Chains
stretched out when rubber expands

cross-links
polymer coils
Equation-of-State for DNA!

8760 Marko and Siggia
high force
Al
rando
10dista
c
T
mono
low force
e
in m
c?
Inset: agreement to high pape

!
force regime scaling
per le
/
L
f
(the
C
- 3
,
the c
(optically
with
1= 0.5r
trapped
is va
J
bead)
/
Kratk
DNA
For t
Sin
P
WLC
30
it is
25 extension z ( p )
35 I
(whe
shou
10-~
10-2
lo-'
loo
10'
altho
force (k
f (kT/nm)
Force
BT/nm)
can c
Figure 2. Fit of numerical exact solution of WLC forceJ. Marko
& E.
Macromolecules
8759
(1995) this p
extension
curve
to Siggia
experimental
data of Smith28,
et a1.l
(97004
Lik
bp DNA,10 mM Na+). The best parameters for a global leastsquares fit are L = 32.8 pm and A = 53 nm. The FJC result
DNA
for b = 2A = 100 nm (dashed curve) approximates the data
(2R02
r
1
1
Ak B T
L 4(1 r / L) 2 4
DNA extension (r/L)
LU
Example Thermodynamic Systems

OK: that is the end of our tour of model systems!
What was the point of this?
(1) That I can describe many different physical systems quite generally in
terms of a relation between temperature and macroscopic thermodynamic
coordinates
(2) To give a taste of the microscopic details for certain important systems, e.g.
ideal gas, photon gas and VdW gas. (We will be seeing these in examples)
(3) To develop expressions for the internal energy of the above systems
At this point we will now return to the main-line of class content. . .
Thermodynamic Process
An equilibrium state: system has well-defined static values for macroscopic
thermodynamic coordinates (e.g. PVT).
A thermodynamic process: a series of actions applied to a system to bring it
from one equilibrium state to another.
(e.g compression/expansion of a fluid at constant pressure or temperature)
Important: in general, only the starting-point and the end-point of the process are
necessarily equilibrium states!
P
(Vf, Pf)
apply some
process. . .
Vi, Pi
(Vi, Pi)
Vf, Pf
V
Consider the following process:
PPP =F/A
ext1
PP
PP
Vi, Pi
Vf, Pf
Equilibrium:
Pext=Pi
Suddenly increase
external pressure
Pext2>Pi
system will be pushed
out of equilibrium!
Wait and let system

equilibrate:
(Vf, Pf)
(Vi, Pi)
V
Pf=Pext2
Alternatively, pressure can be increased
slowly enough, one small slow step at a
time, so that the system is close to
equilibrium over the entire process
Quasistatic Process
Quasistatic Process: Process is designed to take place very slowly with
only very small changes applied to external constraints at each step:
system is effectively passed through a series of very closely spaced
intermediate equilibrium states
P
(Vf, Pf)
quasistatic process
(Vi, Pi)
V
PP
Vf, Pf
PP
...
PP
PP
PP
Vi, Pi
Relaxation Time
How slow is slow enough?
Process must take place slower than the system relaxation time
For example, for a piston gas system:
PP
PP
PP
gas density
PP
Rapid compression creates a pulse of high density that travels across system
(compression wave) reflects and gradually dissipates due to viscous damping
Relaxation time: ~L/vs (vs: speed of sound in gas)
Reversible Process
Reversible Process: a process applied in such a way that the system
can be returned to its original state with no change to the system or its
surrounding environment
remove weight
and let system
equilibrate
place large weight

let flow settle down. .
Frictionless
on
piston
PP
PP
PP
piston
Pext=P1
Pext>P1
Pext=P2
P1, V1
T1
V2
Energy will be dissipated as
turbulent flow caused by fast
moving piston is damped by
viscous forces in gas
P2 , V2
T2
PPPext=P3=P1
P3=P1
T3>T1
V3>V1
System cannot return to initial state by

removing weight: system temperature
will have increased due to dissipation
process irreversible
Reversible Process
OK. Let us divide our weight into smaller masses. In fact, let us divide
the weight into sand grains of infinitesimal size and add them very slowly
so that the piston pressure and gas pressure are almost exactly balanced
and the system is always infinitely close to equilibrium
Frictionless PP
Pext=Pi
piston
Pi Vi
sand
grain
PP
PextP
P,V
PP
PextP
P,V
(I can make Pext as close to P as I want by making the sand grains as

small as I want!)
Reversible Process
PP
PP
PextP
Let us keep adding grains. . .
PextPf
fast
forward
Pf , Vf
If I wish, I can remove the grains one-by-one, exactly retracing my initial path
through PV space: this process is reversible!
PPP P
ext
f
PP
PextPf
PP
Pext=Pi
Pi, Vi
Pf , Vf
P, V
Pressure, volume and

temperature values of
final state equal to initial
state.
Reversible vs Quasistatic
A reversible process is necessarily a quasistatic process
A quasistatic process is not necessarily reversible*
A reversible process is in fact the limit of a quasistatic process as the quasistatic
process is taken through a continuously spaced series of local equilibrium states
P
(Vf, Pf)
Quasistatic
P
continuous limit
(Vi, Pi)
(Vf, Pf)
Reversible
(and quasistatic)
(Vi, Pi)
V
*some textbooks equate reversible and quasistatic processes: when they do, they define
quasistatic in the limiting sense (e.g. as a continuous series of equilibrium states)
What kind of processes are quasistatic but not reversible?
A common example given is a piston with sliding friction:
Such a piston must be pushed with a force high enough to
balance the gas pressure AND overcome the static friction of
the system walls. . .
In this case, it is NOT possible for the applied pressure to
balance the gas pressure as closely as we like at each
point along the way.
The result will be stick and slip motion between discretely
spaced equilibrium states
Reversible process are quasistatic processes where no

dissipative forces such as friction are present (Finn p. 17)
Eq-of-State Models and Experiment

Thermodynamics experiments measure changes in a given
system parameter as another system parameter is varied
Change in volume V as temperature is increased/decreased by T
(at constant pressure)
Change in volume V as pressure is increased/decreased by P
(at constant temperature)
Eq-of-State Model!
Experiment!
V
The ratio:
T
becomes small
V

T P
Partial derivative of
volume with respect to T at
constant P
constant pressure
The ratio:
P
V becomes
V
small

P T
P T
volume with respect to P at
constant T

The total change in volume dV arises from:
(1) The change in volume due to varying T at constant pressure:
V
dT
T P
(2) The change in volume due to varying P at constant temperature:
V
dP
P T
The total change in

volume dV:
V
V
dV = dT + dP
P T
T P

Example: Ideal Gas
Calculate:
Calculate:
PV = Nk B T
V

T P
V

P T
Calculate dV
V
V
dV = dT + dP
P T
T P

Example: Ideal Gas
PV = Nk B T
Nk B
Nk B T
V
=
=
P
T P P
T P
Calculate:
V Nk B T
1
Calculate:
=
Nk
T
=

B
2
P
P
P
T
Calculate dV:
Nk
dP
dV = B dT Nk B T 2
P
P
(We can also go backwards, and

determine
state
an equation
of
from a dV expression!)
V
V
dV = dT + dP
P T
T P

Certain parameters in thermodynamics scale with system
size: these parameters are called extensive parameters
System: (V,P,T,N)
Divide
system in two
System 1:
System 2:
(V/2,P,T, N/2) (V/2,P,T, N/2)
(half of molecules
on one side half on
the other)
The volume of the sub-systems is halved: P and T remain the same
Parameters that remain the same, e.g. do not scale with

system size, are called intensive parameters)

Important detail: we need to normalize to changes in extensive
quantities so that parameters we measure are size-independent:
1 V
Define volume expansivity:

V T P
normalization factor
Define isothermal compressibility:
(fractional change in volume for a given

temperature change at constant
pressure)
change in volume
1 V (fractional
a given pressure change at
for
V P T constant temperature)
1/ B (bulk-modulus)

Lecture 5: Thermodynamic Processes and
Reversible Work
Time: 2:35-3:25
Place: Burnside 1B39
Office Hours: 2-3MW
Rutherford 411
An equilibrium state: system has well-defined static values for macroscopic
thermodynamic coordinates (e.g. PVT).
(e.g compression/expansion of a fluid at constant pressure or temperature)
Important: in general, only the starting-point and the end-point of the process are
necessarily equilibrium states!
P
(Vf, Pf)
apply some
process. . .
Vi, Pi
(Vi, Pi)
Vf, Pf
V
Quasistatic Process
system is effectively passed through a series of very closely spaced
intermediate equilibrium states
P
(Vf, Pf)
quasistatic process
(Vi, Pi)
V
PP
Vf, Pf
PP
...
PP
PP
PP
Vi, Pi
Reversible Process
Reversible Process: a process applied in such a way that the system
can be returned to its original state with no change to the system or its
surrounding environment
remove weight
and let system
equilibrate
place large weight

let flow settle down. .
Frictionless
on
piston
PP
PP
PP
piston
Pext=P1
Pext>P1
Pext=P2
P1, V1
T1
V2
Energy will be dissipated as
turbulent flow caused by fast
moving piston is damped by
viscous forces in gas
P2 , V2
T2
PPPext=P3=P1
P3=P1
T3>T1
V3>V1
System cannot return to initial state by

removing weight: system temperature
will have increased due to dissipation
process irreversible
Reversible Process
OK. Let us divide our weight into smaller masses. In fact, let us divide
the weight into sand grains of infinitesimal size and add them very slowly
so that the piston pressure and gas pressure are almost exactly balanced
and the system is always infinitely close to equilibrium
Frictionless PP
Pext=Pi
piston
Pi Vi
sand
grain
PP
PextP
P,V
PP
PextP
P,V
(I can make Pext as close to P as I want by making the sand grains as

small as I want!)
Reversible Process
PP
PP
PextP
Let us keep adding grains. . .
PextPf
fast
forward
Pf , Vf
If I wish, I can remove the grains one-by-one, exactly retracing my initial path
through PV space: this process is reversible!
PPP P
ext
f
PP
PextPf
PP
Pext=Pi
Pi, Vi
Pf , Vf
P, V
Pressure, volume and

temperature values of
final state equal to initial
state.
A reversible process is necessarily a quasistatic process
A quasistatic process is not necessarily reversible*
A reversible process is in fact the limit of a quasistatic process as the quasistatic
process is taken through a continuously spaced series of local equilibrium states
P
(Vf, Pf)
Quasistatic
P
continuous limit
(Vi, Pi)
(Vf, Pf)
Reversible
(and quasistatic)
(Vi, Pi)
V
*some textbooks equate reversible and quasistatic processes: when they do, they define
quasistatic in the limiting sense (e.g. as a continuous series of equilibrium states)

Change in volume V as temperature is increased/decreased by T
(at constant pressure)
Change in volume V as pressure is increased/decreased by P
(at constant temperature)
Eq-of-State Model!
Experiment!
V
The ratio:
T
becomes small
V

T P
volume with respect to T at
constant P
constant pressure
The ratio:
P
V becomes
V
small

P T
P T
volume with respect to P at
constant T

The total change in volume dV arises from:
(1) The change in volume due to varying T at constant pressure:
V
dT
T P
(2) The change in volume due to varying P at constant temperature:
V
dP
P T
The total change in

volume dV:
V
V
dV = dT + dP
P T
T P

Example: Ideal Gas
Calculate:
Calculate:
PV = Nk B T
V

T P
V

P T
Calculate dV
V
V
dV = dT + dP
P T
T P

Example: Ideal Gas
PV = Nk B T
Nk B
Nk B T
V
=
=
P
T P P
T P
Calculate:
V Nk B T
1
Calculate:
=
Nk
T
=

B
2
P
P
P
T
Calculate dV:
Nk
dP
dV = B dT Nk B T 2
P
P
(We can also go backwards, and

determine
state
an equation
of
from a dV expression!)
V
V
dV = dT + dP
P T
T P

Certain parameters in thermodynamics scale with system
size: these parameters are called extensive parameters
System: (V,P,T,N)
Divide
system in two
System 1:
System 2:
(V/2,P,T, N/2) (V/2,P,T, N/2)
(half of molecules
on one side half on
the other)
The volume of the sub-systems is halved: P and T remain the same
Parameters that remain the same, e.g. do not scale with

system size, are called intensive parameters)

Important detail: we need to normalize to changes in extensive
quantities so that parameters we measure are size-independent:
1 V
Define volume expansivity:

V T P
normalization factor
Define isothermal compressibility:
(fractional change in volume for a given

temperature change at constant
pressure)
change in volume
1 V (fractional
a given pressure change at
for
V P T constant temperature)
1/ B (bulk-modulus)
What about how pressure

changes with temperature?
Partial Derivatives in Thermodynamics

Relations from multi-variable calculus allow us to relate multiple partial
derivatives drawn from a single underlying equation of state
The equation of state defines a relation
among three variables:
f (x, y,z) = 0
We can solve for x, y or z as a function of the

two remaining variables:
x(y,z) , y(x,z) , z(x, y)
In an experiment we want to know how one variable is changed in response

to changes in the other two:
x
x
dx = dy + dz
z y
y z
Partial derivative of x with
respect to y at constant z
(differentiate x with respect

to y with z constant)

z x
y
dy= y
dx + dz
x z
Partial derivative of x with

respect to z at constant y
(differentiate x with respect
to z with y constant)
dz
z
z
= dx + dy
x y
y

We can combine these relations as follows:
x
x
dx = dy + dz
z y
y z
x y
y
= dx + dz
x z
z x
z
y
x
+ dz
z
y
x
x
dx = dy + dz
z y
y z
y
y
dy = dx + dz
x z
z x
in dx and dz)
z
(collect terms
dz
=
dx + dy
x y x
x y
x y 1
y x
dx
+
dz =0
y x z +y z
=0
=0
Wechose x and z to be independent. The only way for this expression to vanish
in brackets to vanish:
for all
independent choices of dx
and dz is for the terms

1
x y
x y
= 1 or =
y zx z
y z x z
reciprocal relation
x y x
z = or
y z
x z y
x y z
= 1
y zz xx y
cyclical rule

These relations seems rather formalwhy are they interesting?
Let x=P, y=V, z=T:
V
1
Volume expansivity:

V T P
Isothermal
1 V

compressability:
V P T
Cyclical rule then gives
P
P V
=
T V V T T P
1 V 1 V

=
V T P V P T
= /
the expansivity and
I know
Once
compressability I get for free
knowledge of how the system
pressure changes with temperature!
x
y x
or
=
y
y zz x z
x y z
= 1
y zz xx y
cyclical rule
x y
1 or
=
y zx z
1
x y
=
y x
z
reciprocal relation
One Dimensional Systems

For a one dimensional system I can analagously define:
Linear expansivity:
L
1
L T
Isothermal Youngs modulus:
L
A

L T
(directly analogous
to the bulk modulus)
Question: How is the change of
tension with temperature at constant L
related to the linear expansivity and isothermal
Youngs modulus?
x y x
= or
y zz x z y
x y z
= 1
y zz xx y
x y
= 1 or
y zx z
cyclical rule
reciprocal relation
x y
=
y z x z
One Dimensional Systems

Question: How is the change of
tension with temperature at
constant L related to the linear
expansivity and isothermal Youngs
modulus?
Answer:
Let x=, z=T and y=L

=
T L
L T
= AY
x y x

or
=
y zz x z y
L

T
L 1
= A
A L T L
L
1
Linear expansivity:

L T

Youngs Modulus Y L
(isothermal):
A L T
x y z
= 1
y zz xx y
cyclical rule
L

T
x y
1 or
=
y zx z
1
x y
=
y x
z
reciprocal relation
Example: Change in Wire Tension

We wish to calculate the change in tension of a
wire heated from temperature T1 to T2:
(The wire is clamped at both ends so the length is fixed)
Say we know Y and from data tables:
T2
T1
T2
T2

dT = AY dT AY dT
T L
T1
T
1
assume varies very weakly

with temperature
)
= AY (T2 T1
The wire is heated so the tension

decreases
(A and Y typically, but not always, positive!)
Example: Change in Wire Tension

Wait a minute: the system is not necessarily
in equilibrium during the heating process!
Actually, we dont care whether the process was reversible!
The tension is defined uniquely for every equilibrium state: it is enough to
know that the process took place between two equilibrium states
Relation between 1D/3D Expansivity

There is a general relation between the quantities and :
Linear expansivity:
Volume expansivity:
L
1

L T

1 V
V T P
V = L x Ly Lz
This is not hard to show:
1
L
L L
x

(L x L y L z )
T P
= x
= y
= 3
L y
1
(L x L z )
=
+
L x Ly Lz
T L x L y L z
T
L z
1
+ (L x L y )
L x Ly Lz
A
=
= PA
(L y L z ) L x
Lz
1 L
1 L y
L z
1
= x +
+
=3
L x T L y T
L z T
( x = y = z )
Ly
Lx
Work
We define the work performed on the system by an applied pressure Pext
(to change system volume by some small increment V) :
W = Pext V
(meaning of sign convention: decrease volume; work positive)
If the change in volume is not small and/or the applied pressure changes
during the process:
Vf
W = Pext dV
Vi
The applied pressure does not in general equal the system pressure!
Only for a reversible process does
Pext = P
Reversible Work
Vf
For a reversible process:
W = PdV
Vi
We can use the equation of state to calculate P(V,T)!
Reversible vs Irreversible Work

Real-world processes can never be completely
reversible!
Reversible processes are a convenient idealization
Moreover there are many interesting thermodynamics
processes that are not even approximately reversible!
Fluid temperature
rises as work is
performed
The mass falls, spinning

the paddle-wheel. Work is
dissipated in fluid by
viscous drag. This is
completely irreversible
work!
This process does not go backwards if I reduce the mass!

A reversible process has a very special property:
A system performs maximal work for a reversible expansion
Consider the following non-reversible process:
PP
Pext=Pi
PP
Pext=Pi/2
PP
(Vi, Pi)
Pext=Pf
(V, Pi/2)
Pi/2
Pi, Vi
P, V
Pf, Vf
(1) External pressure is lowered to

Pi/2 and system expands
Pf and system expands
W=
(Pi /2) (V Vi )
W=
(Vf, Pf)
Pf (V f V )
Work
performed
by system
against external pressure is
equal to shaded area

For the equivalent reversible process, system and external
pressure always balance, so more worked is performed
(Vi, Pi)
reversible
work
(V, Pi/2)
Pi/2
Pf
(Vf, Pf)
Work performed
for non-reversible
example
Work performed by system

Minimal work is performed on system for a reversible compression
Draw a diagram to convince yourself of this!
P
Pext=Pf
Pext=Pf/2
(Vf, Pf)
(V, Pf/2)
(Vi, Pi)

For irreversible compression, external pressure larger
than system pressure
For reversible process, system and external pressure almost
exactly balance, so more worked is performed
P
Pf
(Vf, Pf)
reversible
work
(V, Pf/2)
Pf/2
(Vi, Pi)
Work performed
for non-reversible
example
V
Reversible Work for non-PVT Systems

Work can be defined as well for non-PVT systems and thermodynamic
systems of reduced dimensionality
Lf
Work for 1D systems:
W=
dL
Li
Af
tension
W = dA
Ai
(stretching a wire/polymer)
(increasing surface area)
surface tension
Reversible Work: Ideal Gas

Question: what is the work performed for the reversible expansion/
compression of an ideal gas from an initial volume Vi to a final volume Vf:
(a) For system at constant temperature T?
(b) For system at constant pressure P?
(a) Ideal gas law:
Vf
Vf
W =
Vi
Vf
PV = Nk B T
W = PdV
Vi
Vf
dV
= k B TN ln
PdV = k B TN
Vi
V V
i
(b) W = PdV = P (V V )
f
i
Vf

Consider the work performed on system over two different paths:
Path 1: isothermal (constant temperature)
(Vf, Pf)
W1 =k B TN ln
path 1 (isothermal)
path 2
Vi
Path 2: isobaric (constant pressure)

followed by isochoric (constant volume)
(Vi, Pi)
Vf
V f )
W
2 = Pi (Vi
(contribution
from isochoric path zero)
The work performed along the two paths is NOT the same!
The work can then not be expressed as a simple function of the endpoints of the process
Pressure and volume, in contrast, are uniquely defined at each point in state
space: the difference P and V between any two points in state space is
always the same!
Work and Path Dependence

In thermodynamics, it is very important to distinguish between quantities
whose change in state-space is path-independent or path-dependent
Path-independent quantities: state-variables (P, V, T) or, as we will
encounter soon, state functions (internal energy U)
Path-dependent quantities: work (and heat)
Physically, quantities whose change is path-dependent cannot be assigned a
unique value to each point in state-space
Work is not a function of PV: there is no such thing as the work in a system
Work is a type of energy transfer, an external activity or process that is
performed on or by a body, the amount of work transferred is dependent on
the details of the process. . .
How can we check whether a given quantity is path

dependent or independent? (Next Lecture)

Lecture 6: Heat and The First Law
of Thermodynamics
Time: 2:35-3:25
Office Hours: 2-3MW
Rutherford 411
Finn: p 22-p. 37
Review: Quasistatic Process

system is effectively passed through a series of closely spaced intermediate
equilibrium states
P
(Vf, Pf)
Quasistatic Process
(Vi, Pi)
V
Review: Reversible Process

Reversible Process:
(1) A process applied in such a way that the system can be returned to its
original state with no change to the system or its surrounding environment
(2) an infinitesimal change in an imposed constraint at any point during the
process is enough to reverse the direction of a process in state space
(3) Reversible processes are quasistatic processes which pass through a
continuous succession of equilibrium states
(4) No dissipative processes are present
P
(Vf, Pf)
Reversible
(and quasistatic)
(Vi, Pi)
V
Work
We define the work performed on the system by an applied pressure Pext
(to change system volume by some small increment V) :
W = Pext V
(meaning of sign convention: decrease volume; work positive)
If the change in volume is not small and/or the applied pressure changes
during the process:
Vf
W = Pext dV
Vi
The applied pressure does not in general equal the system pressure!
Only for a reversible process does
Pext = P
Reversible Work
Vf
W = PdV
Vi
We can use the equation of state to calculate P(V,T)!
Reversible Work for non-PVT Systems

Work can be defined as well for non-PVT systems and thermodynamic
systems of reduced dimensionality
Lf
W=
dL
Li
Af
tension
W = dA
Ai
(stretching a wire/polymer)
(increasing surface area)
surface tension

Real-world processes can never be completely
reversible!
Reversible processes are a convenient idealization
Moreover there are many interesting thermodynamics
processes that are not even approximately reversible!
Fluid temperature
rises as work is
performed
The mass falls, spinning

the paddle-wheel. Work is
dissipated in fluid by
viscous drag. This is
completely irreversible
work!
This process does not go backwards if I reduce the mass!

A reversible process has a very special property:
Consider the following non-reversible process:
PP
Pext=Pi
PP
Pext=Pi/2
PP
(Vi, Pi)
Pext=Pf
(V, Pi/2)
Pi/2
Pi, Vi
P, V
Pf, Vf

Pi/2 and system expands
Pf and system expands
W=
(Pi /2) (V Vi )
W=
(Vf, Pf)
Pf (V f V )
Work
performed
by system

For the equivalent reversible process, system and external
pressure always balance, so more worked is performed
(Vi, Pi)
reversible
work
(V, Pi/2)
Pi/2
Pf
(Vf, Pf)
Work performed
for non-reversible
example
Work performed by system

Draw a diagram to convince yourself of this!
P
Pext=Pf
Pext=Pf/2
(Vf, Pf)
(V, Pf/2)
(Vi, Pi)

For irreversible compression, external pressure larger
than system pressure
For reversible process, system and external pressure almost
exactly balance, so less worked is performed
P
reversible
work
Pf
Pf/2
(Vf, Pf)
Work performed
for non-reversible
(V, Pf/2)
example
(Vi, Pi)

Question: what is the work performed for the reversible expansion/
compression of an ideal gas from an initial volume Vi to a final volume Vf:
(a) For system at constant temperature T?
(b) For system at constant pressure P?
(a) Ideal gas law:
Vf
Vf
W =
Vi
Vf
PV = Nk B T
W = PdV
Vi
Vf
dV
= k B TN ln
PdV = k B TN
Vi
V V
i
(b) W = PdV = P (V V )
f
i
Vf

Consider the work performed on system over two different paths:
Path 1: isothermal (constant temperature)
(Vf, Pf)
W1 =k B TN ln
path 1 (isothermal)
path 2
Vi
Path 2: isobaric (constant pressure)

followed by isochoric (constant volume)
(Vi, Pi)
Vf
V f )
W
2 = Pi (Vi
(contribution
from isochoric path zero)
The work performed along the two paths is NOT the same!
The work can then not be expressed as a simple function of the endpoints of the process
Pressure and volume, in contrast, are uniquely defined at each point in state
space: the difference P and V between any two points in state space is
always the same!
Work and Path Dependence

In thermodynamics, it is very important to distinguish between quantities
whose change in state-space is path-independent or path-dependent
Path-independent quantities: state-variables (P, V, T) or, as we will
encounter soon, state functions (internal energy U)
Path-dependent quantities: work (and heat)
Physically, quantities whose change is path-dependent cannot be assigned a
unique value to each point in state-space
Work is not a function of PV: there is no such thing as the work in a system
Work is a type of energy transfer, an external activity or process that is
performed on or by a body, the amount of work transferred is dependent on
the details of the process. . .
How can we check whether a given quantity is path

dependent or independent?
Inexact vs Exact Differential

Infinitesimal changes in path-independent quantities can be expressed as an
exact differential. Consider state function (x, y) with x and y state-variables:`
2

d = dx + dy
x y
y x
Change in due to
varying x with y
constant
Change in due to
varying y with x
constant
(x, y)
dx
dy
Integral performed over

particular path in state space
end-points 1 and 2)
(with
d = 0
Integral over a closed

loop in state space
= (x 2 , y2 )
(x1 , y1 )
Path independence

Consider a general differential form:
dQ = F(x, y) dx +G(x, y) dy
Does there exist some function Q(x,y) defined at every point in state
space with the property that
Q
Q
F(x, y) = ; G(x,
y) =
?
x y
y x
(If so then Q is path-independent)
Necessary and sufficient

condition for Q(x,y) to exist:
Proof
If Q(x,y) exists:
Q
= ; G=
x y
F
G
=
y x x y
Q

y x

2
2
F
Q
G
Q Q Q
= =
= =
=
y x y x y yx xy x y x x y
Differentiation order can be exchanged
This demonstrates
that the condition is
necessary: the
proof of sufficiency
is given in a standard
multi-variable
calculus class

Let us explore some specific examples. . .
dQ = xy dx +x 2 y dy
= F(x, y)
F
= 2xy
y x
= G(x, y)
G
= 2xy
x y
What is Q(x,y)? We guess: Q(x, y) =
Q
Q
2
2
=xy
= x y
x y
y z
(Exact!)
1
2
x 2 y 2 +constant

Let us explore some specific examples. . .
dQ = x y dx +xy dy
= F(x, y)
F
=
y x
= G(x, y)
G
=
x y
y2
(Inexact!)
How do we perform integration of a differential along a

particular
path in state-space?
Line Integration
y
dQ = xy dx +x 2 y dy
(x1=1, y=1)
Path 2
Path 1
(x2=0,
y2=1/2)
Path 1:
2
x (x constant:
x=1, dx=0)
(1,1/ 2)
2
2
xy
dQ
=
dx
+x y dy =
(y constant:
y=1/2, dy=0)
x 2 y dy
(1,1)
1
2
1
2
= y
(0,1/ 2)
xy 2dx = 12
(1,1/ 2)
2 1/ 2
1 1
4 2
x2
0
1
= ( 41 1 ) =
38 =18 (0 1 ) = 1
8
Path 2: you
will work on
HW
(hint: write y in termsof x, given by equation
for particular path,

integrate with respect to x,need to transform dyto dx)
Notation: Inexact Differential

In thermodynamics a special notation is used to denote an inexact differential:
a horizontal bar through the d
A differential of work is written:
dW
dW = PdV
reversible work
The pressure is related to V and T by the systems equation-of-state

The bar through the d reminds us that work is an inexact
differential: the work performed depends on the particular path
taken through state-space during the thermodynamic process
Consequently, the quantity of work performed depends on the details of

the process; it does not have a defined value at a given state
Heat: Intuitive Concept

It is our common experience that when a hot body at higher temperature is
placed in contact with a cold body at lower temperature the two come to
equilibrium at some intermediate temperature
HOT
HOT
COLD
COLD
Intermediate
(luke-warm)
Moreover, it is our experience that special thermally insulating walls exist that will
substantially slow-down the equilibration of objects at differing temperatures
One might postulate that something is being transferred between the two bodies,
and that thermally insulating walls block this exchange, but what exactly is being
exchanged, and how do we quantify whatever it is?
Heat: History
Caloric Concept of Heat: Heat is an indestructible, conserved massless fluid
like substance called caloric that flows from from hotter to colder bodies
(discredited by mid 19th century).
Conversion of mechanical energy to heat:
Count Rumford (1798) observed that the
process of boring cannon could release
substantial heat (cannon boring: iron-bit
rotates within brass cylinder)
He performed an experiment where a cannon
was bored immersed in an insulated water-bath:
after several hours of boring the water was
observed to boil
The source of heat seemed to be
inexhautsible: concept of conserved caloric
substance discredited
1753-1814
Count Rumford (Benjamin Thompson)
Joules Paddle-Wheel Experiment

1818-1889
spins
paddle
wheel
falling
weight
James Prescott Joule
Joule (English scientist and brewer), inspired by Rumfords experiment, conclusively
demonstrated the interconvertablity of mechanical and heat energy (1840-1849)
Paddle wheel experiment: falling weight spins paddle and heats thermally
insulated liquid via viscous friction. Increase temperature of liquid via work alone
Joules Conclusions
Adiabatic Process: Process that takes place in a thermally isolated system
(e.g. a system with special walls that prevent system from reaching thermal
equilibrium with surroundings)
Work performed, as Joule did, under adiabatic conditions is called
adiabatic work
Joule observed the following through detailed experimentation:
(1) Work equivalent to 4.2kJ is required to raise the temperature of
one kg of water by 1K
(2) No matter how adiabatic work performed exactly the same amount of work
is required to increase temperature of the water system by the same degree
(Joule investigated processes involving both dissipation of mechanical work via
the paddle wheel and electrical work dissipated by passing a current through a
resistor immersed in the bath)
First Law for Adiabatic Process

Joules conclusions turn out to be valid experimentally for all adiabatic
processes independent of system details:
If a thermally isolated system is brought from one equilibrium
state to another, the work performed to achieve this change is
independent of the process used
In mathematical terms, adiabatic work is path independent depending only
on the final and initial equilibrium states
Thus, we can introduce a state function* U, which we call the internal energy, with
the property: U 2 U 1 = Wadibatic
(Wadiabatic: adiabatic work; U1: internal energy of state 1; U2 internal energy of state 2)
Thechange ininternal energy between any two states is always the same
*that is a function defined at all equilibrium states
First Law: General Statement

The work performed for a general non-adiabatic process is NOT equal to the
adiabatic work; it is also path-dependent, depending on process details
If in general the work performed is greater or less than the internal energy change
for a given process there must be a missing item in our energy accounting. . .
We quantify heat as this missing line item in our energy budget
The heat transferred Q for a given non-adiabatic process is quantified as the
difference between the internal energy change (adiabatic work) and the nonadiabatic work
In mathematical terms:
U = Q + W = Wadiabatic
(finite change)
= 0 (process adiabatic)
Heat and work are necessarily
inexact differentials; internal
energy is an exact differential
dU = dQ + dW

(differential change)

of Thermodynamics Part II
Time:
Place:
Office Hours:
Rutherford 411
Review: Reversible Work

The differential of work for a reversible process:
dW = PdV
reversible work
Sign convention: work done on system is positive

Heat: Intuitive Concept

It is our common experience that when a hot body at higher temperature is
placed in contact with a cold body at lower temperature the two come to
equilibrium at some intermediate temperature
HOT
HOT
COLD
COLD
Intermediate
(luke-warm)
One might postulate that something is being transferred between the two bodies,
and that thermally insulating walls block this exchange, but what exactly is being
exchanged, and how do we quantify whatever it is?
Joules Paddle-Wheel Experiment

1818-1889
spins
paddle
wheel
falling
weight
James Prescott Joule
Joule (English scientist and brewer), inspired by Rumfords experiment, conclusively
demonstrated the interconvertablity of mechanical and heat energy (1840-1849)
Paddle wheel experiment: falling weight spins paddle and heats thermally
insulated liquid via viscous friction. Increase temperature of liquid via work alone
Joules Conclusions
Adiabatic Process: Process that takes place in a thermally isolated system
(e.g. a system with special walls that prevent system from reaching thermal
equilibrium with surroundings)
Work performed, as Joule did, under adiabatic conditions is called
adiabatic work
Joule observed the following through detailed experimentation:
(1) Work equivalent to 4.2kJ is required to raise the temperature of
one kg of water by 1K
(2) No matter how adiabatic work performed exactly the same amount of work
is required to increase temperature of the water system by the same degree
(Joule investigated processes involving both dissipation of mechanical work via
the paddle wheel and electrical work dissipated by passing a current through a
resistor immersed in the bath)

First Law: General Statement

The work performed for a general non-adiabatic process is NOT equal to the
adiabatic work; it is also path-dependent, depending on process details
If in general the work performed is greater or less than the internal energy change
for a given process there must be a missing item in our energy accounting. . .
We quantify heat as this missing line item in our energy budget
The heat transferred Q for a given non-adiabatic process is quantified as the
In mathematical terms:
(finite change)
Heat and work are necessarily
inexact differentials; internal
energy is an exact differential
dU = dQ + dW

(differential change)
First Law: Parable of the Pond

An analogy may prove helpful in understanding the first law. . .
An enterprising farmer couple construct a special pond
gate
grass
gate
(upstream)
(downstream)
water
grass
The water level in the pond can be varied by raising and lowering upstream and
downstream gates: these have built-in flow meters so the net inflow and outflow
can always be precisely measured

gate
gate
rainfall
evaporation
(upstream)
(downstream)
Water level in the pond will also vary due to rainfall and evaporation
The farmer couple have no direct way to measure the water gained or lost
due to rainfall/evaporation

gate
(upstream)
gate
(downstream)
plastic tarp
However, the farmer couple can place a plastic tarp over the pond and prevent
water from escaping due to evaporation and entering due to rainfall
In this case, water can only be gained or lost by opening closing downstream
gates
pla

gate
(upstream)
gate
(downstream)
stick gauge
With the tarp in place, the farmer couple can quantify the total amount of water
in their pond at any time in the following way:
They drain out all the water and then meter a certain (known) amount in; the water
level of the pond is then marked off on a stick gauge. Repeating this procedure
they can determine the water-level as a function of the gauge-position
pla

gate
(upstream)
gate
(downstream)
stick gauge
The tarp is then removed!

The farmer couple enjoy a well-earned dinner
Meanwhile, their flow meters record the net fluid entering and leaving the pond
pla

gate
(upstream)
gate
(downstream)
stick gauge
The next day, the couple returns to the pond: they have no ideajust by
looking at their stick gaugehow much of the water in the pond is due to
rainfall or inflow
BUT They can integrate over the net inflow/outlfow and subtract this value
from the water level determined via the gauge. ..

Winflow
Qrain
Woutflow
Qevap
Pond first law:
Q = U W
(tarp analagous to
adiabatic process)
Water level: U (analagous to internal energy)

Net inflow/outflow:
W = Winflow Woutflow (analagous to work)
Net gain/loss due to rainfall/evaporation:
Q =Qrain Qevap
(analagous to heat)

And the moral of this
story is. . .
Woutflow
Qrain Qevap
Winflow
Work and heat are forms of

energy transfer
You can arrange for a process that involves only work
(adiabatic/movable walls: using tarp to allow only water inflow)
Or only heat transfer
(rigid/diathermic walls; raising gates to allow only rain/evaporation)
But once the process has occurred, there is only the net result, the
change in system internal energy (water level)
There are in infinite number of different processes (work+heat) that correspond
to a given internal energy change
Heat: Final View Point

Heat is the non-mechanical exchange of energy between a system and its
surroundings arising in the presence of a temperature difference between them
Microscopic View
Energy transfer due to work results in an ordered displacement of constituent
molecules (e.g. when system volume changed all molecules are displaced in
same direction)
Energy transfer due to heat exchange results in an increase in disordered
random motions of constituent molecules
Example: Ideal Gas

Question: what is the total heat exchange (magnitude and sign) for the
reversible compression of an ideal gas from initial to final states
(a) For system at constant temperature T? (along path a)
(b) For isobaric compression followed by isochoric (constant volume)
increase in pressure (path b)
Hint: first law for reversible process
P
dU = dQ + dW
= PdV
Internal energy of ideal gas:
(monotonic)
U = 32 k B NT
(Vf, Pf)
Path a (isothermal)
Path b
(Vi, Pi)
V
Example: Ideal Gas

(a) Isothermal Process (along path 1)
U = 32 Nk B T = 0
Vf
Vf
W = PdV = k B T N
Vi
Vi
= k B TN ln
Vf
Vi
Vf
= k B TN ln
First Law: Q = W
Vi
V f <Vi
Q <0
(system evolves heat to thermal reservoir)
dU = dQ + dW
= PdV
3
U = 2 k B NT
dV
V
(Vf, Pf)
Path a (isothermal)
Path b
(Vi, Pi)
V
Example: Ideal Gas

(b) Isobaric followed by isochoric process (along path 2)
Vf
W1 = PdV = Pi (Vi V f )
dU = dQ + dW
= PdV
3
U = 2 k B NT
Vi
W2 = 0
(dV=0)
What about internal energy?

PiVi Pf V f
T=
=
kB N kB N
Ideal law gives:
W2
PiV f
T =
kB N
(Vf, Pf, T)
Path a (isothermal)
T Path b W1
(Vi, Pi, T)
V
Example: Ideal Gas

(b) Isobaric followed by isochoric process
(along path b)
T=
Vf
Vi
W2 = 0

U 1 = 32 k B N (T T )
3
2
= kB N
PiV f
3
(V
)
=
P
V
f
i
i
2
PiVi
B
Pf V f
kB N
PiV f
kB N
dU = dQ + dW
3
U = 2 k B NT = PdV
(V , P , T)
W2
kB N
T =
( kN kN)
B
(dV=0)
PiVi
Path a (isothermal)
T Path b W1
(Vi, Pi, T)
V
Example: Ideal Gas

(along path b)
T=
Vf
U 1 =
Vi
3
2
Pi (V f Vi )
U
3
=
2
2 k B N (T T )
= 32 k B N
Pf V f
(kN
3
2V
f
W2 = 0 (dV=0)

kB N
PiV f
kB N
Path a (isothermal)
T Path b W1
kB N
dU = dQ + dW
3
U = 2 k B NT = PdV
W2
(Pf Pi )
Pf V f
(V , P , T)
kB N
T =
PiV f
PiVi
(Vi, Pi, T)
V
Example: Ideal Gas

(along path b)
T=
Vf
Vi
U 1 =
3
2
Pi (V f Vi )
PiVi
kB N
T =
Pf V f
kB N
PiV f
kB N
dU = dQ + dW
3
U = 2 k B NT = PdV
W2 = 0 (dV=0)

(V , P , T)
U 2 = 32 V f (Pf Pi )
f f

3
Check: U 1 + U 2 = Pi (V f V )
path a (isothermal)
i
2
W2
3
+ 2 V f (Pf Pi )
T Path b W1
(Vi, Pi, T)
3
V P
= 2 ( f f Vi Pi ) = 0
Example: Ideal Gas

(along path b)
T=
Vf
Vi
U 1 =
3
2
Pi (V f Vi )
W2 = 0 (dV=0)

U 2 = 32 V f (Pf Pi )

First Law:
PiVi
T =
kB N
PiV f
kB N
dU = dQ + dW
3
U = 2 k B NT = PdV
(V , P , T)
kB N
Pf V f
Q1 = U 1 W1 = 52 Pi (Vi V f )
Q2= U
2 W2 = 32 V f (Pf Pi )
W2
Path a (isothermal)
T Path b W1
(Vi, Pi, T)
V
Example: Ideal Gas

(along path 2)
T=
Q1 = U 1 W1 = 52 Pi (Vi V f )
Q2 = U 2 W2 = 32 V f (Pf P
i )
Q = Q1 + Q2

5
= 2 Pi (Vi V f )

+ 32 V f (Pf Pi )
3
2 Vf
PiVi
T =
W2
= V f (Pi Pf ) < 0 = V f Pf
(system evolves heat)

kB N
(V , P , T)
Pf +V f Pi 52 Vi Pi
PiV f
kB N
dU = dQ + dW
3
U = 2 k B NT = PdV
kB N
Pf V f
Path a (isothermal)
T Path b W1
(Vi, Pi, T)
V

of Thermodynamics
Time:
Place:
Office Hours:
Rutherford 411
Review: Reversible Work

The differential of work for a reversible process:
dW = PdV
reversible work
Sign convention: work done on system is positive


Review: First Law

Finite change
dU = dQ + dW
Differential change
transferred Q for a given non-adiabaticprocess is quantified as the

The
heat

Internal Energy
The internal energy U is a function of the state variables (P, V or T)
(we can choose two independent variables, the
third will be determined by the equation of state)
Problem: we want to deduce experimentally how U depends on P, V or T
We will later learn. . .
The volume dependence of U can be obtained directly from the systems
equation of state. . .
What about the temperature dependence of U?
(If we know volume dependence and temperature dependence we get
the pressure dependence through the equation of state)
Heat Capacity
How do we measure a systems internal energy as
a function of temperature?
paddle wheel
falling
weight
(1) Can perform irreversible work on thermally

isolated system and measure temperature
change (e.g. Joule Paddle wheel):
system
Wirreversible = U
Wirreversible = mgh
(experimentally inefficient)
(2) Can perform reversible work on

thermally isolated system and measure
temperature change
P,V
P=Pext=F/A
Wreversible = PdV
Wreversible = U
(experimentally inefficient)
system
(3) Can heat system and measure

change
temperature
(experimentally efficient, but
exactly how do we obtain U(T)?)
diathermal walls
heat source
Heat Capacity
System
Heats flow into a system, changing

its temperature by T
Ti Ti + T
Q
Perform process reversibly by placing the system in contact with a thermal

reservoir* with a temperature infinitesimally higher then the system temperature
The heat capacity is defined as the ratio of
reversible heat introduced over the
temperature rise at T->0
Q dQ
C = Tlim
=
0
T
The specific heat is the heat capacity per unit mass:

system of interest will not alter the reservoir temperature
dT
c = 1 dQ
m dT
*Thermal reservoir: a system at fixed temperature so large that

anyheat flows into or out of the
Heat Capacity
Heat capacities can be defined at conditions of constant system
volume or pressure:
dQ U
CV = =
dT V T V
Heat capacity at constant volume:

(experimentally more difficult)
Tf
Q = CV dT
Ti
(reversible
isochoric)
Heat capacity at constant pressure:
(experimentally easier)
C P dT
Ti
dQ
C P =
dT P
Tf
Q=
dU = dQ +dW
0
= PdV
(reversible isobaric)
Heat capacities at constant pressure and volume are NOT the same
Heat Capacity
General relation between CV and Cp
dQ = dU +PdV
(first law; reversible process)
dU
U(T,V )
U
= T dT
V
U
+ dV
V T

U
dQ = T dT
V
Express V as a
+
+P dV function of T and P V (T,P)
V T
V
V
= dT + dP
P T
T P

U
V
V
U U
dT +
+P dP
= + V +P
T P
V T
P T
T V
dQ
=
dT P
Heat Capacity
U U
dQ
=
+ +P
dT P
T V V T
= CP
= CV
C P = CV +
V
T (from previous slide)
P
U
V
+P
V T
T P
(not necessary to
remember)
Cp is higher than CV due to the heat flow required to
increase
the
system volume at constant pressure

Heat Capacities for Ideal Gas

For an ideal gas there is a very simple relation between Cp and Cv:
The internal energy of an ideal gas is a
function only of temperature:
dU ideal = CV dT
U ideal U(T)
with
U
CV =
T V
For an ideal gas the first law can be written:
= CV dT
dQ = dU dW
The heat capacity at constant pressure:
= PdV
V
dQ
+k
N
=
C
C P = = CV +P
V B
T P
dT P
=1
Nk B d
T
=
P dT
V = Nk BT /P
C P = CV + k B N
Ideal gas
Heat Capacities for Ideal Gas

Obtain heat capacities from equipartition
Monotonic ideal gases (He, Ne, A):
Three translational
degree-of-freedom
z
y
U = N 3 k BT
2
CV =
3
2
N kB
Diatomic ideal gases (H2, O2, N2):

U= N5 2 k B T
CV =

Three translational+two rotational
5
2
N kB
Ideal Gas: Eq. for Adiabatic Process

For an ideal gas the heat capacities can be used to write down a very useful
relation for the curve of a reversible, adiabatic process in state space
For adiabatic process:
dQ = dU +PdV
dQ = 0
PV = Nk BT ; dU = CV dT ; C P = CV + k B N

dV
0 = CV dT +PdV = CV dT +Nk B T
V
dT = Nk dV
dT +Nk dV = 0
C
CV
B
V
B
T
V
V

T
CV ln T = Nk B ln V +constant
Ideal gas:

For adiabatic process:
dQ = dU +PdV
dQ = 0
PV = Nk BT ; dU = CV dT ; C P = CV + k B N

(dividing out
CV ln T = Nk
B ln V +constant
by C )
Ideal gas:
= C P CV 1;
CV
CP
CV
= constant
ln T +Nk B
ln
V
C
V
ln(TV
ln T +( 1) ln V = constant
) = constant
TV 1 = constant


TV
= constant
CP
CV
Monotonic ideal gas:
PV = Nk BT
PV = constant
Reversible adiabatic
process for ideal gas
U = 32 Nk B T
C P CV + Nk B 3/2 +1 5
=
=
=
3/2
3
CV
CV
Rchardts Method
A very clever method for measuring the ratio of heat capacities
crosssectional
area: A
System pressure with ball:
P = Po +mg/ A
Weight of ball slightly
compresses gas
Ball
displacements
change system volume:
glass tube
dV = A y
Positive ball displacements decrease

pressure; negative ball displacements
increase pressure

Lead to restoring force on ball:
F = A dP
metal ball
(mass m)
y
y=0
(equilibrium)
System
(filled with gas)
Equilibrium volume (V)
and pressure (P)_
Rchardts Method
Volume change due to ball
displacements:
Restoring force due to
pressure changes
crosssectional
area: A
dV = A y
F = A dP
glass tube
metal ball
(mass m)
y
Assume oscillations so rapid that heat

transfer does not have time to occur
Process adiabatic
Assume oscillation amplitude so small that
the states can be assumed to always be
approximately in equilibrium
Process reversible
y=0
(equilibrium)
System
(filled with gas)
and pressure (P)_
Rchardts Method
Volume change due to ball
displacements:
pressure changes
dV = A y
F = A dP
crosssectional
area: A
glass tube
metal ball
(mass m)
y
y=0
(equilibrium)
A reversible adiabatic process satisfies:
PV =
constant
P V 1 dV +V dP = 0
P
dV
dP =
V
P
P
2
y

dV = A
F = A
V
V
System
(filled with gas)
and pressure (P)_
Rchardts Method
pressure changes
Newtons law:
P
y
F = A
V
2
crosssectional
area: A
glass tube
metal ball
(mass m)
y
y=0
(equilibrium)
d y
P
m 2 = F = A2 y
dt
System
V
(filled with gas)
d 2y
2 P
2
2
y
A
; o
2 = o
dt
and pressure (P)_
mV
of simple harmonic motion:

Oscillation
period
2
1 mV
(measure ratio of heat capacities by
t
=
=
2
A P
measuring period)
Heat Conduction
While technically the subject belongs to non-equilibrium thermodynamics, we
might want to know the rate at which heat energy is transferred
Consider a slab of material of length x and area A: the material is
contact on one end to a thermal reservoir at temperature T and one
end to a temperature of T+T
A
T+T
Experimentally:
T
Q
A
x
t
(t: time)
Constant of proportionality the thermal conductivity

(material dependent)
dQ
dT
= A
Differential
formulation:
dt
dx
( has units of watts/mK)
Heat Equation
Using the law of heat conduction we can actually derive an equation
that models the time-dependent temperature distribution in a material
Consider a differential section of the material of length dx
(the material has density )
dQm
dt
J(x)
T+T
dQ
J(x) = =
dt
J(x + dx)
dx
dT
A
dx
(heat per unit time transferred at position x)
The heat flowing into differential section:
dQm = J(x) J(x + dx)

dt
m dQ T
T
T (c : specific heat at constant
dQ
= dxA cP
P
= m cP
=
dT t
t
t pressure)
dt
Heat Equation
that models temperature distribution in a material
dQm
T
= dxA cP
t
dt
J(x)
J(x + dx)
T+T
dx
dT
dQm = J(x)
J(x + dx) = dxA cP
dt
dt
J(x) = A dT
J(x + dx) J(x)
1 J
T
dx
c
=
A x
t
Adx
(cP: specific heat)
A
T
2T c p T
=
2
x
t
Heat Equation
T(x,t): time-dependent temperature distribution
T+T
T
T
=K 2
t
x
(thermal diffusivity)
Heat Equation
c p

Lecture 8: Heat Engines
Time: 2:35-3:25
Office Hours: 2-3MW
Rutherford 411
Review: First Law

Finite change
dU = dQ + dW
Differential change
transferred Q for a given non-adiabaticprocess is quantified as the

The
heat

Review: Heat Capacity

System
Heats flow into a system, changing

its temperature by T
Ti Ti + T
Q
Perform process reversibly by placing the system in contact with a thermal

reservoir* with a temperature infinitesimally higher then the system temperature
The heat capacity is defined as the ratio of
reversible heat introduced over the
temperature rise at T->0
Q dQ
C = Tlim
=
0
T
The specific heat is the heat capacity per unit mass:

system of interest will not alter the reservoir temperature
dT
c = 1 dQ
m dT
*Thermal reservoir: a system at fixed temperature so large that

anyheat flows into or out of the
Review: Heat Capacity

Heat capacities can be defined at conditions of constant system
volume or pressure:
dQ U
CV = =
dT V T V
Heat capacity at constant volume:

(experimentally more difficult)
Tf
Q = CV dT
Ti
(reversible
isochoric)
Heat capacity at constant pressure:
(experimentally easier)
C P dT
Ti
dQ
C P =
dT P
Tf
Q=
dU = dQ +dW
0
= PdV
(reversible isobaric)
Heat capacities at constant pressure and volume are NOT the same
Review: Results for Ideal Gas

(from first law)
Relation between heat capacities at constant pressure and volume:
C P = CV +k B N
Ideal gas
Reversible adiabatic process for ideal gas

PV = constant
CP
CV
Heat Conduction
While technically the subject belongs to non-equilibrium thermodynamics, we
might want to know the rate at which heat energy is transferred
Consider a slab of material of length x and area A: the material is
contact on one end to a thermal reservoir at temperature T and one
end to a temperature of T+T
A
T+T
Experimentally:
T
Q
A
x
t
(t: time)
Constant of proportionality the thermal conductivity

(material dependent)
dQ
dT
= A
Differential
formulation:
dt
dx
( has units of watts/mK)
Heat Conduction: Example

Consider two concentric spherical shells at
radius r1 and r2
Heat is conducted between the
shells at a steady (constant) rate:
J=
r2
dQ
dt
What is the temperaturedifference between the shells?
dT
dQ
= A
dt
dx
Recall:
r1
Heat Conduction: Example

Consider two concentric spherical shells at
radius r1 and r2
Heat is conducted between

the shells at a steady rate:
r2
r1
dQ
J=
dt
What is the temperature difference between the shells?
dT
dQ
= A
dt
dx
dT
J 1
J
=
=
dr
4 r 2
A
r
J
J 1 1
dr
J 1 r
=
=

r2 =
T2 T1
4 r
4 r2 r1
4 r r
Recall:
Heat Equation
that models the time-dependent temperature distribution in a material
dQm
dt
J(x)
T+T
dQ
J(x) = =
dt
J(x + dx)
dx
dT
A
dx
(heat per unit time transferred at position x)
The heat flowing into differential section:
dQm = J(x) J(x + dx)

dt
m dQ T
T
T (c : specific heat at constant
dQ
= dxA cP
P
= m cP
=
dT t
t
t pressure)
dt
Heat Equation
dQm
T
= dxA cP
t
dt
J(x)
J(x + dx)
T+T
dx
dT
dQm = J(x)
J(x + dx) = dxA cP
dt
dt
J(x) = A dT
J(x + dx) J(x)
1 J
T
dx
c
=
A x
t
Adx
(cP: specific heat)
A
T
2T c p T
=
2
x
t
Heat Equation
T(x,t): time-dependent temperature distribution
T+T
T
T
=K 2
t
x
(thermal diffusivity)
Heat Equation
c p
Roadmap: Second Law

The first law of thermodynamics is a statement of conservation of
energy (energy book-keeping)
We can exchange energy in one form or another between a system
and its surroundings, but we cannot create it from scratch
The first law rules out certain types of thermodynamic processes:
(1) Objects never spontaneously jump up into the air, become hot or
change state (e.g. without some form of energy input)
(2) We cannot build a device that will work in a cycle and produce
continuous work, or kinetic energy, from nothing . . . (known as
perpetual motion of first kind)
Roadmap: Second Law

But the first law allows certain types of processes that
clearly do not happen!
Coffee in your cup never spontaneously cools down and
starts to swirl around. . .
One end of a spoon resting on a table does not spontaneously
become cold while the other end becomes hot. . .
Air in a room does not suddenly rush into one corner,
suffocating the occupants. . .
(Yet the reverses of these processes can occur. . .)
Roadmap: Second Law

We would like to formulate a new principle of thermodynamics, a
second law, that explains what processes can occur and why
certain processes are excluded. . .
This will be our goal for the next two weeks
Roadmap: Second Law

It is pedagogically traditional to motivate this second law
based on abstract considerations of engine performance
I will follow this traditional approach for three reasons:
Reason 1: It is a fascinating example of how extremely practical
applied considerations led to the uncovering of very deep physical
principles.
Reason 2: Considerations of engine performance/efficiency are of
considerable interest in their own right (even if you dont choose to
become engineers and design power plants!)
Reason 3: Considerations of reversible engine efficiency allow us to
introduce an absolute temperature scale
Roadmap: Second Law

(most
practical)
Heat engines
and Second Law
(most abstract)
Reversible
Heat engines
(Carnot Cycle)
Clausius
Inequality
Entropy based
formulation of
Second Law
Definition of
Entropy, S
Heat Engines
How can I produce heat from work?
Easy! Use Joule-paddle wheel to raise temperature of
liquid reservoir, via viscous friction, then put liquid at
higher temperature in contact with thermal reservoir
Net result: Transfer of work into heat with 100% efficiency!
System 2
System 1
TC
TH
Q
Increase temperature of
reservoir by performing
irreversible work
Thermal
reservoir
TC
Q=W
TH>TC
Heat Engines
How can I produce work from heat?
Consider two thermal reservoirs at TH and TC:
TH
Hot
TC
Cold
Heat Q will spontaneously flow

from the hot to cold reservoir
until equilibrium is reached
How can I divert some of this heat flow to perform useful work W?
TH
Hot
TC
Cold
Heat Engines
Put hot reservoir in diathermal contact with ideal-gas in piston system:
PP
PP
TH
TH
Hot
Hot
Reservoir is placed in diathermal
contact with piston system
PP
Pext=Patm
TH
P=Patm
. . .until gas pressure reaches

atmospheric pressure
Isothermal expansion
of ideal gas
TH
Hot
No change in internal energy

Q
TH
Piston is released and system

expands isothermally. . .
First Law:
Q = W
All work converted into heat BUT system

changes state at end of cycle and
process terminates!
Idealized Heat Engine

In order to be useful, a series of
processes is needed: each process
delivering useful work AND returning
to exactly the same starting point!
The system can be operated
repeatedly over this closed engine
cycle, delivering a fixed work W over
each cycle
TH
Hot
|QH|
closed
engine
cycle
W
|QL|
TC
Cold

Engine efficiency:
TH
W
=
QH
Hot
U = QH QL W = 0
over closed cycle:

system returns to
starting state so U=0
|QL|
TC
what we put in
First law of thermodynamics

applied to engine cycle:
|QH|
closed
engine cycle
what we get out
Cold
W = QH QL
QH QL
QL
=
=1
QH
QH
Heat Engine Examples

General Principle of Reciprocating Engine: confined gas in
cylinder-piston arrangement is alternatively heated and cooled,
undergoing reciprocating expansion/retraction that imparts rotational
motion via a cranck shaft
Crank
shaft
Single piston arrangement
Four-piston arrangement
Crank: converts reciprocating linear motion to rotational motion
(movies from wikipedia)
Heat Engine Examples

External Combustion Engine: Gas temperature/pressure
is increased by heating a surrounding reservoir that is placed
in contact with the reciprocating piston system (e.g. steam
engine, Stirling engine)
Internal Combustion Engine: gas temperature/pressure is
increased by rapid burning of fuel/oxygen in the piston
system itself (e.g. gas/diesel engine)
Working medium: engine can be run with gas, vapor/liquid
(e.g. steam engine), air-gasoline mixtures, can even build
rubber-band engines. . .
Steam engine technology historically the first engine
technology developed
Newcomen Steam Engine (1712)

First practical steam engine
(1) Cylinder filled with steam from boiler
(near atmospheric pressure)
(2) Spray of water condenses steam,
creating a vacuum that pulls piston
downward (and lifts pump handle)
(3) Steam readmitted to cylinder
and water condensate expelled; beam
pulled back to original position by
weight of pump shaft
Used to pump water out of mines

To water pump
(located down
mine shaft)
connected
by chain!
(piston can
only pull!)
Newcomen Steam Engine (1712)
(from animatedengines.com)
Watt Steam Engine (late 1700s)

1736-1819
James Watt: Scottish inventor,

made key improvements to
Newcomen steam engine, laying
technical foundation for industrial
revolution
Watt Steam Engine (late 1700s)
Steam Punk 1: Ticonderoga

Turn-of-century steam paddle wheel boat
At Shelburne Museum Vermont, ~2-3h drive from Montreal

A very nice weekend trip!
Steam Punk 2: Steam Locomotive
First Stroke: Steam from

boiler enters steam chest and
is admitted to cylinder by a
special sliding valve (blue),
pushing piston to left
Exhaust: At end of piston
stroke, valve shifts allowing
remaining steam to escape:
steam escapes in a quick
burst: choo!
Second Stroke:
Simultaneously, sliding valve
admits steam from back of
chamber, pushing piston to the
right
Second Exhaust: after

expansion steam is released
from the rear (choo-choo)!
Content from animated engines
Steam Power: 2012

Steam driven cycles produce most of the worlds electricity
(80% world)
Oil
Coal
steam expands
spinning turbine
Nuclear
steam condenses
into water
water heated to boiling point,
vaporized and superheated
Steam Engine Thermodynamics

Rankine Cycle
steam expands
spinning turbine
|QL|
|QH|
water heated to
boiling point,
vaporized and
superheated
steam condenses
into water
adiabatic
compression
isobaric
heating adiabatic
expansion
spinning turbine
(or pushing
piston)
isobaric
cooling
water-vapor
coexistance
region
Note that a heat |QL| must always be

output to the low temperature
reservoir!
(figures Zemansky and Dittman, Heat and Thermodynamics 2nd Ed)
Stirling Engine
Stirling Engine: reciprocating engine that works with enclosed
ideal gas (no phase transition takes place)
HOT
COLD
Regenerator
The Stirling Engine
Isothermal Compression (1-2)
3
Isochoric
P
|QR|
Isochoric Transfer (2-3)
|QH|
Isothermal (TH)
2
|QL|
Isothermal (TL)
Isochoric
|QR|
V
Isothermal Expansion (3-4)
Gasoline Engine
1: Intake stroke: mixture of gasoline
vapor and air moves into cylinder via
suction as receeding piston enlarges
accessible volume
2: Compression Stroke: Gasoline

vapor-air mixture is compressed by
advancing piston, increasing pressure
and temperature
3: Ignition/Power Stroke: Mixture is

rapidly burned after ignition via a spark-plug: hot
combustion products expand and push piston
away
4: Exhaust/Exhaust Stroke: Combustion

products are exhausted until pressure drops to
atmospheric pressure; piston pushes all remaining
combustion products out of cylinder
(annimation from wikipedia)
The Otto Cycle

Gasoline engine extremely complex to model exactly: friction/turbulent
gas motion, conductive heat losses, chemical reactions. . .
Otto cycle: idealized gas engine cycle, assume:

(1) Working substance at all times air
(can be modeled as ideal gas)
(2) All processes reversible
(3) No friction/turbulence
(4) No heat transfer through walls
The Otto Cycle

1
3A
3B
4A
3A: ignition
|QH|
4B
3B: power stroke

(adibatic)
2
2: compression
stroke (adibatic)
4A: exhaust
1: intake stroke
4B : exhaust stroke
|QL|
V
The Otto Cycle

Otto Cycle Summary:
1: Isobaric expansion
2: Adiabatic compression
3A: Isochoric temperature increase
3B: Adiabatic expansion
4A: Isochoric temperature decrease
3A: ignition
(isochoric)
3B: power stroke
(adibatic)
|QH|
2: compression
stroke (adibatic)
4B: Isobaric compression
1: intake stroke
4B : exhaust stroke
We want to determine the efficiency of the Otto Cycle:

Recall that
QL
=1
QH
(need to calculate QL and QH)
Steps 1 and 4B cancel ; steps 3B and 2 are adiabatic
Need to calculate heat transfer QH and QL
4A: exhaust
|QL|
V
The Otto Cycle

Otto Cycle Summary:
T3
3A
|QH|
3B
T2
4B
We assume that the heat capacities are constant for 3A and 4A
QL
=1
QH
T4 T1
=1
T3 T2
T3
QH =
CV dT = CV (T3 T2 )
T2
T1
QL =
CV dT = CV (T4 T1 )
T4
4A
T1
|QL|
V
The Otto Cycle

Otto Cycle Summary:
=1
V2, T3
|QH|
V
2, T
2
2
1
=
=
T2
T2 T3 T
T3 T2
2
3B
V1, T4
4A
|QL|
V1, T1
4B
1
1
AS 3B and 2 are adiabatic we have: T1 V1 = T2 V
2
T4 V1 1 = T3V2 1
T3
T4 T1 T1 T2 T1 T1 T3 T2
T1
T3 T2
T3 T2
3A
T4 T1
T2
T1
=
T3
T4
V2
T1
=1 =1
T2
V1
The Otto Cycle

V2
T
1
= 1 = 1
T2
V1
Want to have as high a compression ratio as possible!
Gasolineengine:
T1=300K and T2=580K
= 48%
(real gasoline engines have an efficiency closer to 30%)
Quantum Otto Cycle?
(not only relevant for understanding big, noisy smelly machines!)

Lecture 13: Heat Engines and
Second Law
Time: 2:35-3:35
Place: burnside 1B39
Office Hours: 2-3MW
Rutherford 411
Finn: p. 52-62; p. 66-69
Roadmap: Second Law

We would like to formulate a new principle of thermodynamics, a
second law, that explains what processes can occur and why
certain processes are excluded. . .
This will be our goal for the next two weeks
It is pedagogically traditional to motivate this second law

based on abstract considerations of engine performance
Roadmap: Second Law

(most
practical)
Heat engines
and Second Law
(most abstract)
Reversible
Heat engines
(Carnot Cycle)
Clausius
Inequality
Entropy based
formulation of
Second Law
Definition of
Entropy, S

In order to be useful, a series of
processes is needed: each process
delivering useful work AND returning
to exactly the same starting point!
The system can be operated
repeatedly over this closed engine
cycle, delivering a fixed work W over
each cycle
TH
Hot
|QH|
closed
engine
cycle
W
|QL|
TC
Cold

Engine efficiency:
TH
W
"=
QH
Hot
!
W
"U = QH "QL "W = 0
over closed cycle:

system returns to
starting state so !U=0
|QL|
TC
what we put in

|QH|
closed
engine cycle
what we get out
! !
Cold
!
W = QH "QL
QH "QL
QL
"=
=1"
QH
QH
! !
! !
!
Steam Engine Thermodynamics

Rankine Cycle
steam expands
spinning turbine
isobaric
heating
|QL|
|QH|
water heated to
boiling point,
vaporized and
superheated
adiabatic
compression
steam condenses
into water
adiabatic
compression to
boiler pressure
isobaric
cooling
adiabatic
expansion
water-vapor
coexistance
region
Note that a heat |QL| must always be

output to the low temperature
reservoir!
Stirling Engine: Type Alpha

Stirling Engine: reciprocating engine that works with
enclosed ideal gas (no phase transition takes place)
HOT
COLD
Regenerator
Can use any type of external heat source
Stirling Engine: Type Beta
COLD
HOT
!"#$%%&&&'(!)('*+,%-*.!/0)./1%2!*3-(%
4023(%5!/#2'678%5!/#2*39:'!2-1;
The Stirling Engine
Isothermal Compression (1-2)
regenerator
2
|QL|
TL
Isothermal (TL)
|QL|
|WL|
Alpha-type
Stirling Engine
2
<=,3*>;?3(-;!"#$%%&&&'(!)('*+,%-*.!/0)./1%
2!*3-(%4023(%5!/#2'678%5!/#2*39:'!2-1;
The Stirling Engine
3
Isochoric
@
@P
+|QR|
|QR|
2
|QL|
Isothermal (TL)
32
The Stirling Engine
Isothermal Expansion (3-4)
P
Isochoric
|QH|
|QR|
|QH|
Isothermal (TH)
2
|QL|
Isothermal (TL)
4
1
|WH|
42
The Stirling Engine
3
Isochoric
-|QR|
|QR|
|QH|
Isothermal (TH)
2
|QL|
Isothermal (TL)
Isochoric
|QR|
12
Gasoline Engine
1: Intake stroke: mixture of gasoline
vapor and air moves into cylinder via
suction as receeding piston enlarges
accessible volume
2: Compression Stroke: Gasoline

vapor-air mixture is compressed by
advancing piston, increasing pressure
and temperature
3: Ignition/Power Stroke: Mixture is

rapidly burned after ignition via a spark-plug: hot
combustion products expand and push piston
away
4: Exhaust/Exhaust Stroke: Combustion

products are exhausted until pressure drops to
atmospheric pressure; piston pushes all remaining
combustion products out of cylinder
(annimation from wikipedia)
The Otto Cycle

Gasoline engine extremely complex to model exactly: friction/turbulent
gas motion, conductive heat losses, chemical reactions. . .
Otto cycle: idealized gas engine cycle, assume:

(1)! Working substance at all times air
(can be modeled as ideal gas)
(2) All processes reversible
(3) No friction/turbulence
(4) No heat transfer through walls
The Otto Cycle

1
3A
3B
4A
3A: ignition
|QH|
4B
3B: power stroke

(adiabatic)
2
2: compression
stroke (adiabatic)
4A: exhaust
1: intake stroke
4B : exhaust stroke
|QL|
V
The Otto Cycle

Otto Cycle Summary:
3A: ignition
(isochoric)
3B: power stroke
(adibatic)
|QH|
2: compression
stroke (adibatic)
1: intake stroke
4B : exhaust stroke
We want to determine the efficiency of the Otto Cycle:

Recall that
QL
" =1"
QH
(need to calculate QL and QH)
Steps 1 and 4B cancel ; steps 3B and 2 are adiabatic
Need to calculate heat transfer QH and QL
!!
4A: exhaust
|QL|
V
The Otto Cycle

Otto Cycle Summary:
T3
3A
|QH|
3B
T2
4B
We assume that the heat capacities are constant for 3A and 4A
QL
" =1"
QH
T4 " T1
=1"
T3 " T2
T3
QH = "
CV dT = CV (T3 " T2 )
T2
T1
QL = " #
!T
CV dT = CV (T4 " T1 )
T4
4A
!!
!
T1
|QL|
V
Review: Adiabatic Process

"
PV = constant
CP
"#
CV
Reversible adiabatic
process for ideal gas
P = Nk B T /V
Ideal gas law: PV = Nk B T
V = Nk B T / P
TV "!#1 = constant
!
T " / P " #1 = constant
! !
Review: Adiabatic Process

P
(V4, P4)
(V2, P2)
adiabat:
PV " = constant
To
Isotherm:
!
(V3, P3)
!
Two states on isotherm:
Two states on adiabat:
P1V1 = P2V2
"
P3V3 = P4 V4
!
!
"
PV = Nk B To
= constant
(V1, P1)
V
(this is very useful in
problem solving)
The Otto Cycle

Otto Cycle Summary:
" =1"
V2, T3
|QH|
V!
2, T
!2
!
!!
2
1
=
=
!
!
!
! T2
T2 T3 " T
T3 " T2
2
!
!
3B
V1, T4
4A
|QL|
V1, T1
4B
" #1
" #1
AS 3B and 2 are adiabatic we have: T1 V1 = T2 V
2
T4 V1" #1 = T3V2" #1
T3
T4 " T1 T1 T2 "T1 T1 T3 "T2
T1
"
T3 " T2
T3 " T2
3A
T4 " T1
T2
T1
=
T3
T4
( )1
"
%
V2
T1
=1" =1"$ '
T2
# V1 &
!
!
The Otto Cycle

" V2 %
T
1
" = 1 " = 1 "$ '
T2
# V1 &
( )1
Want to have as high a compression ratio as possible!
! !Gasoline!engine:
!
!
T1=300K and T2=580K
" = 48%
(real gasoline engines have an efficiency closer to 30%)
Heat Engines and the Second Law

Historically, the second law of thermodynamics was formulated in
regards to heat engine performance
It is impossible to construct a device that, operating in a cycle, will produce no
effect other than the extraction of heat from a single body at uniform
temperature and the performance of an equivalent amount of work
Kelvin-Planck statement, 2nd Law
NOT ALLOWED!
QL
" =1"
= 100%
QH
TA;H
Hot
closed
engine
cycle
|QH|
! !
|W|
TL !
Cold
Heat must be rejected!

Lecture 14: Carnot Cycle
Time:
Place:
Office Hours:
Rutherford 411
Review: Idealized Heat Engine

Engine efficiency:
TH
W
"=
QH
Hot
!
W
"U = QH "QL "W = 0
over closed cycle:

system returns to
|QL|
TC
what we put in

|QH|
closed
engine cycle
what we get out
! !
Cold
!
W = QH "QL
QH "QL
QL
"=
=1"
QH
QH
! !
! !
!
Review: Steam Engine Cycle

Rankine Cycle
steam expands
spinning turbine
isobaric
heating
|QL|
|QH|
water heated to
boiling point,
vaporized and
superheated
adiabatic
compression
steam condenses
into water
adiabatic
compression to
boiler pressure
isobaric
cooling
adiabatic
expansion
water-vapor
coexistance
region
Review: The Stirling

Engine Cycle
3
COLD
Isochoric
|QR|
|QH|
Isothermal (TH)
2
|QL|
HOT
Isothermal (TL)
Isochoric
|QR|
Review The Otto Cycle

P
3A: ignition
|QH|
3B: power stroke

(adiabatic)
2: compression
stroke (adiabatic)
4A: exhaust
1: intake stroke
4B : exhaust stroke
|QL|

NOT ALLOWED!
QL
" =1"
= 100%
QH
T!"H
Hot
closed
engine
cycle
|QH|
! !
|W|
TL !
Cold
Idealized Refrigerator
Refrigerator efficiency:
TH
QL
"=
W
Hot
!
"U = QH "QL "W = 0
over closed cycle:

system returns to
|QL|
TL
Work we put in

applied to refrigerator cycle:
|QH|
Closed
refrigerator
cycle
Heat we extract
! !
Cold
!
! !
W = QH "QL
1
QL
"=
=
QH "QL QH /QL "1
! !
Refrigerators and the Second Law

The second law for refrigerators!
It is impossible to construct a device that, operating in a cycle, produces no
other effect than the transfer of heat from a colder to hotter body
Clausius statement, 2nd Law
NOT ALLOWED!
TH
Hot
Closed
refrigerator
cycle
|QH|
|QL|
TL
Cold
Work must be performed to transfer

heat from a body of lower to higher
temperature!

Two statements of the second law:
These statements are equivalent!

(we can prove this!)
Equivalence of Kelvin-Planck/Clausius
Statements of the Second Law
We wish to show:
KP True
C True
Equivalent to:
KP True
C True
KP True
C True
AND
or
KP False
C False AND
KP False
C False
This will be our formal strategy
Suppose that the Kelvin statement is untrue:
TH
Hot
closed
engine
cycle
|Q1|
|W|=|Q1|
TL
Cold
Then I could construct an engine that only extracts heat Q1
and delivers work W=Q1. . .
Use work W to power a refrigerator operating between the same reservoirs:
TH
Hot
closed
engine
cycle
|Q1|
|W|=|Q1|
TL
Cold
|Q2|+|Q1|
closed
fridge
cycle
|Q2|
The engine+refrigerator system can be viewed as a single composite device:
TH
Hot
Heat Q2 is
transferred
between the
reservoirs
With NO work
performed!
|Q1|
|W|=|Q1|
|Q2|+|Q1|
|Q2|
The Clausius
formulation of the
second law is
violated!
TL
Cold
The composite device has the effect of extracting heat Q2 from cold body and
delivering heat: |Q2 |+ |Q1 |- |Q1 |= |Q2 | to the hot body
Now it is your turn. . . Show that KP False
C False
(dont use your text!)
Hint: construct a
refrigerator operating
between two reservoirs that
violates the Clausius
formulation. . .
TH
|Q1| closed
|Q1|
TL
fridge
cycle
C False
TH
closed
engine
cycle
|W|
|Q2|
|Q1|
TL
|Q1| closed
fridge
cycle
|Q1|
C False

Composite system:
No heat delivered
to cold reservoir!
TH
|W|
|Q2|
|Q1|
|Q1|
|Q1|
Heat extracted
from hot reservoir
Q=|Q2|-|Q1|
Work performed:
|W|=|Q2|-|Q1|
TL
Only effect of composite

device is to extract heat
from one reservoir and
perform an equivalent
amount of work!
Kelvin-Planck
formulation of
second law
violated!
Carnots Problem
OK: but does thermodynamics tell me what is the maximum
engine/refrigerator efficiency I can achieve?
YES!
Does this efficiency depend on the working medium of the engine?

(steam vs gasoline, etc.)
NO!
1796-1832
Carnot was the first to ask these

questions. . .
And the first develop an idealized
engine model that could be used to
deduce the answers!
Nicholas Leonard Sadi Carnot
Father of thermodynamics
Carnot Cycle
Carnot considered a reversible engine that operates between only two
thermal reservoirs
Such an engine must have the following structure:
(using a gas as a working medium)
Carnot Cycle
2
TH
1!2: Adiabatic compression (Q=0)
QH
2!3: Isothermal expansion at

T=TH. Heat QH enters system
3!4: Adiabatic expansion (Q=0)
4!1: Isothermal compression
at T=TL. Heat QL leaves system
(all processes reversible)
3
1
TL
QL
Carnot Cycle
thermal reservoirs
(using an ideal gas as a working medium)
Why?
QH
3
adiab
atic
(2) If 1!2 and 3!4 NOT adiabatic,

heat will be exchanged: to do this
reversibly will require multiple reservoirs,
but engine only operates between two
reservoirs (by assumption)
TH
ic
2!3 and 4!1 isothermal
t
adiaba
(1) For the heat exchange to be

reversible, system temperature must be
always be infintesimally close to the
reservoir temperature
TL
QL
Carnot Cycle vs Real Engine

P
Carnot Cycle
2
adiaba
TH
TH
Plot in VT space
atic
adiab
tic
3
1
TL
TL
V
Otto Cycle
adiabatic
Plot in VT space
adiabatic
adiabatic
isochoric
isochoric
adiabatic
Need multiple thermal reservoirs

to carry out reversibly
isochoric
isochoric
Need only two thermal reservoirs

to carry out reversibly
Carnot Engine
TH
Hot
2
TH
adiaba
QH
QH
3
Cold
atic
TL
adiab
tic
QL
TL
QL
V
Carnot cycle: only reversible engine operating between two reservoirs at
fixed temperature
Important theoretically but not practically useful!
(reversible heat exchange too slow)
What if I go around the cycle in the counterclockwise direction?
Carnot Refrigerator
TH
Hot
2
TH
adiaba
QH
QH
3
Cold
atic
TL
adiab
tic
QL
TL
QL
V
Performed in opposite direction, Carnot cycle is a refrigeration cycle
Carnot cycle reversible
QH, QL and W are numerically

equal to values of engine cycle
(but with reversed sign)
Carnots Theorem
OK: but why is the Carnot cycle so important?
(other than as a student torture device, that is)
No engine operating between two reservoirs can be more efficient than a
Carnot engine operating between those same two reservoirs (Finn p. 59)
Carnots theorem
Proof:
TH
Hot
Assume that an engine E exists

that is more efficient than the
Carnot cycle
|Q1|
E
W=|Q1|-|Q2|
|Q2|
TL
Cold
Carnots Theorem
Carnots theorem
Proof:
TH
Hot
Introduce a Carnot engine C

operating between the same
reservoirs
Adjust the Carnot cycle so that
the work performed exactly
matches the work produced by
the hypothetical engine
|QC1|
|QE1|
C
E
W=|QE1|-|QE2|
|QE2|
TL
Cold
W=|QC1|-|QC2|
|QC2|
Carnots Theorem
Carnots theorem
Proof:
TH
Hot
The hypothetical engine is

assumed more efficient than the
Carnot engine, so that
"E = W > W = "C

QE1 QC 1
QE1 < QC 1
!
! (i.e.!heat delivered from hot

reservoir smaller for equivalent
!amount of work performed)
|QC1|
|QE1|
E
W=|QE1|-|QE2|
|QE2|
TL
Cold
C
W=|QC1|-|QC2|
|QC2|
Carnots Theorem
Carnots theorem
Proof:
TH
Hot
Now comes the trick: reverse

the direction of the Carnot cycle!
The Carnot engine becomes
a refrigerator
(Carnot cycle is reversible: work and
heat transferred simply change signs,
when the cycle is reversed)
We will let the Carnot

refrigerator be powered by the
work produced by engine E
|QC1|
|QE1|
E
|W|=|QE1|-|QE2|
|QE2|
TL
Cold
C
|QC2|
Carnots Theorem
Carnots theorem
Proof:
TH
Hot
Now consider the behavior of the

composite engine/refrigerator system
Total heat extracted from cold reservoir:
QL = Q2C " QE 2
= ( Q1C " W
!
!
) "( Q1E
= Q1C "QE1 = QH
!
But !
this is equal to heat
delivered !
to hot reservoir!
!
" W)
|Q1C|
|QE1|
C
E
|W|=|QE1|-|QE2|
|QE2|
TL
Cold
|Q2C|=|Q1C| -|W|
Carnots Theorem
Carnots theorem
Proof:
TH
Hot
We have constructed a device that

extracts heat from a cold to hot body
with no work being performed!
The Clausius statement of

the 2nd Law is violated!
(and the proof is complete)
We must have: "E # "C
|Q1C|
|QE1|
C
E
W=|QE1|-|QE2|
QE2
TL
Cold
|Q2C|=|Q1C|-|W|
Corollary to Carnots Theorem

All Carnot engines operating between the same two reservoirs have the
same efficiency (Finn p. 60)
Proof:
TH
Hot
Consider a Carnot cycle CA

operating as an engine and
Carnot cycle B operating as a
refrigerator between the same
thermal reservoirs
The engine is used to power
the refrigerator
The previous argument tells
us that "A # "B
operates as
engine
|QB1|
|QA1|
CA
W=|QA1|-|QA2|
CB
|QA2|
TL
Cold
But we can reverse the cycles and make Carnot cycle A

a refrigerator and Carnot cycle B an engine. . .
operates as
refrigerator
|QB2|

Proof:
But we can reverse the
cycles and make Carnot
cycle A a refrigerator and
Carnot cycle B an engine. . .
Now "B # "A
If both "A # "B and "B # "A
!
!
are true then
"A = "B
!
TH
Hot
|Q1B|
|QA1|
CA
CB
W=|QE1|-|QE2|
|QA2|
|Q2B|
TL
Cold
The
! working substance in the Carnot cycle has no effect on the cycles efficiency

Lecture 15: Clausius Inequality
Time: 2:35-3:25
Rutherford 411
Finn p. 59-66
Finn p. 71-75
Roadmap: Second Law

(most
practical)
Heat engines
and Second Law

(most abstract)
Reversible
Heat engines
(Carnot Cycle)
(today)
Clausius
Inequality
Entropy based
formulation of
Second Law
Definition of
Entropy, S
(Friday)
(today)

NOT ALLOWED!
QL
=1
= 100%
QH
T`H
Hot
closed
engine
cycle
|QH|
|W|
TL
Cold

The second law for refrigerators!
NOT ALLOWED!
TH
Hot
Closed
refrigerator
cycle
|QH|
|QL|
TL
Cold
Work must be performed to transfer

heat from a body of lower to higher
temperature!

Two statements of the second law:
These statements are equivalent!
Carnot Cycle
thermal reservoirs
(using a gas as a working medium)
Carnot Cycle
2
TH
12: Adiabatic compression (Q=0)
QH
23: Isothermal expansion at

34: Adiabatic expansion (Q=0)
41: Isothermal compression
3
1
TL
QL
Carnots Theorem
Carnots theorem
Proof:
TH
Hot
Assume that an engine E exists

that is more efficient than the
Carnot cycle
|Q1|
E
W=|Q1|-|Q2|
|Q2|
TL
Cold
Carnots Theorem
Carnots theorem
Proof:
TH
Hot
Introduce a Carnot engine C

operating between the same
reservoirs
Adjust the Carnot cycle so that
the work performed exactly
matches the work produced by
the hypothetical engine
|QC1|
|QE1|
C
E
W=|QE1|-|QE2|
|QE2|
TL
Cold
W=|QC1|-|QC2|
|QC2|
Carnots Theorem
Carnots theorem
Proof:
TH
Hot
The hypothetical engine is

assumed more efficient than the
Carnot engine, so that
E = W > W = C
QE1 QC 1
QE1 < QC 1
(i.e.heat delivered from hot

reservoir smaller for equivalent
amount of work performed)
|QC1|
|QE1|
E
W=|QE1|-|QE2|
|QE2|
TL
Cold
C
W=|QC1|-|QC2|
|QC2|
Carnots Theorem
Carnots theorem
Proof:
TH
Hot
Now comes the trick: reverse

the direction of the Carnot cycle!
The Carnot engine becomes
a refrigerator
(Carnot cycle is reversible: work and
heat transferred simply change signs,
when the cycle is reversed)
We will let the Carnot

refrigerator be powered by the
work produced by engine E
|QC1|
|QE1|
E
|W|=|QE1|-|QE2|
|QE2|
TL
Cold
C
|QC2|
Carnots Theorem
Carnots theorem
Proof:
TH
Hot
Now consider the behavior of the

composite engine/refrigerator system
Total heat extracted from cold reservoir:
QL = Q2C QE 2
= ( Q1C W
) ( Q1E
= Q1C QE1 = QH > 0
But
this is equal to heat
delivered
to hot reservoir!
W)
|Q1C|
|QE1|
C
E
|W|=|QE1|-|QE2|
|QE2|
TL
Cold
|Q2C|=|Q1C| -|W|
Carnots Theorem
Carnots theorem
Proof:
TH
Hot
We have constructed a device that

extracts heat from a cold to hot body
with no work being performed!
The Clausius statement of

the 2nd Law is violated!
We must have: E C
|Q1C|
|QE1|
C
E
W=|QE1|-|QE2|
QE2
TL
Cold
|Q2C|=|Q1C|-|W|

Proof:
TH
Hot
Consider a Carnot cycle CA

operating as an engine and
Carnot cycle B operating as a
refrigerator between the same
thermal reservoirs
The engine is used to power
the refrigerator
The previous argument tells
us that A B
operates as
engine
|QB1|
|QA1|
CA
W=|QA1|-|QA2|
CB
|QA2|
TL
Cold
But we can reverse the cycles and make Carnot cycle A

a refrigerator and Carnot cycle B an engine. . .
operates as
refrigerator
|QB2|

Proof:
But we can reverse the
cycles and make Carnot
cycle A a refrigerator and
Carnot cycle B an engine. . .
Now B A
If both A B and B A
are true then
A = B
TH
Hot
|Q1B|
|QA1|
CA
CB
W=|QE1|-|QE2|
|QA2|
|Q2B|
TL
Cold
The
working substance in the Carnot cycle has no effect on the cycles efficiency
Absolute Temperature Scale

The efficiency of a Carnot cycle depends only on the temperature of the reservoirs
(is independent of the cycle working substance)
Introduce absolute temperature scale based on Carnot cycle: this scale is
necessarily independent of any particular material properties
L
Define an absolute temperature is such a way that C = 1
H
1 and 2: defined as absolute temperatures of the thermal
reservoirs between which Carnot cycle operates
L
QL
1
C = 1
H
QH
L
QL
=
H
QH
Hot
|QH|
|W|
C
|QL|
Cold
Absolute Temperature Scale

I can assign a temperature to any reservoir in the following way:
Q1 1
=
Q2 2
Carnot Engine C12:
Introduce second Carnot engine C23:
Q2 2
=
Q3 3
Q1 Q2 1 2
=
Q2 Q3 2 3
Q1 1
=
Q3 3
(just the relation for the composite system C13)
Note:
2= 3
Q2
Q3
1 =
3
Q1
Q3
This means I can define the temperature of reservoir 1

and 2 in terms of temperature of reservoir 3
|Q1|
C12
|Q2|
C13
2
|Q2|
C23
|Q3|
I can apply
this argument toany series of reservoirs and
define any range of temperatures in terms of a fixed
reference (e.g. the triple point of water)
|W12|
|W23|
Equivalence of Ideal and Absolute

Temperature Scales
We are finally ready to demonstrate what I claimed at the beginning of this
class: the ideal and absolute temperature scale are one and the same. . .
We do this by taking an ideal gas through the Carnot cycle!
We want to calculate QH and QL:
23: Isothermal expansion at T=TH
2
TH
No change in internal energy, so Q=-W

(1st Law)
V3
Q H = W =
V2
dV
V
V
V
= Nk B TH ln 3
V2
41:Isothermal
compression
at T=TL
V
Q L = Nk B
TL ln 1 (same argument)
V4
QH
|QH|
3
V3
PdV = Nk B TH
= 1 QL
1
TL
|QL|
TL V1 1 = TH V2 1
CP
=
CV
TH
adiaba
(dividing two
equations)
QH
3
V4 V3
=
V1 V2
QH
atic
= 1 QL
adiab
1
1
THV3 = TL V4
tic

Temperature Scales
TL
QL
The ratio of |QL/QH|:
QL Nk B TL ln (V1 /V4 ) TL ln (V4 /V1 ) TL

=
=
=
QH Nk B TH ln (V3 /V2 ) TH ln (V3 /V2 ) TH
= V4 /V1
V
Q H = Nk B TH ln 3
V2
V
Q L = Nk B TL ln 1
V4

Temperature Scales
The efficiency of the Carnot cycle:
scale are one and the same!
QH
atic
The ideal and absolute temperature
QH
adiab
= 1 QL
3
tic
L TL
=
Moreover. . .
H TH
TH
adiaba
C =
TL
1 T
H
TL
QL
Carnot Cycle as Building Block

The Carnot cycle can be viewed as a building block for a general
reversible process
P
Consider a general
reversible cycle. . .
We build this general process out of

a zig-zag path of Carnot cycles!

First Carnot cycle satisfies:
Q1H Q1L
=
T1L
T1H
Q
T1H
= 1H
T1L
Q2L
TiH
|Q1H|
T1H
Q1H Q1L
=0
+
T1H
T1L
(Q1H and Q1L have opposite signs:

heat enteringand leaving system)
|QiH|
T1L
|Q1L|
|QiL|
The ith Carnot cycle satisfies:
TiL
QiH
Q
+ iL = 0
TiH
TiL
I add up contributions from all cycles:
Q
Q
Q3H
1H
2H
+
+
+ +
0=
T1H
T2H
T3H
) +(
Q1L
Q
Q
+ 2L + 3L + +
T1L
T2L T3L
=
i
QiH
TiH
dQ
continuous
T
limit!
H
+
i
QiL
TiL
+ dQ =
T
L
dQ
T

We conclude:
dQ
T
=0
dQ
reversible cycle
But whatif the process is

NOT reversible?
If a single cycle is not reversible, the cycles efficiency is lower than

the Carnot efficiency:
QiL
1Q
iH
<
QiH QiL
+
<0
TiH TiL
QiL
QiH
C = 1 TiL
TiH
>
TiL
TiH
QiL
TiL
>
(more heat is transferred to cold reservoir

for an equivalent irreversible cycle)
QiH
TiH
Clausius Inequality
dQ
T
=0
dQ
reversible cycle
But
what if the process is
NOT reversible?
For single cycle:
QiH QiL
+
<0
T
TiH
iL
Integrating this result over all processes making up general cycle:
dQ
To
<0
In general
irreversible cycle
dQ
To
Clausius inequality
To: reservoir temperature!

T=To only or reversible
process
Clausius Inequality and Entropy

The Clausius inequality may seem amusing but needless
to say it is a highly abstract result. . .
Surgeon Generals Warning: excessive mathematical
formalism not grounded in physical intuition has been
known to be hazardous to your brain!
What is the inequality really telling us?

The Clausius inequality allows us to introduce a new function
of state*: this will be known to us as the entropy!
(*that is a function defined for all equilibrium states)
P
dQ
(breaking up cycle
in two reversible
paths, R1 and R2)
reversible cycle
dQ
dQ
R2
dQ
T
dQ
T
f
2
R1
=0
dQ
Define Entropy S:
This quantity is path

independent!
dQ
=
=
R
R
f
R2
=0
S = S f Si
dQ
T
R: path must
be reversible!

A differential entropy change:
dS =
dQ
T
reversible process
dS: exact differential

dQ: inexact differential
T: converts an inexact differential into an exact differential

(known as integrating factor)
Note that pressure plays the same role for work:
dW = PdV
dW
dV =
P

Lecture 14: Entropy I
Time: 2:35-3:25
Office Hours: 2-3MW
Rutherford 411
Reading: Finn p. 75-84
Roadmap: Second Law

(most
practical)
Heat engines
and Second Law

(most abstract)
Reversible
Heat engines
(Carnot Cycle)
(review)
Clausius
Inequality
Entropy based
formulation of
Second Law
Definition of
Entropy, S
(today)
(review)
Review: Carnot Cycle

Only reversible cycle
between exactly two
thermal reservoirs

23: Isothermal expansion at
2
TH
41: Isothermal compression

QH
3

1
C = 1 QL = 1 TL
QH
TH
Carnot engine efficiency
TL
QL
Review: Carnot Cycle as Building Block

The Carnot cycle can be viewed as a building block for a general
reversible process
P
Consider a general
reversible cycle. . .
We build this general process out of

a zig-zag path of Carnot cycles!

We build a general process out of a
zig-zag path of Carnot cycles!
TiH
QiH
TiH
QiH
=
TiL
QiL
QiL < 0
(Heat rejected)
TiL
= 1
TiH
TiL
QiL
Theith Carnot cycle satisfies:
QiH QiL
+
=0
TiH TiL

We build a general process out of a
zig-zag path of Carnot cycles!
TiH
QiH
If ith cycle is irreversible:
i < C
= 1 QiL
QiH
TiL
QiL
if
So
ith
cycle irreversible:
QiL TiL
>
QiH TiH
QiH
QiL
>
TiH
TiL
V
QiL < 0
QiH QiL
+
<0
TiH TiL
Heat rejected
Review: Clausius Inequality

Integrating over all component
cycles:
dQ
T
dQ
=0
reversible cycle
dQ
To
<0
irreversible cycle
Combining these results:
dQ
To
Clausius inequality
Important: To is the temperature of external reservoir

supplying
heat! System temperature and reservoir
temperature are equal only in the reversible case!
Review: Clausius Inequality and Entropy

P
dQ
T
(breaking up cycle
in two reversible
paths, R1 and R2)
reversible cycle
dQ
R1
dQ
R1
R2
dQ
R2
dQ
i
dQ
T
R2
dQ
T
R1
=0

independent!
R2
=0
V
Define Entropy S: f
S = S f Si dQ
T
R
R: path must be reversible!
Review: Clausius Inequality and Entropy

A differential entropy change:
dS =
dQ
T
reversible process
dS: exact differential

dQ: inexact differential
T: converts an inexact differential into an exact differential

(known as integrating factor)
Example Calculation of Entropy Changes

At this point, while we lack physical intuition into what entropy is in a
physical sense, we possess the mathematical machinery to calculate
its change for thermodynamic processes
Key idea: Entropy is an equation of state. To calculate the change in
entropy for a given process, all we need to know is the entropy in the final
and initial equilibrium states. The actual details of the real process, e.g.
whether it is reversible or irreversible, are irrelevant.

Example 1: heating a beaker of 1kg of water at atmospheric pressure from
20oC to 100oC.
20oC
20oC
100oC
20oC
Initial equilibrium
state
100oC
100oC
Final equilibrium
state
The details of the heating process do not matter: we just need to know the
entropy change between the final and initial equilibrium states
To calculate the entropy change, we need to construct an equivalent
reversible process between the same initial and final equilibrium states

An equivalent reversible process: put
system in contact with an infinite series
of thermal reservoirs. . .
20oC
20.001oC
20.002oC
20oC
Initial equilibrium
state
20.001oC
System temperature and

reservoir temperature will
always be infinitesimally close.
100oC
....
20.002oC
100oC
Final equilibrium
state

Reversible differential heat
exchange at constant pressure:
dQ = C P dT
dS =
dQ
T
C P dT
T
T
T
dT
CP
C
The total change in entropy: S =
dT
P
T
o
o
T T
Ti=20 C; Tf=100
C
T
(C is approximately constant over
temperature range of interest)
20.001oC
373
= C P ln = (4.2kJ/K)
ln 293 1kJ/K
T
Tf
i

Example 2: irreversible expansion of an ideal gas
adiabatic
walls
N molecules
of ideal gas
T
Initial Equilibrium state: gas at temperature T occupies volume V/2
partition
removed
No work done; no
heat transferred;
temperature stays
constant!
Final Equilibrium state: gas at temperature T occupies entire volume V

Equivalent reversible process: isothermal expansion of
an ideal gas
diathermal
walls
N molecules
of ideal gas
Pext=P
Initial Equilibrium state: gas at temperature T occupies volume V/2

gas expands
reversibly
against piston
T
Final Equilibrium state: gas at temperature T occupies volume V

Equivalent reversible process: reversible isothermal expansion of ideal
gas (against a piston applying a differentially balancing pressure P)
The internal energy does not change during
isothermal expansion of ideal gas , so first law tells us:
Q = W
The work performed during the equivalent reversible expansion:

Vf
Vf
Vf
dV
W = PdV = Nk B T
= Nk B T ln
Vi
V V
V
Q
W = Nk
The entropy change is then: S =
=
B ln 2
T
T
(process isothermal so

temperature is
constant)
is performed in real irreversible
Remarkably, no work
process and no heat
is transferred!

Example 3: Entropy change of thermal reservoir: irreversible
heat flow Q
Thermal Reservoir
Temperature T
Equivalent reversible process: reversible heat flow Q
Thermal Reservoir
Temperature T+dT
Thermal Reservoir
Temperature T

Equivalent reversible process: reversible heat flow Q
Thermal Reservoir
Temperature T+dT
Thermal Reservoir
Temperature T
dQ 1 f
Q
S =
= dQ =
T
Ti
i T
Entropy change of thermal reservoir
for heat
flow Q:
S res
Q
=
T

Example 4(a): Irreversible work performed on isolated system
Initial State
TC
Increase temperature of
reservoir by performing
irreversible work
Final State
TH
TH>TC
Equivalent Reversible Process: Reversible isobaric heating.

Place system in contact with series of thermal reservoir ranging in
temperature from TC to TH.

Equivalent Reversible Process: Reversible isobaric heating.
Place system in contact with series of thermal reservoir ranging in
temperature from TC to TH.
Initial State
TC
Final State
TH
TH>TC
dQ = C P dT
Tf
Tf
Tf
dT
dQ = C P
=
dT C P
= C P ln
T
T
T
Ti
Ti T
Ti
Tf

Example 4(b): Irreversible work performed on system in thermal
equilibrium with reservoir
Thermal
reservoir
TC
TC
Q=W
Equivalent Reversible Process: Reversible transfer of heat

Q=W into reservoir.
S =
W
T
Principle of Increasing Entropy

Consider a thermodynamic process where
path from i->f is performed irreversibly and P
path from f->i is performed reversibly
dQ
To
i
f
dQ
To
dQ
To
0
i
+
R
f
i
dQ
T
dQ
T
Irreversible Path
Clausius inequality
Reversible Path
Differential Change:
dQ
T
dQ
To
= S f Si = S
dS

dQ
dQ
To
dS
= dS
reversible
dQ
To
< dS
irreversible
What does this relation tell us?
For irreversible process there is an entropy change dS: this change is

larger than the heat delivered over the temperature of the heat source To
For adiabatic process: dQ = 0
dS 0
S 0

(finite process)

S > 0 (adiabatic process, irreversible)
S = 0 (adiabatic process, reversible)
The entropy of a thermally isolated system increases in

any irreversible process and is unaltered in a reversible
process. This is the principle of increasing entropy
(Finn p. 79)
In addition, if system mechanically isolated from environment, no work can

be performed and the internal energy is constant:
S 0
U = constant
Isolated System
Entropy Change of Universe

In order to apply the principle of increasing entropy in general we
can imagine embedding our system within an isolated enclosure
Reservoir 1: T1
Q1
System
Q2
Reservoir 2: T2
Q3
Reservoir 3: T3
We will call the enclosure our thermodynamic universe

We can further imagine sub-dividing our system into interacting
sub-systems S1, S2, S3. .
Reservoir 1: T1
S1
Q1
S2 S5 S8
S3 S6 S7
S4
Reservoir 2: T2
Q2
Q3
Reservoir 3: T3
Thermodynamic universe

Reservoir 1: T1
Q1
Si
Reservoir 2: T2
c
Q2
Q3
Reservoir 3: T3
S res
(Q2 )
=
T2
Q positive implies
heat flow to
system and away
from reservoir, so
reservoir looses
entropy Q/T
Thermodynamic universe
The net entropy change of all

subsystems and reservoirs must be positive
N
M
S univ
(Qi )
= Si +
0
i=1
i=1 Ti
Entropy change of Entropy change of

subsystems
reservoirs
But the entropy of a

given individual
subsystem or reservoir
can decrease!

S univ 0
Second Law of Thermodynamics
(increasing entropy formulation)
S univ = Ssystem +S env

N
S env=
i=1
f
(Qi )
Ti
(dQ)
To
(exchange with
discrete number
of reservoirs)
(exchange with
continuous series of
reservoirs)

This is simply a reformulation of the Clausius Inequality!
P
dQ
To
Reversible Path
Clausius inequality
(multiply
by -1)
i
f
dQ
To
dQ
i
(dQ )
To
Irreversible Path
0
dQ
T
= Ssystem V
f
(dQ )
To
= S env
dQ
T

Consider a system at constant volume and initial temperature
Ti: the system is brought into diathermal contact with a
reservoir at temperature Tf:
System has a heat
capacity CV
(assume independent of
temperature)
System
Thermal
Reservoir
(Tf)
The system and reservoir are placed inside an adiabatic enclosure
What is the entropy change of the thermodynamic universe?

Consider a system at constant volume and initial temperature
Ti: the system is brought into diathermal contact with a
reservoir at temperature Tf:
System has a heat

capacity CV
System
Thermal
Reservoir
(Tf)
Tf
Tf
T
dT
dQ
Ssystem =
= CV
= CV ln f
T T
Ti
T T
CV (T f Ti )
Q
The entropy change of the
S env = =
environment (reservoir):
f
T
Tf
S univ = CV ln
f /Ti ) +C
(T
V(Ti T f ) /T
f
The entropy change of
the system is:

Lecture 14: Entropy II
Time: 2:35-3:25
Office Hours: 2-3MW
Rutherford 411
Reading: Finn p. 75-84
Roadmap: Second Law

Heat engines
and Second Law

(today)
Reversible
Heat engines
(Carnot Cycle)
Clausius
Inequality
Entropy based
formulation of
Second Law
Definition of
Entropy, S
(review)
(review)
Clausius Inequality
Integrating over all component
cycles:
dQ
T
dQ
construct arbitrary
cycle out of Carnot
cycle building blocks
=0
reversible cycle
dQ
To
<0
irreversible cycle
Combining these results:
dQ
To
Clausius inequality
Important: To is the temperature of external reservoir

supplying
heat! System temperature and reservoir
temperature are equal only in the reversible case!

P
dQ
T
(breaking up cycle
in two reversible
paths, R1 and R2)
reversible cycle
dQ
R1
dQ
R1
R2
dQ
R2
dQ
i
dQ
T
R2
dQ
T
R1
=0

independent!
R2
=0
V
Define Entropy S: f
S = S f Si dQ
T
R
R: path must be reversible!

Principle of Increasing Entropy!
P
dQ
To
Reversible Path
Clausius inequality
(multiply
by -1)
i
f
dQ
To
dQ
i
(dQ )
To
Irreversible Path
0
dQ
T
= Ssystem V
f
(dQ )
To
= S env
dQ
T

S univ 0
Second Law
of Thermodynamics
S env
i=1
f
(Qi )
Ti
(dQ)
To
(exchange with finite number of

reservoirs, temperatures
discretely separated)
(exchange with
reservoirs)
Entropy Change for Adiabatic Process

In the special case of an adiabatic process:
S univ = Ssystem
= Ssystem 0
S univ
Law of Thermodynamics
Second
For a thermally isolated system
S env = 0
Implications of Increasing Entropy

The increasing entropy formulation of the second law is very
powerful. We will go backwards and apply it to specific
examples.
Heat
Conduction:
T1
T2
Heat Q is transferred between two

temperature reservoirs
S univ
1 1
Q Q
=
+ = Q 0
T1 T2
T2 T1
Evidently, T2<T1: heat flows from high to low temperature
If T1=T2 then the transfer can take place reversibly (Suniv=0)
Review: Idealized Heat Engine

Engine efficiency:
TH
W
=
QH
Hot
U = QH QL W = 0
over closed cycle:

system returns to
|QL|
TL
what we put in

|QH|
closed
engine cycle
what we get out
Cold
W = QH QL
QH QL
QL
=
=1
QH
QH

QH QL
Heat Engines: S univ =
+
Hot
TH
TL
solve for |QL|
|QH|
TL
QH
QL = TL S univ +
TH Lost work!
|W|
TL
|QL|
W = QH 1 TL S univ
TH
TL
Cold If engine
S univ = 0
is reversible:
TL
Expected results
Q
Q
=
W = QH QL
H
L T
for Carnot cycle!
H
QL
W
TL
=
=1
W =QH 1
QH
QH
TH

closed
engine
cycle
TH

TH
Hot
closed
engine
cycle
|QH|
|W|
|QL|
TL
Cold
W = QH QL
W QL
=
=1
QH
QH
TL
QH
QL = TL S univ +
TH
TL
W = QH 1 TL S univ
TH
If no heat is rejected: Q = 0
L
T
L QH
TL S univ =

TH
S univ < 0
Therefore it is impossible to construct a cyclic

engine that extracts heat from a reservoir and
performs an equivalent amount of work (KelvinPlanck statement of second law)

Apply the Principle of Increasing Entropy to a Refrigerator
TH
closed fridge
cycle
Hot
|QH|
|W|
|QL|
TL
Cold
W = QH QL
(1) Show that minimum work is required for a

reversible cycle
(2) Use the increasing entropy formulation of the
second law to show that it is impossible to construct
a cyclic refrigerator that only extracts heat from a
reservoir and returns it to a higher temperature
reservoir
(3) I suggest you solve for |QH|.
closed fridge
cycle
QH
QL
For refrigerator: S univ =
TH
TH
TL
Hot
solve for |QH|
TH
|QH|
QH = TH S univ+
QL
TL
T
H
|W|
- 1 +T S
W
=
Q
L
H univ
|QL|
TL
TL
S univ = 0 min work performed

Cold
TH

univ = QH 1 S
<0
W = 0
TL
W = QH QL
(Clausius statement of second law proved)

Lecture 14: Entropy III
Time: 2:35-3:25
Office Hours: 2-3MW
Rutherford 411

S univ 0
Second Law
of Thermodynamics
S env
i=1
f
(Qi )
Ti
(dQ)
To
(exchange with finite number of

reservoirs, temperatures
discretely separated)
(exchange with
reservoirs)
Entropy Change for Adiabatic Process

In the special case of an adiabatic process:
S univ = Ssystem
= Ssystem 0
S univ
Law of Thermodynamics
Second
For a thermally isolated system
S env = 0

In the last lecture we applied the principle of increasing entropy to
engine/refrigerator cycles
In particular, we showed that an increase in the entropy of the
universe SUniv results in a loss of potential work output TLSUniv.
(this result is general, see Finn. p. 94-95)
In every irreversible process with net entropy gain SUniv an

energy TLSUniv becomes unavailable for work
Today, we will revisit some of the examples of the previous lecture where
we calculated entropy changes for certain processes (isobaric heating/

irreversible expansion)
In these examples we calculated the entropy change of the system:
but what is the entropy change of the thermodynamic universe?

Irreversible adiabatic expansion of ideal gas:
partition
removed
N molecules
of ideal gas
T
Entropy change of outside environment:
Entropy change of system:
S env = 0
Ssystem = k B ln 2
Entropy change of thermodynamic universe:
(last lecture)
S univ = k B ln 2
(process adiabatic)

Reversible isothermal expansion of ideal gas:
Q
N molecules
of ideal gas
reversible expansion
against piston
Pext=P
Q = W = Nk B T ln 2
Pext=P
T
Entropy change of outside environment:

Ssystem
In a process performed
reversibly entropy changes in
the environment balance
positive (or negative) entropy
changes in the system
S env = Q/T
= Q/T (process reversible!)
Entropy change of thermodynamic universe:
(last lecture)
S univ = 0

Isobaric heating (irreversible, one-stage)
20oC
20oC
20o
100o
C
Initial equilibrium state C
Entropy change
of system:
Ssystem = C P
Entropy change of environment:

Entropy change of universe:
100o
C
Final equilibrium
state
Tf
Ti
= (4.2kJ/K) ln 373 1.01kJ/K
293
S env = Q/T f = C P (T f Ti ) /T f
S univ = Ssystem +S env 0.1kJ/K
ln
100oC
80
= (4.2kJ/K)
373
0.9kJ/K

Isobaric heating (irreversible, two-stage)
20oC
50oC
20o
50oC
C
Initial equilibrium state
100oC
Final equilibrium state
Ssystem 1.01kJ/K
Entropy change of environment:
373 323
323 293
C
= C P
P
323
373
S univ = Ssystem +S env 0.06kJ/K
= 0.95kJ/k
(entropy change lower, as process

closer to reversible)
(the same!)
S env = Q1 /T50 Q2 /T100
100oC

20oC
An equivalent reversible process: put

system in contact with an infinite series
of thermal reservoirs. . .
20.001oC
20.002oC
20oC
20.001oC
Initial equilibrium
state
dS env
....
dQ
=
T
100oC
20.002oC
100oC
Ssystem 1.01kJ/K
Tf
change of environment:
Entropy
dQ
T
Ti
S env =
S univ = 0
= Ssystem
Final equilibrium
state
Central Equation of Thermodynamics

We can express the first law for a differential/reversible process
= TdS
dU = dW +dQ
= PdV
= TdS PdV
dU

This equation is a relation between state functions and variables
These quantities are defined for every equilibrium state
This equation thus holds true for all processes

We can express the first law for a differential/reversible process
= TdS
dU = dW +dQ
= PdV
= TdS PdV
dU

U
U
dU = dS + dV

V S
S V
=T
= P
Writing U as a function of S and V: U(S, V)

Equivalently, we can express entropy as a
function of U and V:
S(U,V)
1
P
The central equation gives: dS =
dU + dV
T
T
S
S
dS = dU + dV
U V
= 1/T
V U
= P /T
Temperature is related to how a systems entropy increases with energy input
High temperature: low entropy increase with given energy input
(system readily gives up energy)
Low temperature: large entropy increase with given energy input

(readily accepts energy)
Entropy of Ideal Gas

We can use the central equation to deduce the entropy of
an ideal gas
U
CV =
T V
dU = CV dT
Central Equation:
P = C dT
1
P
+ dV
V
dS = dU + dV
T
T T
T
dT
dV
P /T = Nk B /V
= CV +Nk B
V
T

dT
dV
dS = CV
+Nk B
T
V
S = CV lnT +Nk B lnV +S o
(integration by inspection)
= C P CV

For a reversible,
adiabatic process the entropy of the system
is constant:
C
C ) lnV = constant
+(C
lnT
lnT +( 1) lnV = constant

1
= constant
ln T V

TV
= constant
Entropy of Rubber Band

As another example of the formalism for calculating entropy, consider a
rubber band system
tension
The entropy is a function of temperature and the

rubber-band extension L:
S(T, L)
We will assume that the internal energy of the

rubber band is a function purely of temperature:
U(T) = T

The entropy is a function of temperature and the
rubber-band extension L:
S(T, L)
We will assume that the internal energy of the

rubber band is a function purely of temperature:
U(T) = T
0
The first law for the rubber band: dU = dQ + dL
constant
dQ dU
C L = =
=
dT L dT L
AT
(L L o )
Rubber band equation of state: =
Lo
equilibrium
extension of rubber band
L
o :

Central Equation for rubber band:
1
dS = dU dL
T
T
dT A
(L L o ) dL
dS =
Lo
T
A
2
S(T,L)
(L
L
)
+S o
= lnT
o
2L o
band decreases with

Entropy of rubber
increasing extension!
U(T) = T
AT
(L L o )
=
Lo
Rubber Band Adiabat

We can use our expression for rubber band entropy to
deduce the expression for a rubber-band adiabat!
(e.g. relation satisfied by T and L if process is reversible and
there is no heat flow)
A
2
(L
L
)
+S o = constant
S(T,L) = lnT
o
2L o
(for a reversible
adiabatic process)
ln [ T
T

A (LL o ) 2
e 2Lo
] = constant
A (LL o ) 2
e 2Lo
= constant
(temperature of rubber
band increases for
adiabatic stretching!)
TS-Space
Plots of thermodynamic processes in TS-coordinates are quite useful
Isotherms (constant temperature) and adiabats (constant entropy)
are horizontal and vertical lines in TS-space
The Carnot cycle has a particularly simple form:
adiaba
TH
TH
Plot in TS space
adiab
tic
TL
atic
TL
V
The heat exchanged for a reversible process is
the area under the TS curve:
Q=
TdS
Entropy Maximization Principle

What does a system do when a constraint is removed?
(for example a barrier is removed, allowing a gas to expand)
(an adiabatic separating wall is replaced with a diathermal wall)
The system will evolve irreversibly and spontaneously to a new state of
thermodynamic equilibrium consistent with the absence of the constraint
How do we determine this new equilibrium state?

The process must move in a direction that increases the net entropy
of the system+enviornment: when equilibrium is reached the entropy
will no longer increase
In fact, the final state must maximize the net entropy of the system
+enviornment, otherwise a spontaneous process would occur to the
state with greater entropy

This final stronger form of the Second Law of thermodynamics
allows us to predict the equilibrium values adopted by a system
when a constraint is relaxed:
The values assumed by the extensive parameters (U, V, N) in the
absence of an internal constraint are those that maximize the
entropy S over the space of equilibrium states
(Second Law, Entropy Maximization)

Consider two sub-systems that are allowed to exchange energy
connected by a rigid diathermal wall; the entire system is isolated.
U = U1 + U 2
V = V1 +V2
Sub-System 1
Sub-System 2
S1 (U 1 ,V1 )
S 2 (U 2 ,V2 )
is
entropy of the system
The total
dU 1 + dU 2 = 0
S(U,V ) = S1 (U 1 ,V1 ) +S 2 (U 2 ,V2 )
S 2
1 1
S
dS = 1 dU +
dU 2 = dU 1
1
U 2 V
T1 T2
U 1 V
= dU
1
T1 = T2
Entropy maximization implies: dS = 0

(thermal equilibrium)

What if the sub-systems can exchange energy and
volume? (e.g. we introduce a movable, diathermal partition)
Total system energy

and volume constant
(as before)
Sub-System 1
Sub-System 2
S1 (U 1 ,V1 )
S 2 (U 2 ,V2 )
S(U,V ) =
S1 (U 1 ,V1 )
+S 2 (U 2 ,V2 )
will result
Show that entropy maximization
inequality of the temperatures and pressures
Recall the following:
S
S
P /T = ; 1/T =
V U
U V

What if the sub-systems can exchange energy and volume?
(e.g. we introduce a movable, diathermal partition)
U = U1 + U 2
V = V1 +V2
Sub-System 1
Sub-System 2
S1 (U 1 ,V1 )
S 2 (U 2 ,V2 )
The totalentropy of the S(U,V ) =
system is
dV1 + dV2 = 0
,V )
S1
(U 1 ,V1 )+S 2 (U
2 2
S 2
S1
S1
S 2
dS =
dV2
dU 2 +
dV1 +
dU 1+
V2 U
U2 V
V1 U
U 1 V
= dV1
= dU 1
S1 S2
S1 S2

=
dV1
dU 1 +
V
U 1 V U 2 V
1U V2 U
dU 1 + dU 2 = 0

S1 S2
S1 S2
dS =
dU 1 +
dV1

U
1 U V2 U
U 1 V 2 V
1
=0
=0
and volume
are varied
independently)
(energy
Entropy maximization: dS = 0
S1 S 2
U
1 V 2 V
1
T1 = T2
2
S1 S 2
V
1 U
2 U
T1 T2
=
P1 P2
P1 = P2
(and mechanical
equilibrium)
Entropy in Statistical Mechanics

Entropy is clearly a powerful concept: if only we had
some idea of what entropy actually is (physically)!
In order to understand entropy, rather than just exploit it as a formal
tool, we need to introduce concepts from statistical mechanics
In statistical mechanics, entropy is a measure of the number of ways
(microstates) a system has available to store a particular fixed energy
What is a microstate?
A particular microscopic configuration adopted by the physical system
Many microstates are consistent with a given observable
(e.g. macroscopic) state
Entropy and Microstates

Example of microstate: a particular configuration of particles in a box
Microstate 1
Microstate 2
Microstate 3
A system rapidly explores its accessible microstates

Fundamental Postulates of Statistical Mechanics:
A system makes extremely rapid transitions throughout
its available microstates
All microstates of an isolated system have equal probability
An isolated system evolves to a macroscopic state that
maximizes the number of available microstates ()
More microstates available if the gas fills the entire box!

For an isolated system, entropy is maximized; the
number of microstates is maximized. . .
Is entropy just equal to the number of microstates?
Not quite. . .
Entropy is related to the logarithm of the number of microstates ()
(: multiplicity)
S k B ln
(Definition of entropy in
terms of microstates)
maximized implies that S is maximized, but why are they

not simply equal?

Entropy is extensive. . . BUT
If I have subsystem 1 with microstates 1
. . .and subsystem 2 with microstates 2
The total number of microstates is the product 12
(not the sum 1+2)
However, according to our definition, the total system entropy:
S tot k B ln (1 2 ) = k B ln 1 +k B ln 2
= S1 +S 2
. . .is the sum of the entropy of the two subsystems!
(so the logarithm ensures that the entropy is extensive)

Lecture 14: Entropy IV
Time: 2:35-3:25
Office Hours: 2-3MW
Rutherford 411

The values assumed by the extensive parameters (U, V, N) in the
absence of an internal constraint are those that maximize the
entropy S over the space of equilibrium states

Consider two sub-systems that are allowed to exchange energy
connected by a rigid diathermal wall; the entire system is isolated.
U = U1 + U 2
V = V1 +V2
Sub-System 1
Sub-System 2
S1 (U 1 ,V1 )
S 2 (U 2 ,V2 )
is
entropy of the system
The total
dU 1 + dU 2 = 0
S(U,V ) = S1 (U 1 ,V1 ) +S 2 (U 2 ,V2 )
S 2
1 1
S
dS = 1 dU +
dU 2 = dU 1
1
U 2 V
T1 T2
U 1 V
= dU
1
T1 = T2
Entropy maximization implies: dS = 0


What if the sub-systems can exchange energy and
volume? (e.g. we introduce a movable, diathermal partition)
Total system energy

and volume constant
(as before)
Sub-System 1
Sub-System 2
S1 (U 1 ,V1 )
S 2 (U 2 ,V2 )
S(U,V ) =
S1 (U 1 ,V1 )
+S 2 (U 2 ,V2 )
Show that entropy maximizationwill result in

equality of the temperatures and pressures of the
two sub-systems
Recall the following:
S
S
P /T = ; 1/T =
V U
U V

What if the sub-systems can exchange energy and volume?
(e.g. we introduce a movable, diathermal partition)
U = U1 + U 2
V = V1 +V2
Sub-System 1
Sub-System 2
S1 (U 1 ,V1 )
S 2 (U 2 ,V2 )
The totalentropy of the S(U,V ) =
system is
dV1 + dV2 = 0
,V )
S1
(U 1 ,V1 )+S 2 (U
2 2
S 2
S1
S1
S 2
dS =
dV2
dU 2 +
dV1 +
dU 1+
V2 U
U2 V
V1 U
U 1 V
= dV1
= dU 1
S1 S2
S1 S2

=
dV1
dU 1 +
V
U 1 V U 2 V
1U V2 U
dU 1 + dU 2 = 0

S1 S2
S1 S2
dS =
dU 1 +
dV1

U
1 U V2 U
U 1 V 2 V
1
=0
=0
and volume
are varied
independently)
(energy
Entropy maximization: dS = 0
S1 S 2
U
1 V 2 V
1
T1 = T2
2
S1 S 2
V
1 U
2 U
T1 T2
=
P1 P2
P1 = P2
(and mechanical
equilibrium)
Entropy in Statistical Mechanics


Microstate 1
Microstate 2
Microstate 3


Not quite. . .
(: multiplicity)
S k B ln

not simply equal?

(not the sum 1+2)
= S1 +S 2
How to Calculate the Entropy?

Now that we have defined the entropy in explicit physical terms, can we
calculate the entropy directly for some systems of interest?
The answer is, yes we can: but once we do so we are no longer doing
thermodynamics, this is the proper domain of statistical mechanics!
While statistical mechanics is not the primary focus of this class, I have
decided to present some examples of entropy calculations
Entropy of two state systems (pedagogical warm-up)
Entropy of ideal gas (from which we can derive the ideal gas law!)
These examples will be considerably more mathematically involved
than what we have done up to this point, but I think the class can
follow these calculations, and I think (hope) will find them rewarding
(I will have some problems on this material, but no exam/test coverage)
Microstates of Two-State System

Consider a system that can exist in only two states
The two-state system is an excellent toy model for statistical
interpretation of entropy in terms of microstates
Moreover, two-state systems play a fundamental role in quantum
theories of magnetic phenomena
(e.g. quantum mechanics tells us that the magnetic dipole moment
of a spin particle can only have two possible orientations, parallel
and anti-parallel to the magnetic field direction)
Also serve as useful models for problems in classical statistical

physics, such as polymer conformation and even DNA melting
The mathematics is analogous to coin flipping!

Let us denote these states: heads and tails
Heads State
Tails State
The mathematics is analogous to coin flipping!

H
H
T
T
H
H
T
T
H
T
H
T
T
T
H
H
H
Microstate 5
Microstate 4
Microstate 3
Microstate 2
Microstate 1
Let us consider 8 successive tosses of a fair coin
H
T
H
H
Macrostate: T
3
(# heads) H
4
H
2
H
5
H

While each microstate occurs with equal
probability, some macrostates have more
associated microstates than others
Probability of
obtaining nH heads:
(nH )
All
Multiplicity associated
with nH heads
Total number of
microstates
To make this concrete, let us consider an example with 3

successive
tosses (where the multiplicities can be easily
enumerated)

(3) = 1
(2) = 3
(1) = 3
(0) = 1
All = 8

OK, so how do I calculate (nH) for N fair tosses?
Multiplicity of zero heads for N tosses:
Multiplicity of 1 head for N tosses:
Multiplicity of 2 heads for N tosses:
3
4
5
(1) = N
first toss in the series

to return
heads
(each of the N tosses

could returns heads)
(2) = N (N 1) /2
N ways to choose the
1
2
(0) = 1
N-1 ways to choose

which second toss in
the series will return
heads
For a given pair of

tosses chosen to
return heads, the
exact order in which
the elements are
chosen does not
give rise to unique
microstates

Multiplicity of zero heads for N tosses:
Multiplicity of 1 head for N tosses:
(0) = 1
(1) = N
Multiplicity of 2 heads for N tosses:
(2) = N (N 1) /2
Multiplicity of 3 heads forN tosses:
(2) = N (N 1) (N 2) / 3 2
Multiplicity of nH headsfor N
tosses:
(N nH +1)
(N
1)
(N
2)
N
(nH ) =
nH (nH 1) 3 2 1
two ways to
choose which
will be the
second to be
selected. . .
Three ways to choose

which of the three
elements
will be the
first to be selected;

Answer:
(N nH + 1)
(N
1)
(N
2)
N
(nH ) =
nH (nH 1) 3 2 1
(N nH +
1) (N
nH
) (N nH 1) 3 2 1
N (N 1)
3 2 1
nH(nH 1) 3 21 (N n
H ) (N n H 1)
: number of
N N choose nH
distinct ways
of choosing
nH ! (N n H )!
n H
nH elements out of N
N!
=
Recall that the factorial function is defined:
N (N 1) (N 2)
N!=
3 2 1
Entropy of Two-State System

S k B ln
The entropy of our heads and tails system is then
S(nH ) = k B ln
N!
nH ! (N nH )!
OK, but how do we deal with logarithms of a factorial function?
Stirlings Approximation
For N large I can approximate log N! via the following:
ln N! N ln N N
This is not hard to show:
ln N! = ln1 + ln 2 + ln 3 + + ln(N 1) + ln N
N
> ln
N dN
= N ln N N +1
good to within 1% for N=100

Approximation
negligable when N
is large
For macroscopic size systems N~1023 !

The entropy of our heads and tails system is:
S(nH ) = k B ln
N!
nH ! (N nH )!
We wish to apply Stirlings approximation:
S(nH )/ k B =
lnN! ln nH ! ln (N nH )!
= N ln N N nH ln nH +nH
(N nH ) ln (N nH ) +(N nH )
lnN! N ln N N


So we have from previous slide:
1
kB
S(nH ) = N ln N nH ln nH (N nH ) ln (N nH )
The entropy is maximized at nH=N/2
(this must be true, but you can confirm it via dS/dnH=0)
of the
Let us
investigate
the
behavior

n
=
+s
N
/2
H
entropy near the maximum:
1
kB
S(s) = N ln N ( N2 + s ) ln ( N2 + s )
N
( N2 s ) ln
( 2 s)
On next slides we will Taylor expand this expression for small s

1
kB
S(s) = N ln N ( N2 + s ) ln ( N2 + s )
(continued from
previous slide)
We will assume that s is small:

(Taylor expand
natural
log
2s
term
to
second
order
in
s)
N
N
2
(1 +
( N2 s ) ln
<< 1
N
2
ln (1 +
+
s
= N ln N ( N2 + s ) ln N
(
)
2
2
( s ) ln
N
2
N
2
(
N
2
) (
s ln 1 2s
N
2s
2s
1
( N)
1 2s 2
2 N
( )
( N2 s )
2s
N
2s
N
2s
N
1 2s 2
2 N
( )

1
kB
)
2
2s
1
2s
N 2 (N)
(continued
N
2s
N
s
1
s
(
)
ln
ln
(2 ) ( N)
from previous
2
slide)

1 2s 2
2s
N 2 (N)
S(s) = N ln N ( N2 + s ) ln
N
2
( N2 + s ) ln (1 +
N
2
= Nln N N ln N2
4 s 2+ N2s2
N 2 N
= N ln 2
( )
2
= 2s
N
2s
N

So near its maximum the entropy has the form:
1
kB
S(s) = N ln 2
with s = nH N /2
S(nH ) = k B ln (nH )

2(n
S
/
k
N
(nH
) = e = ( 2 ) e
B
H nH / N
Let
2s 2
N
2
N
/
2)
H
N
(H ) = ( 12 ) e
2N (H 12 ) 2
Multiplicity and Equilibrium

(nH ) = ( 12 ) e
with
(nH )
2N (H 12 ) 2
H = nH / N
As systems approach macroscale
size the macrostate of highest
multiplicity will be extraordinarily
sharply defined
N=10000
This is why well-defined

equilibrium states exist in nature!
N=1000
N=1000
1
2

Rubber elasticity is directly related to entropy!
Let us consider a toy model of a polymer: the polymer lives in 1D
and consists of a chain that can only take steps of size a backwards
and forwards along the x-axis (so it is a two-state system!)
Microstates of the polymer are the total sequence of backwards
and forward steps
a
N=12
L=6a
L=a
Microstate 1
L=2a
Microstate 2
Microstate 3
Macrostate: total distance moved on x-axis (# of heads-# of tails)

We can calculate the entropy of the chain using the heads and tails model!
Let the total number of forward steps: n+
(n+=nH)
Let the total number of backwards steps: n-
L = a (n+ n ) = a (2n+ N )
The macrostate:
The steps also satisfy:
N = n+ + n
n+ = N n
The multiplicity
corresponding to a given macrostate is then the total number

of ways to select n+ steps out ofN!
N N!

(same expression as for heads/tails)
(n+ ) = =
n
!
n+ + (N n+ )!
Using Stirlings
approximation
1
kB
S(n+ ) = N ln N n+ ln n+ (N n+ ) ln (N n+ )

The entropy:
1
kB
L = a (2n+ N )
The macrostate:
n+ = 1
2

L
+N
a
of L with L/a<<N.
We
want
to expand
S
in
terms
is exactly the same algebra

we
performed
this
(but
for the heads/tails model with s=L/2a)
Previous result for heads/tails:
1
kB
S(s) = N ln 2
S(L)/ k B = N ln 2
L2
2a 2 N
(stretching the
polymer decreases
the number of available microstates!)
2s 2
N
No temperature
dependence
(did not assign an
energy to the system)

S(L)/ k B = N ln 2
1
dS = dU dL
T
Equation of state of rubber-band:
L2
2a 2 N
S
kB L
= = 2
L U a N
T
arisesas system
(chain tension
desires to increase entropy)
k BT
2
a N

Lecture 14: Entropy IV
Time: 2:35-3:25
Office Hours: 2-3MW
Rutherford 411

For a thermally isolated system, the values assumed by the
extensive parameters (U, V, N) of the sub-systems in the absence of
an internal constraint are those that maximize the total entropy of the
system over the space of equilibrium states
Review: Entropy in Statistical Mechanics

Review: Entropy and Microstates

Microstate 1
Microstate 2
Microstate 3


Not quite. . .
(: multiplicity)
S k B ln

not simply equal?

(not the sum 1+2)
= S1 +S 2
Review: Heads Tails Model

Let us denote these states: heads and tails
Microstate of heads tails system: a particular sequence of
coin-tosses (e.g. HTTHTTHHHT. . .)
Macrostate of heads tails system: the number of heads
returned for the particular sequence of tosses (nH)
N choose nH: number of
distinct ways of choosing
nH elements out of N
N
N!
=n ! (N n )!
n H
H
H
Review: Entropy of Two-State System
S k B ln
The entropy of our heads and tails system is then
S(nH ) = k B ln
N!
nH ! (N nH )!
OK, but how do we deal with logarithms of a factorial function?
Answer: Stirlings Approximation
ln N! N ln N N

Review: Entropy of Two-State System

In last lecture. . .
We applied Stirlings approximation to heads/tails entropy:
1
kB
S(nH ) = N ln N nH ln nH (N nH ) ln (N nH )
Then Taylor expanded entropy about maximum (nH=N/2):
nH =
N /2 +s
2s
N
1
kB
S(s) =N ln 2
<< 1
Then found the resulting multiplicity:
(nH ) = e
2s
N
S / kB
Multiplicity and Equilibrium

Result:
(nH ) =
2N (H
H = nH / N
with
(nH )
( 12 )
1 2
2)
As systems approach macroscale

size the macrostate of highest
multiplicity will be extraordinarily
sharply defined
N=10000
N=1000
This is why well-defined

equilibrium states exist in nature!
N=1000
1/2

We can use the heads/tails model to describe a polymer!
Let us consider a toy model of a polymer: the polymer lives in 1D
and consists of a chain that can only take steps of size a backwards
and forwards along the x-axis (so it is a two-state system!)
Microstates of the polymer are the total sequence of backwards
and forward steps
a
N=12
L=6a
L=a
Microstate 1
L=2a
Microstate 2
Microstate 3
Macrostate: total distance moved on x-axis (# of heads-# of tails)

We can calculate the entropy of the chain using the heads and tails model!
Let the total number of forward steps: n+
(n+=nH)
Let the total number of backwards steps: n-
L = a (n+ n ) = a (2n+ N )
The macrostate:
The steps also satisfy:
n+ = N n
N = n+ + n
The multiplicity
to a given macrostate is then the total
corresponding
number of ways to select n+

stepsout of N!
N N!
(n+ ) = =
n+ n+ ! (N n+ )!
Using Stirlings
approximation
1
kB
(same expression as for heads/tails)

The entropy:
1
kB
L = a (2n+ N )
The macrostate:
n+ = 1
2

L
+N
a
of L with L/a<<N.
We
want
to expand
S
in
terms
is exactly the same algebra

we
performed
this
(but
for the heads/tails model with s=L/2a)
Previous result for heads/tails:
1
kB
S(s) = N ln 2
S(L)/ k B = N ln 2
L2
2a 2 N
(stretching the
polymer decreases
the number of available microstates!)
2s 2
N
No temperature
dependence
(did not assign an
energy to the system)

S(L)/ k B = N ln 2
1
dS = dU dL
T
Equation of state of rubber-band:
L2
2a 2 N
S
kB L
= = 2
L U a N
T
arisesas system
(chain tension
desires to increase entropy)
k BT
2
a N
Microstates of Ideal Gas

Can we calculate the entropy of an ideal gas by
direct numeration of its microstates?
YES!
Well do this by introducing fancy mathematical techniques
to count microstates, in particular our derivation will utilize
the formula for the volume of a d-dimensional hypershere!
Comment: Finn p. 90-94 provides a simplified treatment of this
problem. I will provide a considerably more rigorous but also
mathematically more involved approach.

Let us consider first a single-molecule gas of energy U
We would expect the following:
The multiplicity 1 of the single particle gas (e.g. the
number of accessible microstates) is proportional to:
(1) The available volume V
(2) The number of allowed velocity orientations
(alternatively momentum orientations), Vp
VP: Volume in momentum space
1 V V p

OK: but there are two difficulties:
(1) What is the constant or proportionality?
(i.e. how do we get an explicit numerical value for ?)
(2) How do we evaluate the volume in momentumspace given the constraint of fixed energy?

Question I: what is the constant of proportionality?
We cannot answer this question within classical physics
Quantum mechanics tells us that the position and momentum of a particle are
not precisely defined quantities, but can have a certain spread x and px
Quantum mechanics also tells us that there is a tradeoff in the precision with
which I can measure x and px:
If x is precisely defined, so x is small, then px will be large (and vice-versa)
This trade-off is embodied in the uncertainty principle. The uncertainty principle
says the minimum possible value of the product xpx is:
p x x h
h: Plancks constant
(6.626x10-34 J s)

Minimum possible value of product x px:
p x x h
The total number of possible states the particle can

access along x is simply: (L/x)
The total number of possible momentum
states the
particle can access is simply: (Lp/ px)

p x x h

states the
particle can access is simply: (Lp/ p)
Number of distinct states in 1D =
L L p LL p
=
x p x h
VV p
= 1
h 3


Question II: how do we deal with the constraint on
momentum necessitated by the condition of fixed energy?
2
2
2
p
p
p
U KE = x + y + z
2m 2m 2m
p x2 + py2 + pz2 = 2mU KE = R 2p
The particle has a fixed

kinetic energy:
pz
The allowed momentum

states are
constrained to lie on a shell of
radius:
R
KE
P = 2mU
The shell has a thickness dRp, arising

from a fundamental imprecision U on
the system energy. U/U<<1
Rp
dR
py
px

What would be the multiplicity for a two-molecule gas?
First guess:
Not quite right:
(for each state of molecule 1, there are

1 states accessible to molecule 2)
2 = 1 1
The position states factorize but the momentum states

do not, due to the constraint on the total energy
1 2
Second guess: 2 =

6 V V2 p
h
of shell in 6-dimensional momentum space shell with
V2 p : Volume
radius R
p
2
2
2
p x1 + py1
+ pz1
)+(
momentum coordinates
of particle 1
2
2
2
p x 2+ p y 2 + p z 2
2
=
R
) = 2mU KE p
of particle 2

Second guess:
V2 p :
1 2
2 = 6 V V2 p
h
Volume of shell in 6-dimensional

momentum space shell with radius Rp
Still not quite right!
are distinguishable
Only
true if the particles
1
2
2
1

Second guess:
V2 p :
1 2
2 = 6 V V2 p
h

It is deep fact
of nature that
the molecules are indistinguishable
1
2
We can not treat these as

different states!
=
Third
guess:
2
1
prevents
overcounting
states
1 1 2
2 =
V V2 p
6
2 h

What would be the multiplicity for a N-molecule gas?
N =
VNp :
1
h
3N
1 N
V VNp
N!
Volume of shell in 3N-dimensional momentum space

shell with radius Rp
2
2
2
+
p
+
p
( yi zi ) = 2mU KE = R p
2
p xi
i=1
N! :
All possible permutations of N molecules, total number of ways

of interchanging molecule identities

Question: what is the probability a gas in a container of volume V will
occupy 50% of the volume? (say N=100)
Total number of microstates:
N (V ) V N
Microstates corresponding to (V/2):
N (V /2) (V /2)
Probability of occupying half the volume:
N=100
30
Probability ~ 10
N (V ) / N (V /2)(1/ 2)N

Answer:
N =
1
h 3N
1 N
V VNp
N!
OK. But how do we calculate the volume of our 3Ndimensional shell in momentum-space?
sphere
of d-dimensional hypershere of radius R!
Vd
(R) : Volume
VNp =
sphere
Vd
(R p
+ dR) Vdsphere (R p )

Answer:
N =
1
h
3N
1 N
V VNp
N!
VNp = Vdsphere (R p + dR) Vdsphere (R p )

d /2
sphere
d
(R) =
Vd
R
(d /2)!
It is possible to show that the d-dimensional hypersphere volume is:
But what is a factorial

of half an integer?
Gamma Function and Factorials

of half an integer?
sphere
Vd
(R)
d /2
d
=
R
(d /2)!
The factorial function can be related to a special function called the

gamma-function:
s1 x
(s)
x e dx (s > 0)
x
x
(1) = e dx = e 0 = 1
0
(s)
s1
x
x
s1
(e
)
e
x
dx = x
0 u
dv

x
s2
(e
)
(s
1)
x
dx
0
v
0
du
= (s1)(s 1)
Integrationby parts

of half an integer?
sphere
Vd
(R)
d /2
d
=
R
(d /2)!

gamma-function:
(1) = 1 ; (s) = (s 1) (s 1)
Let n be an integer:
(n) = (n1) (n 1) = (n 1) (n 2) (n 2)
= (n 1) (n 2) (n 3) (n 3)
= (n 1)!
(1)
2
1
(n 2)
= (n 1)
= 1

of half an integer?
sphere
Vd
(R)
d /2
d
=
R
(d /2)!

gamma-function:
(1) = 1 (s) = (s 1) (s 1)
(n integer)
n! = (n + 1)
The gamma function

can be used to generalize the factorial function to halfinteger arguments:
y x
1/ 2 x
1
( 2 ) = x e dx =
0
1
y
y 2
e (2ydy) = 2 e dy
1 1 dx 0
dy =
= dx /2y
2 x

Evaluate hypersphere volume for d=1:
V1sphere =
R = 2R
(1/2)!
(1/2)! = (
3
2
( 12 )
=
= ( 12 )
()
1
2
d /2
Vdsphere (R) =
Rd
(d /2)!
( 12 ) =
1) (s 1)
(s) = (s
=
(n
+
1)
n!
2
sphere
Evaluate hypersphere
V2
= R
volume for
d=2:

3/2
4 3
3
sphere
R
R =
V3
=
volume for d=3:

3
(3/2)!
3 1 1 =3
5
(3/2)! = ( 2 ) = (
2 ) ( 2 ) ( 2 )
Return to Microstates of Ideal Gas

OK, end of mathematics digression. . .
Multiplicity of N-molecule gas:
VNp =
sphere
Vd
(R p
3N / 2
1 1 N
N = 3N
V VNp
h N!
3N / 2
3N / 2
(2m) 3N / 2 [ (U
+
U
U
)
]
=

(3N /2)!
RP = 2mU KE
d /2
Vdsphere (R)
d
=
R
(d /2)!

Insert expression from previous slide for

1 1 N
N = 3N
V VNp momentum space volume
h N!
VN
3N / 2
3N / 2
3N / 2
3N / 2
= 3N
U
U
+
U
2m
(
)
[
]
(
)
h N! (3N /2)!
N
3N / 2 3N / 2
3N / 2
= V (2m)
3N / 2
U
U
1 + 1
3N
U
h N! (3N /2)!
3N / 2
2/3
3N / 2
(2 m) V U 1
1
U
=
1 +
1
U
N!
(3N
/2)!

(2 m) V
N =
h2
2/3
(from previous slide)
3N / 2
U 1
1
N! (3N /2)!

f (U,V )
1/g(N )
The
gas entropy! S
= k ln
B
U 3N / 2
1 +
1
U
h
3
S
/ k B = N ln f (U,V ) ln g(N ) + ln h (U /U )
2
Stirlings
Use
Approximation to simplify ln N! terms


Apply Stirlings approximation to the entropy:
3
S / k B = N ln f (U,V ) ln g(N ) + ln h (U /U )
2
ln N! N ln N N
ln g(N ) = ln N!+ ln(3N /2)!
3
3
ln
N
= N ln N N + N 2
2N
3
2
N ln N
N ln32 + 32
= N ln N 52 N + 32
5
2
5
2
= N ln N N + 32 N ln 32

5/2
ln
N
=N
3
) 5
2 f (U,V
S / k B = 2 N ln
2 N + ln h (U /U )
5/3
3N

One last step: we must take the limit: U /U 0
S / kB =
3
2
N ln
2 f (U,V )
3N 5 / 3
ln h (U /U ) = ln
(N
extremely
large ~1023)
52 N + ln h (U /U )
U 3N / 2
1 +
1
U 3N / 2 3
ln 1 + = 2 ln
U
U /U 0
U
1 +

So now we are finished!
S / kB =
3
2
N ln
2 f (U,V )
52 N
3N 5 / 3
(4 m) V 2 / 3 U
3
5
= N ln
N
2
2
5/3
2
N
3h

3 U
V
S / k B N= ln + ln +S o Sackur-Tetrode
equation
2
N
N

Note that this result is
explicitly extensive
(entropy is proportional
to N)
f (U,V ) =
(2 m) V 2 / 3 U
Thermodynamic Implications
3
V
U
S / k B N = ln + ln +S o
2
N
N
Sackur-Tetrode equation
Recall that we can obtain the temperature and pressure from
the entropy
in the
from S(U,
V, N):
1 S 3
1
= = N
T U V 2
U
P
=
T
S k B N
=
VU V
U=
3
N kB T
2
PV=Nk B T
(so we have finally derived

the ideal gas law!)

Lecture 14: Entropy VI
Time: 2:35-3:25
Office Hours: 2-3MW
Rutherford 411

In statistical mechanics, entropy is related to the logarithm of the
number of microstates () available to a system:
S k B log
maximized implies that S is maximized but the

logarithm ensures that S is extensive

Can we calculate the entropy of an ideal gas by
direct numeration of its microstates?
YES!
Well do this by introducing fancy mathematical techniques
to count microstates, in particular our derivation will utilize
the formula for the volume of a d-dimensional hypershere!
Comment: Finn p. 90-94 provides a simplified treatment of this
problem. I will provide a considerably more rigorous but also
mathematically more involved approach.

Let us consider first a single-molecule gas of energy U
We would expect the following:
The multiplicity 1 of the single particle gas (e.g. the
number of accessible microstates) is proportional to:
(1) The available volume V
(2) The number of allowed velocity orientations
(alternatively momentum orientations), Vp
VP: Volume in momentum space
1 V V p

OK: but there are two difficulties:
(1) What is the constant or proportionality?
(i.e. how do we get an explicit numerical value for ?)
(2) How do we evaluate the volume in momentumspace given the constraint of fixed energy?

Quantum mechanics: the position and momentum of a particle are not
precisely defined and have a spread (x, px)
Quantum mechanics tells us minimum
possible value of product x px:
p x x h
(uncertainty principle, from last lecture)

states
the

p x x h
(from last lecture)

states the
L L p LL p
=
x p x
h
VV p
= 1
h 3


Question II: how do we deal with the constraint on
momentum necessitated by the condition of fixed energy?
2
2
2
p
p
p
U KE = x + y + z
2m 2m 2m
p x2 + py2 + pz2 = 2mU KE = R 2p
The particle has a fixed

kinetic energy:
pz
The allowed momentum

states are
constrained to lie on a shell of
radius:
R
KE
P = 2mU
The shell has a thickness dRp, arising

from a fundamental imprecision U on
the system energy. U/U<<1
Rp
dR
py
px

First guess:
Not quite right:
(for each state of molecule 1, there are

1 states accessible to molecule 2)
2 = 1 1
The position states factorize but the momentum states

do not, due to the constraint on the total energy
1 2
Second guess: 2 =

6 V V2 p
h
of shell in 6-dimensional momentum space shell with
V2 p : Volume
radius R
p
2
2
2
p x1 + py1
+ pz1
)+(
of particle 1
2
2
2
p x 2+ p y 2 + p z 2
2
=
R
) = 2mU KE p
of particle 2

Second guess:
V2 p :
1 2
2 = 6 V V2 p
h

are distinguishable
Only
true if the particles
1
2
2
1

Second guess:
V2 p :
1 2
2 = 6 V V2 p
h

It is deep fact
of nature that
the molecules are indistinguishable
1
2
We can not treat these as

different states!
=
Third
guess:
2
1
prevents
overcounting
states
1 1 2
2 =
V V2 p
6
2 h

N =
VNp :
1
h
3N
1 N
V VNp
N!
Volume of shell in 3N-dimensional momentum space

shell with radius Rp
2
2
2
+
p
+
p
( yi zi ) = 2mU KE = R p
2
p xi
i=1
N! :
All possible permutations of N molecules, total number of ways

of interchanging molecule identities

Answer:
N =
1
h 3N
1 N
V VNp
N!
OK. But how do we calculate the volume of our 3Ndimensional shell in momentum-space?
sphere
of d-dimensional hypershere of radius R!
Vd
(R) : Volume
VNp =
sphere
Vd
(R p

Answer:
N =
1
h
3N
1 N
V VNp
N!
VNp = Vdsphere (R p + dR) Vdsphere (R p )

d /2
sphere
d
(R) =
Vd
R
(d /2)!
It is possible to show that the d-dimensional hypersphere volume is:

of half an integer?

of half an integer?
sphere
Vd
(R)
d /2
d
=
R
(d /2)!

gamma-function:
s1 x
(s)
x e dx (s > 0)
x
x
(1) = e dx = e 0 = 1
0
(s)
s1
x
x
s1
(e
)
e
x
dx = x
0 u
dv

x
s2
(e
)
(s
1)
x
dx
0
v
0
du
= (s1)(s 1)
Integrationby parts

of half an integer?
sphere
Vd
(R)
d /2
d
=
R
(d /2)!

gamma-function:
(1) = 1 ; (s) = (s 1) (s 1)
Let n be an integer:
(n) = (n1) (n 1) = (n 1) (n 2) (n 2)
= (n 1) (n 2) (n 3) (n 3)
= (n 1)!
(1)
2
1
(n 2)
= (n 1)
= 1

of half an integer?
sphere
Vd
(R)
d /2
d
=
R
(d /2)!

gamma-function:
(1) = 1 (s) = (s 1) (s 1)
(n integer)
n! = (n + 1)
The gamma function

can be used to generalize the factorial function to halfinteger arguments:
y x
1/ 2 x
1
( 2 ) = x e dx =
0
1
y
y 2
e (2ydy) = 2 e dy
1 1 dx 0
dy =
= dx /2y
2 x

Evaluate hypersphere volume for d=1:
V1sphere =
R = 2R
(1/2)!
(1/2)! = (
3
2
( 12 )
=
= ( 12 )
()
1
2
d /2
Vdsphere (R) =
Rd
(d /2)!
( 12 ) =
1) (s 1)
(s) = (s
=
(n
+
1)
n!
2
sphere
V2
= R
volume for
d=2:

3/2
4 3
3
sphere
R
R =
V3
=
volume for d=3:

3
(3/2)!
3 1 1 =3
5
(3/2)! = ( 2 ) = (
2 ) ( 2 ) ( 2 )

OK, end of mathematics digression. . .
VNp =
sphere
Vd
(R p
3N / 2
1 1 N
N = 3N
V VNp
h N!
3N / 2
3N / 2
(2m) 3N / 2 [ (U
+
U
U
)
]
=

(3N /2)!
RP = 2mU KE
d /2
Vdsphere (R)
d
=
R
(d /2)!

Insert expression from previous slide for

1 1 N
N = 3N
V VNp momentum space volume
h N!
VN
3N / 2
3N / 2
3N / 2
3N / 2
= 3N
U
U
+
U
2m
(
)
[
]
(
)
h N! (3N /2)!
N
3N / 2 3N / 2
3N / 2
= V (2m)
3N / 2
U
U
1 + 1
3N
U
h N! (3N /2)!
3N / 2
2/3
3N / 2
(2 m) V U 1
1
U
=
1 +
1
U
N!
(3N
/2)!

(2 m) V
N =
h2
2/3
(from previous slide)
3N / 2
U 1
1
N! (3N /2)!

f (U,V )
1/g(N )
The
gas entropy! S
= k ln
B
U 3N / 2
1 +
1
U
h
3
S
/ k B = N ln f (U,V ) ln g(N ) + ln h (U /U )
2
Stirlings
Use
Approximation to simplify ln N! terms


Apply Stirlings approximation to the entropy:
3
S / k B = N ln f (U,V ) ln g(N ) + ln h (U /U )
2
ln N! N ln N N
ln g(N ) = ln N!+ ln(3N /2)!
3
3
ln
N
= N ln N N + N 2
2N
3
2
N ln N
N ln32 + 32
= N ln N 52 N + 32
5
2
5
2
= N ln N N + 32 N ln 32

5/3
3
= 2 N ln N
3
) 5
2 f (U,V
S / k B = 2 N ln
+ 2 N + ln h (U /U )
5/3
3N

One last step: we must take the limit: U /U 0
S / kB =
3
2
N ln
2 f (U,V )
3N 5 / 3
ln h (U /U ) = ln
(N
extremely
large ~1023)
+ 52 N + ln h (U /U )
U 3N / 2
1 +
1
U 3N / 2 3
U
ln 1 + = 2 N ln 1 +
U
U
U /U 0

So now we are finished!
S / kB =
3
2
N ln
2 f (U,V )
+ 52 N
3N 5 / 3
(4 m) V 2 / 3 U
3
5
= N ln
+
N
2
2
5/3
2
N
3h

3 U
V
S / k B N= ln + ln +S o Sackur-Tetrode
equation
2
N
N

Note that this result is
explicitly extensive
(entropy is proportional
to N)
f (U,V ) =
(2 m) V 2 / 3 U
3
V
U
2
N
N
the entropy
in the
from S(U,
V, N):
1 S 3
1
= = kB N
T U V 2
U
P
=
T
S k B N
=
V U V
U=
3
N kB T
2
PV=Nk B T

the ideal gas law!)
Entropy of Ideal Gas Mixtures

Piston permeable to
molecule of type A
How can we compute

the entropy of a
mixture of ideal gases?
Piston permeable to
molecule of type B
Gas A+Gas B
Consider the following

reversible isothermal
T
process carried out in
this peculiar thoughtapparatus
Vacuum
Diathermal walls
(system at temperature T)
The coupled sliding pistons

are connected in such a way
that they maintain a constant T
separation
Gas A
+Gas B
Gas A
T
Gas B
Gas A
Coupled sliding pistons
Vacuum
Gas B

Piston permeable to
molecule of type A
What is the net force felt by

the coupled sliding pistons?
Piston permeable to
molecule of type B
Gas A+Gas B
Sum of forces to the left:
Vacuum
(PA+PB)(piston area)
Sum of forces to the right:
Diathermal walls
Net force on coupled

sliding pistons is zero!
Gas A
+Gas B
Gas B
Gas A
Vacuum
No work is performed to
move sliding pistons!
Gas A
T
Gas B

Piston permeable to
molecule of type A
The system is isothermal,

internal energy of ideal
gas a function only of T:
Piston permeable to
molecule of type B
Gas A+Gas B
Vacuum
U = 0
Gas A
T S = 0
Si = S f
Gas A
+Gas B
Gas A
T
Diathermal walls
Gas B
As no work is performed in
process the first law gives:
Vacuum
Gas B

Ideal Gas A
+Ideal Gas B
Vacuum
Initial state of system
Ideal
Gas A
Ideal
Gas B
T
Final state of system
The initial and final entropies of the above process are equal
In a mixture of ideal gases the entropy is the sum of the entropy
each gas would have if it alone occupied the entire volume
Gibbs theorem
Entropy of Mixing
Ideal Gas A
Volume: V
Ideal Gas B
Volume: V
Equal moles of A and B
remove
partition and
gases mix
Ideal Gas A
+Ideal Gas B
Volume: 2V
What is the entropy change?

Initial Entropy:
V
3
V 3 UB
U
A
Si / Nk B = ln + ln + ln
+ ln +2S o
2
N
N 2
N
N
Entropy is the sum of the
entropy of each gas
occupying volume V
3
V
U
S / k B
N=
ln + ln +S o
N
N
Entropy of ideal gas
Entropy of Mixing
Ideal Gas A
Volume: V
Ideal Gas B
Volume: V
remove
partition and
gases mix
Ideal Gas A
+Ideal Gas B
Volume: 2V

Final Entropy:
2V
3
3 UB
U
2V
A
S f / Nk B = ln + ln + ln
+ ln +2S o
2
N
N
N
N 2
Entropy is the sum of the entropy
each gas would have if it alone
occupied the entire volume
3
V
U
k B
N = ln
+ ln +S o
S /
2
N
N
Entropy of Mixing
Ideal Gas A
Volume: V
Ideal Gas B
Volume: V
remove
partition and
gases mix
Ideal Gas A
+Ideal Gas B
Volume: 2V
Final Entropy:
2V
3 UA
3 UB
2V
+ ln +2S o
2
N
N
N
N 2
Initial Entropy:
V
V 3 UB
UA
3
Si / Nk B = ln
+ ln + ln
+ ln +2S o
2 N N 2 N N
S = S f Si = 2Nk B ln 2
(entropy of mixing!)
Entropy of Mixing
Ideal Gas A
Volume: V
Ideal Gas A
Volume: V
Ideal Gas A
remove
partition and
gases mix
Volume: 2V
What if gas A is the same as gas B?
Final Entropy:
S f = 2Nk B
3 UA
2V
+2S o
ln + ln
2
2N
2N
Initial Entropy:
Si = Nk B 2 3 ln U A +2 ln V +2S o
N
2 N
S = S f Si = 0 (as MUST be true!)

Lecture 22: Thermodynamic
Formalism
Time: 2:35-3:25
Office Hours: 2-3MW
Rutherford 411
3
V
U
2
N
N
the entropy
in the
from S(U,
V, N):
1 S 3
1
k
N
= =
B
T U V 2
U
U=
P S k B N
= =
T V
V
U
PV=Nk B T
3
N kB T
2

the ideal gas law!)

Piston permeable to
molecule of type A
How can we compute

the entropy of a
mixture of ideal gases?
Piston permeable to
molecule of type B
Gas A+Gas B
Consider the following

reversible isothermal
T
process carried out in
this peculiar thoughtapparatus
Vacuum
Diathermal walls
The coupled sliding pistons

are connected in such a way
that they maintain a constant T
separation
Gas A
+Gas B
Gas A
T
Gas B
Gas A
Vacuum
Gas B

Piston permeable to
molecule of type A
What is the net force felt by

the coupled sliding pistons?
Piston permeable to
molecule of type B
Gas A+Gas B
Sum of forces to the left:
Vacuum
Sum of forces to the right:
Diathermal walls
Net force on coupled

sliding pistons is zero!
Gas A
+Gas B
Gas B
Gas A
Vacuum
No work is performed to
move sliding pistons!
Gas A
T
Gas B

Piston permeable to
molecule of type A
The system is isothermal,

internal energy of ideal
gas a function only of T:
Piston permeable to
molecule of type B
Gas A+Gas B
Vacuum
U = 0
Gas A
T S = 0
Si = S f
Gas A
+Gas B
Gas A
T
Diathermal walls
Gas B
As no work is performed in
process the first law gives:
Vacuum
Gas B

Ideal Gas A
+Ideal Gas B
Vacuum
Initial state of system
Ideal
Gas A
Ideal
Gas B
T
Final state of system
The initial and final entropies of the above process are equal
In a mixture of ideal gases the entropy is the sum of the entropy
each gas would have if it alone occupied the entire volume
Gibbs theorem
Entropy of Mixing
Ideal Gas A
Volume: V
Ideal Gas B
Volume: V
remove
partition and
gases mix
Ideal Gas A
+Ideal Gas B
Volume: 2V

(equal temperature and pressure)

Initial Entropy:
V
3
V 3 UB
U
A
Si / Nk B = ln + ln + ln
+ ln +S oA +S oB
2
N
N 2
N
N
Entropy is the sum of the
entropy of each gas
occupying volume V
3
V
U
S / k B
N=
ln + ln +S o
N
N
Entropy of Mixing
Ideal Gas A
Volume: V
Ideal Gas B
Volume: V
remove
partition and
gases mix
Ideal Gas A
+Ideal Gas B
Volume: 2V


Final Entropy:
2V
3
3 UB
U
2V
A
+S oA +S oB
+ ln
2
N
N
N
N 2
Entropy is the sum of the entropy
each gas would have if it alone
occupied the entire volume
3
V
U
S/ k
B N = 2ln + ln +S o
N
N
Entropy of Mixing
Ideal Gas A
Volume: V
Ideal Gas B
Volume: V
remove
partition and
gases mix
Ideal Gas A
+Ideal Gas B
Volume: 2V

Final Entropy:
2V
3 UA
3 UB
2V
+ ln +S oA +S oB
2
N
N
N
N 2
Initial Entropy:
V
V 3 UB
UA
3
Si / Nk B = ln
+ ln + ln
+ ln +S oA +S oB
2 N N 2 N N
S = S f Si = 2Nk B ln 2
(entropy of mixing!)
Entropy of Mixing
Ideal Gas A
Volume: V
Ideal Gas A
Volume: V
Ideal Gas A
remove
partition and
gases mix
Volume: 2V

What if gas A is the same as gas B?
Final Entropy:
S f = 2Nk B
3 2U A
2V
+S o
ln + ln
2
2N
2N
Initial Entropy:
Note that treating the

particles as
indistinguishable is
critical to proving that
indeed S=0!
Si = Nk B 2 3 ln U A +2 ln V +2S o
2 N N
S = S f Si = 0 (as MUST be true!)
Thermodynamic Formalism
Over the next two-three weeks we will develop
further the formal structure of thermodynamics
-We will introduce the chemical potential (relax constraint on fixed N)
- Develop the formalism of thermodynamic potentials (Entropy,
Internal Energy, Hemholtz Free Energy, Enthalpy. Gibbs Free
Energy)
-Develop strategies for manipulation of thermodynamic quantities
that follow from the formal structure of the theory
-Use the formalism to cover applications such as Throttling processes,
chemical reactions and osmotic pressure, phase equilibria

For a thermally isolated system, the values assumed by the
extensive parameters (U, V, N) of the sub-systems in the absence of
an internal constraint are those that maximize the entropy of the
system over the space of equilibrium states
(for example an internal partition is removed, allowing a gas to expand)
(an adiabatic separating wall is replaced with a diathermal wall
allowing the two sub-systems to exchange energy)
The entropy as function of the system extensive parameters
completely specifies the systems thermodynamic state
S(U,V, N )
1 S
= >0
T U V
U(V,T)
Temperature is
non-negative for
equilibrium
systems
P S
=
T V U
P(V,T)
1
P
dS = dU + dV
T T
(Central relation of thermodynamics)
Chemical Potential
What if we allow molecule number N to vary?
S(U,V, N )
assume only one

chemical species
present
S
S
=
=
T
U V ,N T N V ,U
U(V,T)
(V,T)
P S
=
T V U ,N
P(V,T)
Chemical potential:
Energy increase per
molecule added to system
P
+ dV dN
dS = T dU
T
T
= TdS PdV +dN
dU
Chemical Potential
If two systems are allowed to exchange molecules, in equilibrium
maximization of the entropy will require that their chemical potentials
are equalized. This is known as chemical equilibrium.
(you will show this for HW next week)
Particles flow from regions of high chemical

potential to regions of low chemical potential
(just
as volume flows from regions of high to low pressure,

and heat flows from regions of high to low temperature)
Chemical Potential of Ideal Gas

Calculate the chemical potential of an ideal gas:
=
T
N V ,U
3
V
U
2
N
N
4 m 5
S o
= ln 2 +
2
3h
Chemical Potential of Ideal Gas

S
= = k B 3 ln U + ln V +S o k B N ( 2N5 )
N V ,U 2 N
T
N
= 32 k B T
Function of
temperature
3 U
V +
k
T
+
ln
ln
+
f
(T)
=
c
k
T
ln
= B
o
o
B
2 N N

= 1/c (number density)
4 m
o = ln 2
3h

with
4 m 5
S o = ln
+
2
2
3h
3
V
U
2
N
N
Euler Relation
We can derive some very general relations among a
systems thermodynamic parameters
Scale all extensive parameters by some factor :
U(S,V, N )
U( S, V, N ) = U(S,V, N )
V V
S S
N N
U
dU
U
U
=
V +
S +
N =U
d
( S) V ,N ( V ) U ,N ( N ) U ,V
This relation holds for any , so let =1
Euler Relation
U
U
dU U
=
S +
V +
N =U
d ( S) V ,N ( V ) U ,N ( N ) U ,V
This relation holds for any , so let =1
U
S
S V ,N
=T
= P
U
+ N = U
N U ,V
=
= TS PV
+N
U
U
+ V
V U ,N
(Euler relation)
dU = TdS PdV +dN
Gibbs-Duhem Relation
The chemical potential is in fact not independent of T and P
We just showed:
U = TS PV +N
Differentiate the Euler relation:
dU = SdT +TdS PdV VdP +dN +Nd

= TdS PdV +dN
dU = TdS PdV +dN
SdT
VdP
+Nd = 0
S
V
d = dT + dP
N
N
relation)
(Gibbs-Duhem
Energy Minimization Principle

The principle of entropy maximization applies generally to a
thermally isolated system (e.g. adiabatic walls in place)
In practice, thermally isolated can lead to three scenarios:
after internal constraints
removed. . .
If system isolated. . .
entropy of system maximized at
constant energy and volume
S
>
But note that as
U V ,N
If system allowed to perform adiabatic

work while reaching equilibrium. . .
The greatest possible entropy increase

will always occur for a spontaneous
process in an isolated system!
If work performed irreversibly. . .

system entropy is maximized while
system internal energy decreases

removed. . .

What determines the final

equilibrium state in this case?
If work performed reversibly. . .
system entropy constantno
entropy increase at all! but system
internal energy decreases


How do we determine the equilibrium state
of a system at constant entropy?
Sub-System 1
Sub-System 2
S1 (U 1 ,V1 )
S 2 (U 2 ,V2 )
But of course we
expect the final
equilibrium state
to have P1=P2!
Wall movable but adiabatic
The first law tells us:
dU 1 = P1 dV1
dU 1 P1
P
P
identically for
dS1 =
+ dV1 = 1 dV1 + 1 dV1 = 0 (follows
sub-system 2)
T1
T1
T1
T1
theentropy is constant for this process (always
In other words,
maximum) and the entropy maximization condition tells us nothing!

System
External system filled with

highly viscous fluid: dissipates
energy with increasing entropy
What will happen to this system is in fact an indefinite oscillation of the partition
after it is released: there is no mechanism for the system to come to equilibrium!
We can introduce such a mechanism by creating a means of the system to
output work into a dissipative environment (such as using work to drive piston in
a viscous liquid)
Now place isolating boundaries around composite system
(energy of composite system fixed; entropy of composite system will be maximized)

U system
(total for both

sub-systems)
U d (S d )
Energy of composite system (fixed):
U d (S d ) :
Monotonic increasing
function of Sd
Entropy of composite system:
External system filled with

highly viscous fluid: dissipates
energy with increasing entropy
U T = U system +U d
System energy
must be minimized!
S T = Ssystem +Sd
constant (by assumption)
maximized if Sd
is maximized
Maximized as total
entropy maximized

V = V1 +V2
dV1 + dV2 = 0
Sub-System 2
U 1 (S1 ,V1 )
U 2 (S 2 ,V2 )
Sub-system entropies
are constant so total
system entropy is
constant
Sub-System 1
dU = dU 1 + dU 2 = P1 dV1 P2 dV2 = (P2 P1 ) dV1 = 0
Energy minimization!
Systems are in mechanical equilibrium

For a system at constant entropy, the values assumed by the
extensive parameters (S, V, N) of the sub-systems in the absence of
an internal constraint are those that minimize the total energy of the
system
Formal Demonstration:
Let us consider a general system with an entropy:
S(U, X1, X2. . .)
(U: total internal energy; X1, X2 extensive parameters of subsystems)
=0
X i U ,other X
Entropy maximization:
(constant energy)
Energy minimization:
(constant entropy)
S / X i
other X
<0
S(U, X1, X2. . .) =constant
S
0 = dS = dU
U other X
+
dX i
Xi U ,other X
(hold other extensive

parameters constant)

Formal Demonstration Continued. . .
S(U, X1, X2. . .)

(constant entropy)
S
S
0 = dS = dU +X dX i
U other X
i U ,other X
U
=
dX i
X i S,other x
U
S
S

+
=0
U other X Xi S,other
XXi U ,other X

other X
S / X i U
(
)
U
=
X i S,other X (S /U )
other X

S(U, X1, X2. . .)


other X
(S /X i )U
U
other X
= T (S /Xi )U
=
=0
other X
You
that 2 S / 2 X i
can also show
2U / 2 X i
other X
<0
other X
S
>0
Entropy Maximization/Energy Minimization

Equilibrium states are in fact states of both maximum entropy
(at constant energy) and minimum energy (at constant entropy)
This may seem paradoxical, but note that while entropy maximization
and energy minimization lead to very different ways of reaching a given
equilibrium state, once equilibrium is reached both extremal criteria will
be simultaneously satisfied.
S
U
State A maximizes
the entropy at fixed
internal energy
And minimizes the

energy at fixed
entropy
Thermodynamic Formalism in Energy Representation
U(S,V, N )
U
=
T=
S V ,N
1
T(S,V, N )
U

N V ,S P =
U

V S,N
P(S,V, N )
(S,V, N )
+dN
dU = TdS PdV

Lecture 22: Thermodynamic
Formalism
Time: 2:35-3:25
Office Hours: 2-3MW
Rutherford 411
Thermodynamic Formalism in Entropy Representation
S(U,V, N )
S
S
=
=
T
U V ,N T N V ,U
U(V,T)
(V,T)
assume only one

chemical species
present
P S
=
T V U ,N
P(V,T)
dS
= dU + dV dN
T
T
T

removed. . .
S
>
But note that as
U V ,N

The greatest possible entropy increase

will always occur for a spontaneous
process in an isolated system!


removed. . .

What determines the final

equilibrium state in this case?
If work performed reversibly. . .
system entropy constantno
entropy increase at all! but system
internal energy decreases


For a system at constant entropy, the values assumed by the
extensive parameters (S, V, N) of the sub-systems in the absence of
an internal constraint are those that minimize the total energy of the
system
Formal Demonstration:
S(U, X1, X2. . .)
=0
X i U ,other X
(constant energy)
(constant entropy)
S / X i
other X
<0
S
0 = dS = dU
U other X
+
dX i
Xi U ,other X


S(U, X1, X2. . .)

(constant entropy)
S
S
0 = dS = dU +X dX i
U other X
i U ,other X
U
=
dX i
X i S,other x
U
S
S

+
=0
U other X Xi S,other
XXi U ,other X

other X
S / X i U
(
)
U
=
other X

S(U, X1, X2. . .)


other X
(S /X i )U
U
other X
= T (S /Xi )U
=
=0
other X
You
that 2 S / 2 X i
can also show
2U / 2 X i
other X
<0
other X
S
>0

Equilibrium states are in fact states of both maximum entropy
(at constant energy) and minimum energy (at constant entropy)
This may seem paradoxical, but note that while entropy maximization
and energy minimization lead to very different ways of reaching a given
equilibrium state, once equilibrium is reached both extremal criteria will
be simultaneously satisfied.
S
U
State A maximizes
the entropy at fixed
internal energy
And minimizes the

energy at fixed
entropy
U(S,V, N )
U
=
T=
S V ,N
1
T(S,V, N )
U

N V ,S P =
U

V S,N
P(S,V, N )
(S,V, N )
+dN
dU = TdS PdV

An example may help illuminate some of these points. . .
Consider two bodies initially with temperatures TiH and TiL:
The bodies are NOT thermal reservoirs
(e.g. they have a finite heat capacity CV)
TH
closed
engine cycle
|QH|
|W|
|QL|
TL
I will take the bodies to equilibrium at some

final temperature, but in doing so will run a
heat engine between the bodies that outputs
a work W (not necessarily a Carnot cycle)
(the system is otherwise isolated from the
environment)
Yes, this example is like your HW
problem! (but we will consider it from a
different view-point)

An example may help illuminate some of this formalism. . .
Consider two bodies at temperature TiH and TiL:
The entropy change of the system (you showed for HW):
TH
closed
engine cycle
|QH|
|W|
|QL|
T
L
f
f
TL
TH
i
i
V
V
TL
TH
(yes, TfH =TfL, but I will explicitly show this)
S = C ln
+C ln
There is a work output to the environment,

so the systems internal energy changes:
U = W
that the
Let us assume
further
internal energy of the high and
low temperature reservoirs is given by:
U H = CV TH
U L = CV TL
S = CV ln
TH
closed
engine cycle
+CV ln
TLf
TLi
U = W = U L +U H
|QH|
(first law)
|W|
THf
THi
|QL|
TL
= CV (TLf TLi ) = CV (THf THi )
THf
= C1 W (TLf TLi ) +TH
i
terms of the initial temperatures and T :

Sin
Express

i
i
f
L
1
+(TH + TL ) TLf
W
C
1
i
U H = CV TH C S = ln
TH
TLf
Maximize with
+ ln i
U L = CV TL
f !
respect
to
T
L
TL
S
= ln
CV
closed
engine cycle
TH
i
+(TH
TLf
THi
|W|
|Q |
TL
i
+ TL )
TLf
+ ln i
TL
Maximize with respect to Tf L!
|QH|
C1V
1
-1
1 d(S) =
+ f
i
i
f
CV dTLf C1
W +(TH +TL ) TL TL
=0
U H = CV TH
U L =CV TL
f
TL
C1V
+(THi
+ TLi )
f
TL
i
i
f
1
f
T
+
T
H
L
W
=
T
TL =
H
2C V
2
First law relation:
i
f
i
f
1
+T
TH = C W (TL TL ) H
V

So entropy maximization gives us:
closed
engine cycle
TH
f
TL
f
TH
|QH|
|Q | |W|
L
TL
THi + TLi 1 W
=
2C V
2
Tm
If there is no work output, we just get the

arithmetic mean of the temperatures
(this
is just what you found on HW for the two bodies
when they irreversibly reach thermal equilibrium!)
Work
lowers the final temperature (e.g.
some energy is output to the environment)
The entropy change (in terms of W, To):
U H = CV TH
U L = CV TL
S
=
CV
2 ln
Tm 2C1 W
V
TLi THi
(the larger the work

output the lower the
entropy change and
vice versa)

The entropy change (in terms of W, Tf):
TH
closed
engine cycle
|QH|
|QL|
2 ln
TLi THi
If the process is reversible:
|W|
TL
UH
S
=
CV
Tm 2C1 W
1
Tm 2C W
i
i
TL TH
V
= CV TH C V
=1
i i
i
i
i
i
= 2Tm 2 TL TH = TH + TL 2 TL TH
i
i
=
T
T
H
L
U L = CV TL
S = 0
(reversible work: maximum

possible output for process)

Now let us try to approach the problem via
energy minimization!
TH
We will assume that there is a fixed entropy change:
closed
engine cycle
|QH|
S = CV ln
|W|
|QL|
THf
TL
/THi
=e
f
TL
TLi
( )
S /C V
Total internal energy

change:
f
TH
THi
(TLi /TLf )
U = U L +U H
= CV (TLf TLi ) +CV (THf THi )

U H =CV TH
f T i T i e S /C
i
i
(TH + TL )
TL + H L f
=
C
V
U L = CV TL
TL
f !
Minimize
with
respect
to
T
L


U
closed
engine cycle
TH
|W|
U H = CV TH
U = C T
V L
(T )
TLf =
i i S /C
1 d(U)
TH TL e
0=
=
1
f
C
dT
V
f 2 Use
L
|QL|
TL
Minimize with respect to Tf L!
|QH|
f T i T i e S /C
i
i
(TH + TL )
= CV TL + H L
f
TL
S / 2C V
i i
TH TL e
constant S
constraint
= THf
When there is no entropy

change the final temperature
is simply the geometric mean of the two initial
temperatures! (just as you showed in HW)
also derive this formula from our entropy

(You can
maximization approach by replacing the work with the
equivalent entropy change)

This example illustrates some very general features of
thermodynamic processes in thermally isolated systems:
When internal constraints are removed, the approach towards equilibrium can be
characterized by either an entropy increase S or equivalently a work output |W|.
There are two possible limits:
(1) Process is completely irreversible: the entropy increase is
maximized at constant energy (U=0). There is no work output, as
W=U=0. The entropy increase has the highest possible value for this
process (Smax).
(2) Process is reversible: there is no entropy change (S=0, entropy is
constant). The work output |Wmax| has the highest possible value and the
internal energy, which decreases by U=-|Wmax|, is minimized.
Intermediate Cases: there is an entropy change S: 0<S<smax and an
internal energy change U=-|W| with |W| satisfying 0<|W|<|Wmax|. The
equilibrium state can be found by either entropy maximization (for fixed change
U) or energy minimization (for fixed S)
Thermodynamic Potentials
The entropy as a function of the extensive parameters (U, V, N)
contains all thermodynamic information about the system
But the entropy cannot be directly measured

Moreover, U, V and N often are NOT fixed and
cannot be easily controlled experimentally
For example. . .
The system may be at atmospheric pressure
(so conditions are isobaric, V is not fixed but P is fixed )
The system may be at constant temperature fixed by a thermal reservoir

(so conditions are isothermal, U is not fixed but T is fixed )
The system may even be in contact with a very large reservoir of

particles at a fixed concentration
(in this case, more subtly, N is not fixed but the chemical potential is fixed)
It is always possible to model the interaction of a system with a given
reservoir and then apply entropy maximization to an isolated enclosure
containing the system+reservoir. . .
(But this is very cumbersome!)

We will introduce a series of thermodynamic potentials that naturally
express the equilibrium condition for the system when pressure,
temperature or the chemical potential (or combinations of these variables)
are held constant by an external reservoir or applied force
Thermodynamic Potentials:
Enthalpy (H): Natural potential for fixed S, P and N
Hemholtz Free Energy (F): Natural potential for fixed T, V and N
Gibbs Free Energy (G): Natural potential for fixed T, P and N
Grand Canonical Potential (): Natural potential for fixed T, V and
The Enthalpy
The enthalpy is defined:
H = Ucc +PV
Differentiating the enthalpy:
dH = dU +PdV +dPV
= (TdSPdV +dN ) +PdV +dPV
dN
TdS
+VdP
dH
=
Theenthalpy is naturally expressed as a function of (S, P, N):
H(S,P,N )
dU = TdS PdV +dN
The Enthalpy
Thermodynamic Formalism in Enthalpy Representation
H(S,P, N )
H
=
T=
S P,N
1
T(S,P, N )
H
H

N P,S V = P
S,N
(S,P, N )
V (S,P, N )
c
dH = TdS +VdP +dN
The Enthalpy
OK, so what is the Enthalpy in a physical sense?
Consider a piston exerting a certain pressure Po: initially there
nothing in the chamber so the piston is pushed against the wall
Po
Now add N moles of an ideal gas
at temperature T through a little
trap door (which is
subsequently closed)
What is the increase in energy

of the system and piston after
the gas is loaded?
+V
-V
Po
The piston gets pushed

back by V to make
room for the gas
Pos
(Positive work
PV done on
piston when V>0)
U total = U gas +U piston

= U gas +PV = H
The Enthalpy
The internal energy of a system plus the work needed to make room for it
To make a rabbit out of nothing, the magicianwho is necessarily

thermodynamically literatemust summon not only the internal
energy of the rabbit but also the additional energy PV required to
push the atmosphere out of the way. . .
(cartoon from D. V. Schroeder, Introduction to Thermal Physics)
The Enthalpy
Cute, but why do we care?
The enthalpy is useful in thermodynamic processes which are performed
at constant pressure or with pressure as the controlled variable
(e.g. chemistry at atmospheric pressure or engineering processes where
controlled pressures differences are imposed)
The most significant property of the enthalpy is its relation to heat flow for
a process at constant external pressure Po and molecule number:
H = U +Po V = Q +W +Po V = Q
= Po V
This is somewhat analogous to the internal energy being a potential for work
in an adiabatic process:
Since enthalpy and internal energy are functions
0
of state, heat and work flows for these processes
(respectively constant pressure and adiabatic)
are path-independent, depending only on final
adiabatic
and initial states

U = Q+W= W
The Enthalpy
Cute, but why do we care?
For a differential process:
reversible process
dH = TdS +VdP +dN
dH = TdS = dQ
constant N and P
S
U
S
dQ H
C P = = =T ; CV = = T
dT T
T
V ,N
V
,N
P,N
P,N
P,N
The Enthalpy and Equilibrium

Recall that the internal energy is
minimized at constant entropy
System
Po
Applying
Pos
Pressure
reservoir

Lecture 24: Thermodynamic Potentials I
Time: 2:35-3:25
Office Hours: 2-3MW
Rutherford 411
Reading: 40-41, 46-47, 98-99, 135-137 (Finn)
But the entropy cannot be directly measured as a

function of U, V, N: these quantities often are NOT
fixed and cannot be easily controlled experimentally
For example. . .
The system may be at atmospheric pressure
(so conditions are isobaric, V is not fixed but P is fixed )
The system may be at constant temperature fixed by a thermal reservoir

(so conditions are isothermal, U is not fixed but T is fixed )
The system may even be in contact with a very large reservoir of

particles at a fixed concentration
(in this case, more subtly, N is not fixed but the chemical potential is fixed)
It is always possible to model the interaction of a system with a given
reservoir and then apply entropy maximization (or energy minimization)
to an isolated enclosure containing the system+reservoir. . .
(But this is very cumbersome!)

Grand Canonical Potential (): Natural potential for fixed T, V and
The Enthalpy
The enthalpy is defined:
H = Ucc+PV
Differentiating the enthalpy:
dH = dU +PdV +dPV
= (TdSPdV +dN ) +PdV +dPV
dN
TdS
+VdP
dH
=
Theenthalpy is naturally expressed as a function of (S, P, N):
H(S,P,N )
dU = TdS PdV +dN
The Enthalpy
H(S,P, N )
H
=
T=
S P,N
T(S,P, N )
H
H

N P,S V = P
S,N
(S,P, N )
V (S,P, N )
c
dH = TdS +VdP+dN
The Enthalpy
Consider a piston exerting a certain pressure Po: initially there
nothing in the chamber so the piston is pushed against the wall
Po
Now add N moles of an ideal gas
at temperature T through a little
trap door (which is
subsequently closed)
What is the increase in energy

of the system and piston after
the gas is loaded?
+V
-V
Po
The piston gets pushed

back by V to make
room for the gas
Pos
(Positive work
PV done on
piston when V>0)
U total = U gas +U piston

= U gas +PV = H
The Enthalpy
The internal energy of a system plus the work needed to make room for it
To make a rabbit out of nothing, the magicianwho is necessarily

thermodynamically literatemust summon not only the internal
energy of the rabbit but also the additional energy PV required to
push the atmosphere out of the way. . .
(cartoon from D. V. Schroeder, Introduction to Thermal Physics)
The Enthalpy and Equilibrium

Consider a system in equilibrium with a
pressure reservoir: e.g. a piston holding
the system at constant pressure Po
Recall that the internal energy is
minimized at constant entropy
System
Po
Pos
Pressure
reservoir
Vres = V
Thus, the internal energy of the system+reservoir should be

minimized at constant entropy:
dU total = dU system +dU reservoir = dU systemPo Vres = dU system +Po V = dH

dU total = 0
dH = 0
Enthalpy is minimized in equilibrium for a system

held at constant entropy and pressure
The Enthalpy and Heat Flow

The most significant property of the enthalpy is its relation to heat flow for a
process at constant external pressure Po=P (and constant molecule number):
H = U +Po V = Q +W +Po V = Q
= Po V
Note that, in contrast, the change in internal energy gives the heat flow in a
constant volume process
0
U = Q+W= Q
isochoric
Since enthalpy and internal energy are

functions of state, heat flows for these
processes (respectively isobaric and isochoric)
are path-independent, depending only on final
and initial states
The Enthalpy and Heat Flow

For a differential process:
reversible process
dH = TdS +VdP +dN
dH = TdS = dQ
constant N and P
S
U
S
dQ H
C P = = =T ; CV = = T
dT T
T V ,N T V ,N
P,N T P,N
P,N
These relations can be used to extract entropy and enthalpy values from
integration over heat capacity data
The Enthalpy and Throttling

A particularly important engineering process where the enthalpy is used is a throttling
process (also known as a Joule-Thomson expansion process, Finn p. 46-47)
adiabatic walls
Pi
Pi,Vi
Pf<Pi
Non-equilibrium transition state

Pi
Pf<Pi
porous adiabatic plug

(or narrow constriction)
The porous adiabatic plug (throttling

valve) prevents heat transfer between the
two chambers and allows a constant
higher pressure Pi and lower pressure Pf
to be maintained on either side of the plug
(while allowing for transport of gas
between the chambers)
Pi
Pf,Vf
Pf<Pi

A particularly important engineering process where the enthalpy is used is a throttling
process (also known as a Joule-Thomson expansion process, Finn p. 46-47)
adiabatic walls
Pi
Pf<Pi
Pf
Pi,Vi
Pi

porous adiabatic plug
(or narrow constriction)
Pf,Vf
0 (process adiabatic)
U = U f U i = Q +W = W
The first law tells us:
The work done for the constant pressure process:

Vf
W = Pf dV Pi dV = V
f Pf +Vi Pi
V
0

i
U f +V f Pf = U i +Vi Pi
H f = Hi
Throttling process: enthalpy of initial and final states the same

Note that this peculiar double-piston arrangement is only a
theoretical model for what throtting devices look like
Pi
Pi,Vi
Pf
In real devices gases are

continuously pumped
through the throttling valve/
plug: every mole of gas that
passes through the plug will
have equal enthalpy (before
and after crossing the plug)
Pf<Pi
Pi
Pf,Vf

High pressure
Low pressure
Pump
Constant
high pressure
Constant
low pressure
Throttling plug

The throttling process is used to cool (and ultimately liquefy) gases
Pi
Pi, Ti
Pf<Pi
Pf, Tf
Pi
Pf<Pi
Start with 1 mole of gas (say) at temperature Ti and pressure Pi. The gas is
subjected to a throttling process between a pressure Pi and Pf<Pi.
The final gas temperature Tf is then measured as a function of final pressure Pf.
Experimentally it is found for
real gases that the final
temperature will rise and then
begin to decrease past a critical
final pressure
Tf
isenthalps
Tf5
Tf6
Tf4
Tf3
Ti2
Tf2
Tf1
Ti1
Pf

Isenthalps for Nitrogen
Temperature rises with
throttling outside region
Temperature (K)
(from H. B. Callen 2nd Ed.)
Temperature falls with

throttling in inversion region
10
20
Inversion curve
(point on isenthalp where
Tf begins to fall)
30
Pressure (MPa)
40
50

What is the physical origin of the isenthalp inversion?
Enthalpy of ideal gas (monoatomic):
H Ideal = U + PV = 32 Nk B T +Nk B T = 52 Nk B T
Constant enthalpy
Constant temperature!
(VdW model):
Enthalpy
of real gas
2
aN
+PV
H VdW = U +PV = 32 Nk B T
V
At lower pressures volume per particle will be
larger, so this negative term will be smaller (and
internal energy will be higher)
Temperature will fall

to maintain constant
enthalpy
Standard Refrigeration Cycle

Enthalpy and throttling play a key role in
refrigeration/cooling processes in thermodynamics
We will analyze two types of processes as applications
of the enthalpy:
(1) Standard vapor-compression refrigeration cycle
(standard refrigeration cycle)
(2) Hampson-Linde cycle for liquefaction of gases

Recall how we characterize refrigerator performance:
Coefficient Refrigerator Performance:
TH
QL
=
W
Hot
U = QH QL W = 0
over closed cycle:

system returns to
|QL|
TL
Work we put in

applied to refrigerator cycle:
|QH|
Closed
refrigerator
cycle
Heat we extract from low T reservoir

W = QH QL
1
QL
=
=
QH QL QH /QL 1
Cold

Standard refrigerators use a two phase (liquid-gas) working
medium (the refrigerant, e.g. freon or ammonium)
The refrigeration cycle has the
following steps:
Step 1: Vaporization. The refrigerant is
vaporized by absorption of heat QL (in
evaporator)
Step 2: Compression. the vapor is
compressed (by compressor), with work input
|W| increasing vapor pressure and temperature
Step 3: Condensation. The vapor is
condensed into liquid (in the condensor),
rejecting hear QH.
Step 4: Throttling. The liquid is passed through
a throttling valve (expansion valve) leading to a
drop in pressure and temperature
|QH|
Step 3
|W|
Step 4
Step 1
|QL|
Step 2
(from www.central-air-conditioner-and-refrigeration.com: how

your air-conditioning system works!)
Step 3:
Condensation
Step 4: Throttling
Step 1: Vaporization
1
QL
|W|
Liquid
QH
Step 1: Isobaric Step 3: Isobaric

Step 2: Adiabatic Step 4: Isenthalpic!
Pressure
Step
|QH|
Step 3:
Condensation
Step 4:
Throttling
2
Step 2:
Compression
Vapor
Step 1:
Vaporization
Step 2:
Compression
|QL|
Volume
Pressure
Liquid
Pressure
Step 1: Isobaric Step 3: Isobaric

Step 2: Adiabatic Step 4: Isenthalpic!
Step 4:
Throttling
Vapor
1
Volume
Step 3:
Condensation
Step 1:
Vaporization
Step 2:
Compression
1
Enthalpy
We can also express the refrigeration cycle in a pressure

versus enthalpy plot
Pressure

3
Step 3:
Condensation
|QH|
Step 2:
Compression
Step 4:
Throttling
|QL|
Step 1:
Vaporization
Step 1: Isobaric
Step 2: Adiabatic
How to calculate the

coefficient of performance for
the refrigerator cycle?
The heat gained or evolved during
the isobaric steps can be expressed
in terms of the net enthalpy change:
QL = H 1 H 4
QL
QH = H 2 H 3
H 1 H 4
=
=
Enthalpy
QH QL H 2 H 3 H 1+H 4

Step 3: Isobaric
Step 4: Isenthalpic! For throttling process: H 3 = H 4
H H
=

H H
1
2
Pressure

3
Step 3:
Condensation
|QH|
Step 2:
Compression
Step 4:
Throttling
|QL|
Step 1:
Vaporization
Enthalpy
H 1 H 4
=
H 2 H 1
So how do we obtain the

enthalpy of the refrigerant?
Practically, this is done by
referring to thermophysical data
tables for the refrigerant in
question (enthalpy tables)
These tables give enthalpy/
entropy/specific volume values as
a function of temperature and
pressure
The data in enthalpy tables is
referenced to a standard state,
at which the enthalpy is set
equal to zero (often but not
always 1 atm and 25oC)
Pressure
Thermophysical Data Tables

Hliquid
Hgas
HFC-143A (tetrafluorethylene) is a
standard refrigerant used in domestic cooling
applications
HFC-143A was introduced in the 1990s to
phase out freon 12 (an ozone depleting agent)
1
Enthalpy
Saturated Tables for HFC-143A

(material at liquid-vapor coexistance, for 1kg)
Pressure

3
Hgas
HFC-143A (tetrafluorethylene) is a
standard refrigerant used in domestic cooling
applications
HFC-143A was introduced in the 1990s
to phase out freon 12 (an ozone depleting
agent)
1
Enthalpy
OK, so how do we use

the tables?
Superheated (Gas) Tables for HFC-143A

(material in vapor phase, for 1kg)
Pressure

OK, so how do we use the tables?
PH=10 bar
PL=1 bar
Enthalpy
As an example, say we have a household

refrigerator using HFC-143a: the refrigerator
operates with pressures of 1 and 10 bar
We need to find the enthalpy values at points
1, 2 and 4 (equivalently 3)
H 1 H 4
=
H 2 H 1
H1
H1=231 kJ/kg
H3=105 kJ/kg
What
about H2?
H3
Pressure
Refrigerator Example
3
PH=10 bar
PL=1 bar
The path 1->2 is an adiabat so the

entropy is constant:
S1=0.94 kJ/K kg =S2

1
Enthalpy

H 1 H 4
=
H 2 H 1
H1
H1=231 kJ/kg
H3=105 kJ/kg
What
about H2?
H3
S1
Pressure
3
PH=10 bar
PL=1 bar
The gas table gives me the value of the

enthalpy and entropy at 10 bar for three
different temperature values
I need to interpolate from the table to find the
enthalpy/temperature that corrresponds to S2.
Enthalpy
H 1 H 4
=
H 2 H 1
H1=231 kJ/kg
H3=105 kJ/kg
S
1=0.94 kJ/K kg =S2

Pressure
I will use a linear interpolation scheme:
3
PH=10 bar
PL=1 bar
0.943 0.907
280 269 (0.94 0.907) 279 kJ/kg

+
H 2 269
0.943
0.907
1
Enthalpy
H 1 H
4
=
H
H2
1
H1=231 kJ/kg
H3=105 kJ/kg
S
1=0.94 kJ/K kg =S2
H2=279 kJ/kg
o
50
40
(0.94
0.907)
49.2 C
T2 40+
Pressure
3
PH=10 bar
PL=1 bar
The coefficient of performance is then given by
279 - 231
= 2.63
Compare to Carnot cycle:
Enthalpy
H
1 H 4
=
H 2 H 1
C =
H1=231 kJ/kg
H3=105
kJ/kg
H2=279 kJ/kg

231 -105
1
1
=
QH /QL 1 TH /TL 1
1
=
322.2 /246.6 1
= 3.23
TH = T2 = 49.2 C
TL = T1= 26.4 o C
(from previous
slide)
(from saturated
table)
Liquefaction of Gases
In cryogenic applications it is important to produce liquefied
gases (e.g. liquid nitrogen, hydrogen, helium)
Efficient gas liquefaction requires a special type of throttling process
In order to cool N2, we need to work at a
temperature below the maximum
inversion temperature
The maximum temperature drop for a
given pressure is always obtained by
choosing an initial pressure on the
inversion curve
We can cool N2 by throttling at room
temperature, but the temperature drop is
low and we cant create liquefaction until
we are below around 160 K
Inversion curve for N2

Maximum inversion
temperature
The situation is even more difficult for hydrogen and helium. . .
Inversion curve for H2
Temperature (K)
Maximum inversion
temperature
Pressure (MPa)
Maximum inversion
temperature close to 200K
The situation is even more difficult for hydrogen and helium
Inversion curve for 4He
Maximum inversion
temperature
Maximum inversion
temperature around 43 K
Hampson-Linde Cycle
Liquefaction can be achieved via a special process called the
Hampson-Linde cycle
After throttling the gas is fed back into

a countercurrent heat-exchanger
where it cools the incoming gas
The effect is to successively lower the initial
throttling temperature until liquefaction occurs
Hampson-Linde Cycle
The final steady-state reached by a Hampson-Linde cycle can be
obtained in the following way:
We assume that the throttle valve and
heat-exchanger are completely insulated
The enthalpy per mole of gas entering
the exchanger (hi) must be equal to the
enthalpy per mole of liquefied
component (hLf) and the enthalpy per
mole of the emerging gas (hGf) :
y: mole fraction that is liquefied
hi = y h fL +(1 y) h Gf
y=
h Gf hi
We wish to
maximize y by
minimizing hi
h Gf h Lf

adjust hi by varying Pi)
(We can

Hampson-Linde Cycle
Cyclic rue:
hi: enthalpy per mole of gas entering

exchanger
hfG: enthalpy per mole of gas leaving
exchanger
f (x, y,z) = 0
x y z
= 1
y z z xx y
hfL: enthalpy per mole of liquid formed
y=
h Gf hi
We wish to
maximize y by
minimizing hi
h Gf h Lf
hi
=0
Pi T =T
i
We can write this partial in a

more convenient way by
the cyclic relation
recalling
hi P T
i i = 1
Pi T Ti h hi P
Ti
hi T
hi
i
= = cP
Pi h
Pi T Ti P Pi h
Ti
Need to choose Pi so
= 0 that starting state is on
Pi h inversion curve

Lecture 24: Thermodynamic Potentials I
Time: 2:35-3:25
Office Hours: 2-3MW
Rutherford 411
Reading: 100-107, 109-117 (Finn)
But the entropy cannot be directly measured as a

function of U, V, N: these quantities often are NOT
fixed and cannot be easily controlled experimentally
Enthalpy (H): Natural potential for fixed U, P and N
(one last application)

(today)
(start today)
Grand Canonical Potential (!): Natural potential for fixed T, V and
Review: The Enthalpy and Throttling

The throttling process is used to cool (and ultimately liquefy) gases
Pi
Pi, Ti
Pf<Pi
Pf, Tf
Pi
Pf<Pi
Last lecture we showed that the initial and final states have equal enthalpy
! Measure Tf as a function of final pressure Pf:
! Experimentally it is found for
final pressure
Tf
isenthalps
Tf5
Tf6
Tf4
Tf3
Ti2
Tf2
Tf1
Ti1
Pf
In cryogenic applications it is important to produce liquefied
gases (e.g. liquid nitrogen, hydrogen, helium)
Efficient gas liquefaction requires a special type of throttling process
In order to cool N2, we need to work at a
temperature below the maximum
inversion temperature
The maximum temperature drop for a
given pressure is always obtained by
choosing an initial pressure on the
inversion curve
We can cool N2 by throttling at room
temperature, but the temperature drop is
low and we cant create liquefaction until
we are below around 160 K

Maximum inversion
temperature
The situation is even more difficult for hydrogen and helium. . .
Inversion curve for H2
Temperature (K)
Maximum inversion
temperature
Pressure (MPa)
Maximum inversion
temperature close to 200K
The situation is even more difficult for hydrogen and helium
Inversion curve for 4He
Maximum inversion
temperature
Maximum inversion
temperature around 43 K
Hampson-Linde Cycle
Liquefaction can be achieved via a special process called the
Hampson-Linde cycle
After throttling the gas is fed back into

a countercurrent heat-exchanger
where it cools the incoming gas
The effect is to successively lower the initial
throttling temperature until liquefaction occurs
Hampson-Linde Cycle
The final steady-state reached by a Hampson-Linde cycle can be
obtained in the following way:
We assume that the throttle valve and
heat-exchanger are completely insulated
The enthalpy per mole of gas entering
the exchanger (hi) must be equal to the
enthalpy per mole of liquefied
component (hLf) and the enthalpy per
mole of the emerging gas (hGf) :
hi = y h fL +(1 ! y) h Gf
y=
h Gf !hi
h Gf !h Lf
We wish to
maximize y by
minimizing hi
(We can adjust hi by varying Pi)
Hampson-Linde Cycle
Cyclic rue:
hi: enthalpy per mole of gas entering

exchanger
hfG: enthalpy per mole of gas leaving
exchanger
f (x, y,z) = 0
" !x % " !y % " !z %
$ ' $ ' $ ' = !1
#!y & z #!z & x#!x & y
hfL: enthalpy per mole of liquid formed
y=
h Gf !hi
We wish to
maximize y by
minimizing hi
h Gf !h Lf
"!hi % "!P % "!T %

$ ' $ i ' $ i ' = !1
#!Pi &T #!Ti & h #!hi & P
i
"!hi %
$ ' =0
#!Pi &T =T
i
We can write this partial in a

more convenient way by
recalling the cyclic relation
"!Ti %
#"hi & "!T %
"!hi %
i
$ ' = !% ( $ ' = !cP $ '
#!Pi & h
#!Pi &T $"Ti ' P #!Pi & h
i
"!Ti %
$ ' =0
#!Pi & h
i
Need to choose Pi so
that starting state is on
inversion curve
The Hemholtz Free Energy

The Hemholtz Free Energy is defined:
Differentiating the
Hemholtz Free Energy:
F = U !TS
dF = dU !TdS !SdT
= (TdS!PdV +dN ) !TdS !SdT
dF = !SdT !PdV +dN

The Hemholtz free energy is naturally
expressed as a function of (T, V, N):
F(T,V,N )
dU = TdS !PdV +dN

Thermodynamic Formalism in Hemholtz Representation
F(T,V, N )
# "F &
=
S = !% (
$ "T 'V ,N
S(T,V, N )
" !F %
$ '
#!N &T ,V
(T,V, N )
# "F &
P = !% (
$"V 'T ,N
P(T,V, N )
dF = !SdT !PdV +dN
Law of Decreasing Free Energy

Consider a system with fixed volume in diathermal contact
with a thermal reservoir at temperature To
The reservoir and system are
placed in an isolated enclosure
Consequently the total energy of
the system and reservoir is fixed
Reservoir
To
System
T=To
The law of increasing entropy implies:
(!Q)
+!Ssystem ! 0
!S = !S res +!Ssystem =
To
First Law:
Q = !U system
"U system
To
(no work can be performed)
+!Ssystem! 0
!U system !To "Ssystem = !F ! 0
Hemholtz free energy

must decrease for
spontaneous process
at fixed T and V!
Hemholtz Free Energy and Equilibrium

The reservoir and system are
Reservoir
To
dQ
System
T=To
Q: What condition will ensure the reservoir and system come to equilibrium?
A: Maximization of the entropy of system+reservoir at constant (total) energy!
Differential entropy change:
First Law:
dS = dS res +dSsystem =
dQ = dU system !dW
Total energy fixed:

no work output
dU system !To dSsystem = 0

=T
(!dQ)
+dSsystem = 0
To
equilibrium
condition
!dU system /To +dSsystem = 0
dF = dU system !TdSsystem = 0
(Free energy minimized!)
Hemholtz Free Energy and Equilibrium

Now place the reservoir and system in an
adiabatic enclosure allowing work output
Assume work performed reversibly: total
entropy of the system and reservoir is fixed
Reservoir
To
dQ
System
T=To
dW
Q: What condition will ensure the reservoir and system come to equilibrium?
A: Minimization of the energy of system+reservoir at constant (total) entropy!
Differential energy change:
Total entropy Constant:
dU = dU res+dU system= To dS res +dU system= 0
dS res = !dSsystem

=T

dF = dU system !TdSsystem = 0
(Free energy minimized!)
Hemholtz Free Energy and Maximum Work

So we conclude the free energy is minimized at fixed temperature and system
volume for both irreversible processes (constant total energy) and reversible
processes (constant total entropy). Overall we find:
The Hemholtz Free Energy is minimized in equilibrium for a

system held at constant temperature and volume
If the system is not isolated, work can be performed as the
system comes to equilibrium.
Entropy change as system
comes to equilibrium:
First Law:
!
!
"S = "S res +"Ssystem =
W = "U system "Q
("Q)
+"Ssystem " 0
To
W " "U system

To
+"Ssystem " 0
!
! ! !
!
!
W " "U system "To #Ssystem = "F (work output implies W<0)
!T !
=
!
!
!
!
!

The maximum work that can be output for a process at constant T and
V, or the minimum work required to affect a certain change away from
equilibrium, is given by the Hemholtz Free Energy.
From previous slide:
For work output:
W " "U system "To #Ssystem = "F
Woutput = "W # Wmax = "#F

(the maximum work output possible when the system
comes to equilibrium from!
a certain starting state)
!
For work input:
Winput = W " Wmin = "F
! (the minimum
!
! work!input required to affect a
!
certain change away from equilibrium)
The free energy has for this reason the interpretation of

! to do!useful work
! (i.e. free energy)
energy!
available
Note that increasing system entropy increases the supply of
available free energy by drawing heat from the thermal reservoir

The maximum work that can be output for a process at constant T and
V, or the minimum work required to affect a certain change away from
equilibrium, is given by the Hemholtz Free Energy.
For work output:
Woutput = "W # Wmax = "#F

comes to equilibrium from a certain starting state)
Winput = W " Wmin = "F

! (the minimum
! work!input required to affect a
For work input:
Note that it is possible to increase the free energy by

! system
!
performing work
!
! on the
Even if there is no internal energy change, I can always use work
input to drive heat flow to the reservoir (decreasing system entropy)
The entropy of a thermally isolated system, in contrast,
only goes in one direction, i.e. increases.
Isothermal Ideal Gas Expansion

Consider an example of free energy changes in ideal gas expansion:
Irreversible
expansion
N molecules
of ideal gas
(System surrounded by thermal

reservoir at temperature T)
Free Energy Change:
"F = "U "T#S

(ideal gas)
"S = k B N ln(V f /Vi ) = k B N ln 2

! !T ln 2
! = "Nk
"F
B
!
"S res = 0 !; "S univ! = "S

!
Isothermal Ideal Gas Expansion

Consider an example of free energy changes in ideal gas expansion:
N molecules
of ideal gas
Reversible
expansion
"F = "U "T#S

(ideal gas)
"S = k B N ln(V f /Vi ) = k B N ln 2
Woutput = Nk B T ln 2 = "#F
(in this case the free energy
!can!be completely
change
!
converted into useful work)
Free Energy Change:
"S univ = "S res + "S = 0
Pext=P
Pext=P
(System surrounded by thermal

reservoir at temperature T)
! !T ln 2 (the same)
! = "Nk
"F
B
"S res = "Q/T
! /T = k B N ln 2
! =W
!

F = U "TS
The Hemholtz Free Energy embodies the competing
effects of entropy and internal energy in determining a
systems equilibrium state at constant temperature
! !!
At low temperature internal energy wins and equilibrium will be

determined by energetic considerations
At high temperature entropy wins and equilibrium will
be determined by entropy maximization
We will develop a simple model of dimerization to explore
these effects
Free Energy Example: Dimerization Model

Consider one-dimensional gas of two molecules
that can bond pairwise to form dimers
When molecules are adjacent they

are in a dimer-state
When molecules are apart they

are in a monomer state
There are V sites on the lattice (N=2)

Molecules in dimer-state
have a free energy:
= k B ln "dimer
Fdimer = U dimer "TSdimer
"!
#
!dimer=V-1:
(There are V-1 ways to place
one dimer on the lattice)
! = "#
(bonding
energy)
"k B T ln(V "1)

V sites on the
lattice (N=2)

Molecules in monomer-state
have a free energy:

= k B ln " mono
Fmono = U mono "TS mono
=!0 (no interactions)
To find multiplicity of monomer state, note that it will be equal to the total
number of distinct ways to place two molecules on the lattice (V choose 2)
minus the number of these states that would be consistent with dimerization
" mono = " total "#dimer
V!
"(V "1) = (V "1) (V /2 "1)
=
(V " 2)!
2!!

V sites on the
lattice (N=2)

Molecules in monomer-state
have a free energy:

Fmono = U mono "TS mono

= k B T ln (V /2 "1) (V "1)
Molecules in dimer-state
have a free energy:
Fdimer = "#
!
!
V>4
"k B T ln(V "1)
The state with the lowest

free
! will be favored
! energy
!

V sites on the
lattice (N=2)


Fmono = k BT ln (V /2 "1) (V "1) F 0

"#
F
= "# "k BT ln(V "1)
Fmono
dimer
(monomer
! has steeper
! free energy
slope as a function of T)
! favored at high temperature;

Monomer
! state
dimer state a lower temperature
Fdimer
dimer
monomer
To
The Gibbs Free Energy

The Gibbs Free Energy is defined:
G = U "TS +PV
Differentiating the Gibbs

free energy:
dG = dU "TdS "SdT +PdV +VdP

= (TdS"PdV +dN ) "TdS "dTS +PdV +VdP
! !! !
+dN
dG ="SdT
+VdP
!
! ! ! ! !
is naturally
!The Gibbs!free energy
! G(T,P,N )
!
!
expressed as a function of (T, P, N):
dU = TdS "PdV +dN

Thermodynamic Formalism in Gibbs Representation
G(T,P, N )
$#!
G'
=
S = "& )
% #T ( P,N
S(T,P, N )
!
!
# "G &
# "G &
% (
$"N 'T ,P V = %$ "P ('T ,N
V (T,P, N )
(T,P, N )
!
dG
! = "SdT +VdP!+dN
!
Gibbs Free Energy and Chemical Potential

The Gibbs free energy has a close relation to the chemical potential
Gibbs Free Energy:
G = U "TS +PV
Recall that the internal energyusing the

Euler relationcan be written as:
U = TS "PV +N
! +N ) "TS +PV = N
! "PV
! G =!(TS
For a one component system:
! ! ! !
! !
G! =!N !
! !
Law of Decreasing Gibbs Free Energy

Consider a system with fixed volume in contact with a
thermal and pressure reservoir at Po and To
The reservoirs and system are
Reservoir
To
("Q)
+"Ssystem " 0
"S = "S res +"Ssystem =
!
To
First Law:
"U system = Q +W = Q "Po #Vsystem
Po "Vsystem+"U system
!
!
!"
! +"Ssystem " 0
To
! ! "T
!
"U system !
+Po "V
system !o #Ssystem = "G " 0
!
System
T=To;
P=Po
W
Po
!
Gibbs Free
energy must
decrease for
spontaneous
process at
fixed P and T!

Gibbs Free energy must decrease for
spontaneous process at fixed P and T!
This result is extremely important for indicating whether a given
chemical reaction can or cannot go forward
(chemistry normally takes place at conditions of constant P and T!)
If the "Greaction<0: reaction can spontaneously go forwards
If the "Greaction>0: reaction can only proceed spontaneously
in backwards direction
If the "Greaction=0: recants and products exist at equilibrium
Oxidation of glucose:
Photosynthesis:
C6H12O6 +6O2
6CO2 +6H2O
"Greaction= - 2870 kJ/mole (25oC): can go forwards
!
"
CO2+H2O " CH2O +O2

"Greaction= + 470 kJ/mole (25oC): cannot go forwards
(requires external energy source: sunlight!)
Gibbs Free Energy and Equilibrium

Show that the following statement is true using either entropy
maximization (fixed energy) or energy minimization (fixed entropy)
The Gibbs Free Energy is minimized in equilibrium for a system
held at constant temperature and pressure
Reservoir
To
dQ
System
T=To;
P=Po
dW
Po
G = U!"TS +PV
Hint 1: What does entropy maximization (dS=0) or energy minimization
(dU=0) tell us? (pick one approach)
Hint 2: What does the first law tell us? (entropy maximization) How do constraints relate
changes of volume and entropy of system and reservoir? (energy minimization)
! !! !

Reservoir
To
First Law:
dQ
System
T=To;
P=Po
dW
dS = dS!
res +dSsystem =
dQ =!dU system"dW
Po
("dQ)
+dSsystem = 0
To
equilibrium
= "Po dVsystem
!
!
!
!
! )dV
!
"dU system /To "(Po /T
o
system +dSsystem = 0
!
! !
dG = dU system +PdVsystem "TdSsystem = 0
!
!
condition

The Gibbs potential combines the equilibrium condition of the
enthalpy and Hemholtz Free Energy.
The Gibbs potential plays an essential role in thermodynamic
theories of chemical reactions and phase equilibria
(due to the ubiquity of constant pressure/temperature conditions)
Gibbs Free Energy and Maximum Work

The Gibbs free energy, like F, provides a measure of energy
available for work as a system proceeds to equilibrium
How does the interpretation of G and F as free energies differ?
Hemholtz Free Energy: gives the total energy available for
work (includes PV work involved in expansion/contraction)
Gibbs Free Energy: gives the energy available for work NOT
including PV work involved in volume expansion/contraction
So what other forms of work remain? (chemical work, electrical
work, photochemical work)
Demonstration:
"G = "U "T#S +P"V = Wother

= "F = "P#V +Wother

Lecture 26: Thermodynamic Potentials III
Time: 2:35-3:25
Office Hours: 2-3MW
Rutherford 411
Reading: 100-107, 109-117 (Finn)

(short
review)
(today)
Review: Hemholtz Free Energy

The Hemholtz Free Energy has two key properties:
The Hemholtz Free Energy is minimized in equilibrium for a
system held at constant temperature and volume
The change in Hemholtz Free Energy gives the maximum work that
can be output for a process at constant T and V; or the minimum
work required to affect a certain change away from equilibrium
The free energy, when referring to processes involving work

output, consequently has the interpretation of energy available to
do useful work (i.e. free energy)
Review: Hemholtz Free Energy (Work Output)

The Hemholtz Free Energy gives the maximum work output
possible as a system at constant T and V comes to equilibrium
For work output:
output
Woutput = W Wmax
= F
comes to equilibrium from a certain starting state)
This maximum energy available for work output (-F) arises from two sources:
output
Wmax
= F = U +TS
Decreases in system
Internal energy
output
to surroundings)
(energy
Increases in system entropy that

induce a heat flow from the
thermal reservoir to the system
This heat flow can do extra

work and hence increases the
net free energy change
Review: Hemholtz Free Energy (Work Input)

The Hemholtz Free Energy gives the minimum work input
necessary to affect a certain change away from
equilibrium for a system held at constant T and V
For work input:
input
Winput = W Wmin
= F
(the minimum work input required to affect a
Conversely, performing the minimum work input (F) can have

system:
on the
two effects
input
Wmin
= F = U TS
Increase internal energy

of system
Decrease system entropy

(inducing a heat flow to the
reservoir)

One last slide on Hemholtz Free Energy!
F(X)
System falls to free

energy minimum
X: some thermodynamic
coordinate
Xo
XE

F(X)
Max potential work
output for process:
max
W output
= F
Xo
XE

F(X)
Min work input required to
drive system away from
equilibrium and back to Xo:
W min = F
input
Xo
XE

The Gibbs Free Energy is defined:
G = U TS +PV
Differentiating the Gibbs

free energy:
dG = dU TdS SdT +PdV +VdP

= (TdSPdV +dN ) TdS dTS +PdV +VdP

+dN
dG =SdT
+VdP

is naturally
The Gibbsfree energy
G(T,P,N )
expressed as a function of (T, P, N):
dU = TdS PdV +dN

Thermodynamic Formalism in Gibbs Representation
G(T,P, N )
G
=
S =
T P,N
S(T,P, N )
G
G

N T ,P V = P T ,N
V (T,P, N )
(T,P, N )
dG
= SdT +VdP+dN
Gibbs Free Energy and Chemical Potential

The Gibbs free energy has a close relation to the chemical potential
Gibbs Free Energy:
G = U TS +PV
Recall that the internal energyusing the

Euler relationcan be written as:
U = TS PV +N
+N ) TS +PV = N
PV
G =(TS
G =N

Consider a system with fixed volume in contact with a
thermal and pressure reservoir at Po and To
The reservoirs and system are
Reservoir
To
(Q)
+Ssystem 0
S = S res +Ssystem =
To
First Law:
U system = Q +W = Q Po Vsystem
Po Vsystem+U system
+Ssystem 0
To
U system
+Po V
system o Ssystem = G 0
System
T=To;
P=Po
W
Po
Gibbs Free
energy must
decrease for
spontaneous
process at
fixed P and T!

Gibbs Free energy must decrease for
spontaneous process at fixed P and T!
This result is extremely important for indicating whether a given
chemical reaction can or cannot go forward
(chemistry normally takes place at conditions of constant P and T!)
If the Greaction<0: reaction can spontaneously go forwards
If the Greaction>0: reaction can only proceed spontaneously
in backwards direction
If the Greaction=0: recants and products exist at equilibrium
Oxidation of glucose:
Photosynthesis:
C6H12O6 +6O2
6CO2 +6H2O
Greaction= - 2870 kJ/mole (25oC): can go forwards
CO2+H2O CH2O +O2

Greaction= + 470 kJ/mole (25oC): cannot go forwards
(requires external energy source: sunlight!)

Show that the following statement is true using either entropy
maximization (fixed energy) or energy minimization (fixed entropy)
Reservoir
To
dQ
System
T=To;
P=Po
dW
Po
G = UTS +PV
Hint 1: What does entropy maximization (dS=0) or energy minimization
(dU=0) tell us? (pick one approach)
Hint 2: What does the first law tell us? (entropy maximization) How do constraints relate
changes of volume and entropy of system and reservoir? (energy minimization)

Reservoir
To
First Law:
dQ
System
T=To;
P=Po
dW
dS = dS
res +dSsystem =
dQ =dU systemdW
Po
(dQ)
+dSsystem = 0
To
equilibrium
= Po dVsystem
)dV
dU system /To (Po /T

o
system +dSsystem = 0

dG = dU system +PdVsystem TdSsystem = 0
condition

The Gibbs potential combines the equilibrium condition of the
enthalpy and Hemholtz Free Energy.
The Gibbs potential plays an essential role in thermodynamic
theories of chemical reactions and phase equilibria
(due to the ubiquity of constant pressure/temperature conditions!)
Gibbs Free Energy as a Free Energy

The Gibbs free energy (like F) provides a measure of energy
available for work as a system proceeds to equilibrium
The Gibbs free energy (also like F) gives the minimum work
input required to affect a certain change in a systems state
How does the interpretation of G and F as a form of
work input/output differ?
Recall that
G = U +PV TS = H TS
(at constant P and T)
In comparison:
F = U TS
Heat exchange
with reservoir
Instead
ofinternalenergy
changes,
the Gibbs Free
Energy involves enthalpy changes
Gibbs Free Energy as Free Energy

Let us review certain properties of the enthalpy
Heat transferred to
system or evolved in
reactions
The first law:
System
V, P
U = PV +Q +Wother
Work performed on
system by pressure
reservoir
Other work!
(electrical,
photochemical)
Pos
Pressure
reservoir
System is in contact with pressure

reservoir (e.g. atmosphere)
Now
I can rewrite this as:
H = U + PV = Q +Wother
Energy gain of pressure reservoir
(due to work performed on reservoir)

For a system in contact with a pressure reservoir. . .
Heat input or input of other work can have two effects:

(1) These inputs can increase system internal energy
(2) Theycan alsolead

to work performed against the pressure reservoir,
increasing PV (i.e. by increasing system volume at constant pressure)
Conversely, system can output other work/heat energy in

two ways:
(1) By decreasing system internal energy
(2) By letting pressure reservoir perform work, decreasing PV
(i.e. by decreasing system volume at constant pressure)

BUT often I dont care exactly how the energy input is distributed
between U and PV or what the source of the energy output is!
All I need
to know
is the net enthalpy change,
which takes both of these effects into account!

Returning to the Gibbs Free Energy:
For a system in equilibrium with both pressure and thermal reservoirs:
G = H TS = Q +Wother TS
= TS +Wother TS = Wother
Gibbs Free Energy as Max Work Output: at fixed

pressure/temperature (-G) gives the energy available for
other work
output (e.g. NOT including output of PV work
against reservoir)
Gibbs Free Energy as Min Work Input:
at fixed pressure/
temperature G gives minimum other work required to affect
change away from equilibrium (e.g. NOT including PV work
input by reservoir)
Example: Electrolysis of Water

The Gibbs free energy measures the additional other work
that must be performed to drive a chemical reaction
Water molecules can be separated into hydrogen and oxygen by applying a

voltage drop and running an electrical current
Electrolysis:
H 2O H 2 +
Hydrogen bubbles form at
negative electrode
1
2O
Oxygen bubbles
form at positive
electrode

Water molecules can be separated into hydrogen and oxygen by applying a
voltage drop and running an electrical current
Electrolysis:
H2O H2 + 21 O
We can obtain (from reference tables) the enthalpy and entropy changes:
H = 286 kJ
S = 163 J/K
(enthalpy change for electrolysis of 1 mole of water)
(entropy change after producing 1 mol of hydrogen

and 0.5 oxygen from 1 mole of water)
The entropy increase implies that additional energy will enter as heat:
Q = TS = (298K ) (163 J/K) = 49 kJ
(this is energy supplied by

the thermal reservoir!)

As a side note, you might wonder how much of the enthalpy increase required
arises from internal energy changes and how much arises from work performed
on the atmosphere (e.g. work required to make room for the gases!)
The work performed in creating 1.5
moles of an ideal gas at 1atm:
Vgas = Nk B T / Patm
W = Nk B T = 1.5N av k B T = 1.5RT
= 1.5
(8.314 J/K) (300K) = 3.7 kJ
U = H
PV= 286kJ 3.7kJ =282 kJ
W = Patm Vgas
(the volume of the original water

can be neglected as being very
small in comparison with the gas
volume)

Electrolysis:
H2O H2 + 21 O
We can obtain (from reference tables) the enthalpy and entropy changes:
H = 286 kJ
S = 163 J/K
TS = 49 kJ
(enthalpy change for electrolysis of 1 mole of water)
(entropy change after producing 1 mol of hydrogen

and 0.5 oxygen from 1 mole of water)
(energy supplied as heat from thermal reservoir)
The change in Gibbs Free Energy is then:
G = H TS = 237 kJ
This
is the energy that must be supplied by the battery
to drive the reaction forward!

H2O H2 + 21 O
Electrolysis:
The change in Gibbs Free Energy is then:
G = H TS = 237 kJ
that must be
This is the energy
supplied by the battery
to drive the reaction forward!
The electrical work that must be

supplied to drive the reaction:
Welectrical = G
Welectrical = q V = (2e N av ) V
V = G /(2e N av )
1.6
10
/(2
= 237 kJ
19 C 6.022 10 23 )
= 1.2 V

(voltage required to drive electrolysis)
Example: Hydrogen Fuel Cell

Electrolysis:
H2O H2 + 21 O (G = +237 kJ)
Hydrogen/Oxygen Burning:
H2 + 21 O H2O
(G = 237 kJ)
energy available
for
work output!
This is
Principle of hydrogen fuel

cell technology
Hydrogen oxidized at porous anode
releasing electrons and protons
Electrons travel through external
circuit performing electrical work
Protons travel through electrolyte medium
to combine with electrons and oxygen gas
at cathode, producing water and
completing reaction

Lecture 27:
Legendre Transformation and Maxwell Relations
Time: 2:35-3:25
Office Hours: 2-3MW
Rutherford 411
Reading: 100-107, 109-117 (Finn)
Thermodynamic Potentials and The

Legendre Transformation
So far we have introduced H, F and G and discussed some
of their applications and interpretations
The potentials were introduced on an ad-hoc basis: you
might wonder if there is a systematic procedure to deduce the
potentials?
The answer is YES: the potentials can be derived using the
concept of Legendre transformation
The Legendre transformation is a useful mathematical
concept which is widespread in many areas of physics: it
is worth spending some time to introduce it
Thermodynamic Potentials and The

Legendre Transformation
The thermodynamic potentials repackage the formalism when an
intensive variable, like T, P or is considered to be independent
Recall that the intensive variables (T, P or ) are obtained from
partial derivatives of the internal energy or entropy
The fundamental mathematical question is:

In general terms, how do we express the complete information
embodied by a given functional relationship in terms of the value of
the function and its derivative at x, rather than the value of the
function and x itself?
The Legendre Transformation

Consider some mathematical curve described by Y(X):
Now, let us consider

the slope of this curve:
Y(X)
We can solve for X(P)

and write:
dY
P
dX
Y Y (P)

Consider some mathematical curve described by Y(X):
Y1(X)
Y(X)
Y2(X)
Now, let us consider

the slope of this curve:
We can solve for X(P)
and write:
dY
P
dX
Y Y (P)
does not contain

But Y(P)
all the information of the
original
curve!
Curves Y1 and Y2 would yield the same relation Y(P)!

(these curves yield the same value Y for a given slope P)

So what is the solution to this difficulty?
Y
A given curve can be

represented in TWO ways:
Y=Y(X)
(1) By a locus of points described by Y(X)

Each point in the plane is determined
by two numbers (X, Y)
The curve selects a subset of the
points (X,Y) satisfying Y=Y(X)

So what is the solution to this difficulty?
Y
A given curve can be

The tangent lines Y(X)
represented in TWO ways:
making up curve
satisfy Q=Q(P)
(1) By a locus of points described by Y(X)
dY
dX
(2) As the envelope of a family of

tangent lines!
Each tangent line is specified by two

numbers, its slope and intercept (P, Q)
X
Q: y-intercept
of tangent lines!
The relation Q=Q(P) selects a subset

of all lines and hence the curve of
which they constitute the envelope

I want a transformation: (X, Y) (P, Q)
Y
We can obtain this transformation

by calculating the slope of the
tangent line at (X, Y):
Y(X)
dY
P
dX
P=
(X, Y)
Y Q
X 0
Q = Y PX
Using Y(X) and X(P)
Q(P) = Y (P) PX(P)

(Legendre Transform)

What about the inverse problem? (P, Q) (X, Y)
Y
Y(X)
Say I know:
Q(P) = Y PX
dQ = dY PdX XdP
dY
P
dX
But dY = P dX
dQ = XdP

dQ
(X, Y)
X =
dP
X
which we can solve for P(X)
This givesus: X(P)
Y
(X) = Q(X) + P(X)X

To make this concrete let us consider a simple example
Let Y(X) be the quadratic function:
Y (X) = X 2
To find the Legendre Transform:
dY
P=
= 2X
X = P /2
dX
Q(P) = Y (P) PX(P) = P 2 / 4 P 2 /2 = P 2 / 4
To
go backwards:
dQ
= P /2
X =
dP
Y (X) = Q(X) + P(X)X
2
2
2
=
X
= X +2X

Y
Y = X2

The quadratic function Y=X2
expressed as an envelope of
tangent lines

(Multi-Variable Case)
The Legendre transformation generalizes naturally to the
multi-variable case, i.e. Y(Xo, X1. . .)
In this case, we can either visualize the function as the locus of
points (Xo, X1, Y) or as an envelope of tangent hyperplanes
Y
Y=Q (intercept)
Slope P1
Slope Po
(Xo, X1, Y)
Xo
Y
Y
Po
; P1
X 1 X
X o X
1
Equation of tangent
X1 hyperplane at (Xo, X1):
Q = Y Po X o P1 X 1

For a function of two independent variables. . .
Legendre transform
Inverse Legendre transform
(X o , X 1 , Y ) (Po , P1 , Q)
(Po , P1 , Q) (X o , X1 , Y )
Y
Y
Po
; P1
X o X
X 1 X
Q
Q
X o
; X 1
P1 P
Po P
Solve to find: Xo(Po, P1) and X1(Po, P1)
Solve to find: Po(Xo, X1) and P1(Xo, X1)
Q(Po
,P1 ) = Y Po X o
P1 X 1
Y (X o ,
X 1 ) = Q +Po X o +P1 X 1

For a function of N independent variables. . .
Legendre transform
(X o , , X N , Y ) (Po ,,PN , Q)
Y
Pk
X k all X
(Po ,,PN , Q) (X o , , X N , Y )
Q
X k
Pk all P
ik
Solve to find: Xk(P0,. . .PN):
ik
Solve to find: Pk(X0,. . .XN):
Q(P1 ,,PN ) = Y Pk X k
k=1
Y (X 1 ,, X N ) = Q + Pk X k
k=1

(Multi-Variable Case, Partial)
We can also choose to perform a Legendre transform with respect to
a particular sub-set of the independent variables
For example, we can choose to perform a Legendre transformation
for one or two variables of a three variable function (in this case, Xo)
Legendre transform
(X o , X 1 , X 2 , Y ) (Po , X 1 , X 2 , Q)
Y
Po
X o X ,X
(X o , X1 , X 2 , Y )
Q
X o
Po X ,X
Solve to find: Xo(Po, X1, X2)
Q(Po , X 1 , X 2 ) = Y Po X o
(Po , X 1 , X 2 , Q)
Solve to find: Po(Xo, X1, X2)
Y (X o , X 1 , X 2 ) = Q +Po X o
The Legendre Transformation and

Thermodynamics
The Gibbs potential is simply the Legendre transformation of
the internal energy with respect to S and V
Legendre transform
(S, V, N, U) (T, P, N, G)
(T, P, N, G) (S, V, N, U)
U
U
T ; P
S V ,N
V S,N
G
G
S ; V
P T ,N
T P,N
Solve to find: S(T, P, N) and V(T, P, N)
G(T,P,
N ) = U TS+PV
Solve to find: T(S,V,N) and P(S,V,N)
U (S,V.N
) = G +TS PV
Free Energy (F) is the Legendre transform of U with

The Hemholtz
respect to S; the Enthalpy (H) is the Legendre transformation of U
with respect to V

Calculate the Legendre Transformation of U with respect to S
and N: this function is known as the Grand Canonical Potential.
For reference: below is shown a transformation of two out of three variables
Legendre transform
(X o , X 1 , X 2 , Y ) (Po , P1 , X 2 , Q)
Y
Pk
X k X
ik

(Po , P1 , X 2 , Q)
(X o , X1 , X 2 , Y )
Q
X k
Pk P
ki
Solve to find: Xo(Po, P1, X2)
Solve to find: Pi(Xo, X1, X2)
Q(Po ,P1 , X 2 ) = Y Po X o
Y (X o , X 1 , X 2 ) = Q +Po X o
P1 X 1
+P1 X 1

Calculate the Legendre Transformation of U with respect to S and
N: this function is known as the Grand Canonical Potential .
Legendre transform
(S, V, N, U)
(T, V, , )

(T, V, , )
(S, V, N, U)
U
U
T
N S,V
S V ,N

S N
TV ,
T ,V
(T,V, ) = U TS N
U (S,V.N ) =
+TS + N
The Maxwell Relations

U(S,V, N )
U
T= =
S V ,N
U
U
P =

V S,N
N V ,S
What if we consider forming mixed 2nd order partial derivatives of U

with respect to its natural variables?

2U P
U
S V S,N SV S V .N
V ,N
T P
=
V S,N S V .N
Notational nightmere!
Equality of mixed partials
2
U
U = T

V
S V ,N S,N VS V S,N
A Maxwell relation

H(S,P, N )
H
T=
=

S P,N
H
V
2H
=

S P S,N P,N SP S P.N
H
H
V=

P S,N
N P,S
T V
=
P S,N S P,N
2
H
T
H
=

P S P,N S,N PS P S,N
Another Maxwell
relation

Thermodynamic Formalism in Hemholtz Representation
F(T,V, N )
F
S =
TV ,N
F
F
=
P =
V T ,V
N V ,T
Find a Maxwell relation following from the mixed partial of F with respect
to T and V. . .

2 F P
F
T V T ,N TV = T
V .N
V ,N
S
P
=
T V ,N V T .N
2
F
S
F

=
T V ,N T ,N VT
V
T ,N

Proceeding in this wayand also equating partial derivatives including
Nwe can construct three Maxwell relations for each thermodynamic
potential that can be obtained from U by Legendre transform!
We can create a whole sea of Maxwell relations (21 in all)!
Simply mind numbing!
Nonetheless, the Maxwell relations are extremely useful for

expressing partial derivatives of the entropy in terms of
partial derivatives that can be measured or obtained from a
thermodynamic equation of state
How can one possibly remember them all?

There is a mnemonic diagram for the most useful
Maxwell relations. . .
Society for the Prevention of the Teaching of Vectors

How do you use the diagram?
T T
V S
Partial of T with respect to V at constant S. . .

T T
V S
and S
I pick up a negative sign

whenever I traverse
the leg
of the square between P
P

P S V
Partial of T with respect to V at constant S. . . Is equal to. . .

Negative of partial of P with respect to S at constant V

Another example. . .
T T
P S
V V

S P
V
T
=
S P P S

Here is an example of the use of Maxwell relations (Finn, 122-123)
Let us consider the isothermal, reversible
compression of a block of metal:
Pi Pf
Constant temperature
Question: What is the heat transfer to or from the metal during

the compression?
dQ = TdS
Express entropy in terms of P and T: S(P,T)
Process reversible:
0
S
S
V
S
dS = dP + dT = dP = dP
T P
P T
T P
P T
Using a Maxwell relation!

(obtained from Gibbs Free Energy)

Let us consider the isothermal, reversible
Pi Pf
compression of a block of metal:
Constant temperature
Question: What is the heat transfer to or from the metal during
the compression?
Process reversible:
Pf
dQ = TdS= T dP = T V dP
T P
Q = T V dP TV
Pi
Pf
dP = TV (Pf
Pi
Pi )
(Heat is
evolved from the
if is positive)
metal
Thermodynamic Manipulations
In thermodynamics it possible to form a large number of partial
derivatives involving state functions and state variables
Some quantities are hard if not impossible to measure directly:
Derivatives involving entropy and internal energy
Derivatives where the volume is held constant
Some quantities are relatively easy to measure:
(1) Heat Capacity at constant pressure CP
1 V
(2) Volume expansivity :
V T P
1
(3) Isothermal compressibility T: T
V
temperature
(4) Pressure and
V

P T

(1) Heat capacity at constant pressure CP
(3) Isothermal compressibility T:
(4) Pressure and temperature
We would like to be able to relate quantities which are hard

to measure to quantities which are easy to measure
We will show how this can be done using the Maxwell relations and
other formal relations among partial derivatives drawn from a single
equation of state (e.g. cylic relation)
Difference in Heat Capacities

We can use Maxwell relations to deduce an expression for the
difference between Cp and CV in terms of the volume expansivity ()
and isothermal compressibility (T)
Recall:
S
S
CV = T ; C P = T
T P
T V
Now expand the entropy in terms of dT and dV:
= CV
S
S
TdS =T dT +T dV Express dV in terms of dT and dP

T V
V T V
V
= dT + dP
=
C
P
T P
P T
V S
= CV +T
dT +V dP
T PV T

P T

We can use Maxwell relations to deduce an expression for the difference
between Cp and CV in terms of the volume expansivity () and isothermal
compressibility (T)
= V
2
V S
V
From last slide: C = C +T
=
C
+T
P
V
T PV T V
T
P
holding the
This derivative still involves
= (Maxwell relation!)
system at constant volume
T V
(hard to arrange

experimentally)
P T V
= 1
Recall cyclic relation f (V,P,T) = 0
T V P
V
P
P V 1 V 1
= =
T V
V T T P
V T P V
V
= / T
P T

Lecture 28: Thermodynamic Manipulations
Time: 2:35-3:25
Office Hours: 2-3MW
Rutherford 411
Reading: Finn Chapter 7
In thermodynamics it possible to form a large number of partial
derivatives involving state functions and state variables
(1) Heat Capacity at constant pressure CP
1 V
V T P
1
(3) Isothermal compressibility T: T
V
temperature
(4) Pressure and
V

P T

(1) Heat capacity at constant pressure CP
(3) Isothermal compressibility T:
(4) Pressure and temperature
We would like to be able to relate quantities which are hard

to measure to quantities which are easy to measure
We will show how this can be done using the Maxwell relations and
other formal relations among partial derivatives drawn from a single
equation of state (e.g. cylic relation)

There is a mnemonic diagram for the most useful
Maxwell relations. . .
Society for the Prevention of the Teaching of Vectors

T T
V S
Partial of T with respect to V at constant S. . .

T T
V S
and S
I pick up a negative sign

whenever I traverse
the leg
of the square between P
P

P S V
Partial of T with respect to V at constant S. . . Is equal to. . .

Negative of partial of P with respect to S at constant V

We can use Maxwell relations to deduce an expression for the
difference between Cp and CV in terms of the volume expansivity ()
and isothermal compressibility (T)
Recall:
S
S
CV = T ; C P = T
T P
T V
Now expand the entropy in terms of dT and dV:
= CV
S
S
TdS =T dT +T dV Express dV in terms of dT and dP

T V
V T V
V
= dT + dP
=
C
P
T P
P T
= C +T
V S dT +T S V dP
V
T PV T
V T P T

We can use Maxwell relations to deduce an expression for the difference
between Cp and CV in terms of the volume expansivity () and isothermal
compressibility (T)
= V
2
V S
V
From last slide: C = C +T
=
C
+T
P
V
T PV T V
T
P
holding the
This derivative still involves
= (Maxwell relation!)
system at constant volume
T V
(hard to arrange

experimentally)
P T V
= 1
Recall cyclic relation f (V,P,T) = 0
T V P
V
P
P V 1 V 1
= =
T V
V T T P
V T P V
V
= / T
P T
Derivative of Heat Capacities

What about partial derivatives of the heat capacity?
C V
S

= T =T
V T
V T T V
T V
S

V T
(change differentiation order)
Maxwell
relation
2 P
P
=T =T 2
T V
T V T
(which we can calculate

from the equation of state)
Derivative of Heat Capacities

2 P
C V
=T 2
V T T
The ideal gas law:
2 P
2 =0
T V
PV = Nk B T
C
V
=0
V T
CV must
be independent
Thus
of volume for an ideal gas!
(we
already knew this, but it is quite remarkable that this property
follows simply from the ideal gas law)
The Energy Equation

Remarkably, from the equation of state alone, it is also possible to
determine how the internal energy of a system depends on the volume
dU = T dSP dV
S
S
(Expanding dS in
dT +T P dV
terms of dT and dV) = T
T V
V T
U
S
U
= T P
=
V T
V T
V T
= (Maxwell Relation)
T V
The first law:
The Energy Equation

U
P
= T P
V T
T V
PV = Nk B T
P Nk B
P Nk B T
T =
=
=P
T V V
T V
V
U
U ideal = U (T)
=0
VT
The ideal gas law:
The Energy Equation

U
P
= T P
V T
T V
Find U(T, V) for a Van der Walls fluid
Equation-of-state for
der Walls fluid:
Van
Nk B T
N2
P=
a 2
V Nb
V
U
CV =
T V
The Energy Equation

U
P
= T P
V T
T V
P
Nk B
P Nk B T
N2
= P +a 2
=
=
T
T V Nb
T V V Nb
V
V
U
N2
=a 2
Nk B T
N
Van der Walls fluid:
P=
V Nb
The Energy Equation

U
U
dU = dT + dV
T V
V T
= CV
(independent of volume!)
C V
=T
V T
N2
=a 2
V
2
P
2 = 0
T V
2
U = CV (T) dT aN /V
(I decide NOT to assume

that CV is independent of T)
Van der Walls fluid:
Nk B T
N
P=
a 2
V Nb
V
Joule Coefficient for Free Expansion

It is useful to calculate how the temperature of an isolated gas
changes upon expansion or compression
An isolated system receives no heat flow and performs no
work so it has constant internal energy during expansion
An ideal gas would have constant temperature for such a
process, but we wish to analyze the situation in general terms
The key partial derivative:
T

V U
= J
Requiring that U be kept

constant makes life hard!
(called the Joule coefficient)

The key partial derivative:
T

V U
Requiring that U be kept

constant makes life hard!
The trick to dealing with the constant U during differentiation is

to use the cyclic rule
Realize that
f (T,V,U) = 0
T V U
= 1
V U U T T V
Energy equation
U U
1 U 1
= =
=
P
V U V T T V CV V T CV
P
T
T V

T
P
J = = P T
V U CV
T V
Note that J vanishes for an ideal gas
(we showed this in regards to the energy equation)
willhave a non-vanishing J
Real gases
While we could use a VdW equation of state to describe real gas

behavior, an alternative is to use a virial expansion
Virial Expansion
In a virial expansion the gas pressure is expressed as a
power series in terms of the molecule number density c=N/V:
2nd Virial Coefficient
Virial expansion:
PV
= Nk B T 1 +
N 2
N
B(T) +C(T) + +
V
V
Ideal gas behavior
3rd Virial Coefficient
The second virial coefficient measures the binary interactions
between molecule pairs (~N2)
The second virial coefficient follows a

semi-empirical relation:
B(T) = e
/T
The values of , and can be determined from tables for different gases
(see http://www.kayelaby.npl.co.uk/chemistry/ for example)

T
P
J = = P T
V U CV
T V
Nk
P
B
For the virial expansion:
+ +
1
+
B(T)
(keep only terms up to N/V)
T
V
V V
Nk B T dB N
2
2
+
k B T N dB
J =
dT V
V
2
CV V dT

PV
1
+
B(T)
= Nk
T
N
N
+C(T) + +
V
V
Joule Coefficient for Throttling Process

You may recall the Throttling process: a gas is forced through a
small valve or porous membrane between some initial pressure Pi
and final pressure Pf.
Pi
Pi, Ti
Pf<Pi
Pf, Tf
Pi
Pf<Pi
This process occurs at constant enthalpy (lecture 24)

final pressure
Tf
Tf5
Tf6
Tf4
Tf3
Ti2
Tf2
Tf1
Ti1
Pf

Temperature (K)

10
20
Inversion curve
Tf begins to fall)
30
Pressure (MPa)
40
50

In a throttling process, the key partial derivative is: T

(for example, on the inversion curve this derivative is 0) P H
= JK
As before we use cyclic relations to deal with the
requirement of holding H constant
Realize that
f (T,P, H) = 0
T P H
= 1
P H H T T P
T
1 H

=

C P P T
P H
H H
=
P H
P T T P
(we will deal with this partial
derivative on the next slide)

The enthalpy: dH = T dS+V dP
S
S
(Expanding dS in
dT +T +V dP
terms of dT and dP) = T
T P
P T

H
=
P T
T
S
1 H
1
= C = T +V
CP
P H
P P
P T
T
Maxwell relation
V
=
V
( T 1 )
CP
= = V
T P

JK
On the inversion
curve:
T
= 0
P H
= 1/T
T
= = V ( T 1 )
P H C P
=0
H
You will explore his more fully in

your HW using the VdW Eq of State
Example Manipulation Problem

Express the derivative
T

P S
in terms of and CP
Some reference information:

This might or might not be provided on the final!
S
1 V

CP T
T P
V T P
This will NOT be provided on the final:
f (x, y,z) = 0
x y 1
= ;
y z x z
Reciprocal relation
x y z
= 1
y zz xx y
Cyclic Relation

T

P S
in terms of and CP
Step 1: Apply Cyclic Relation:
S
T
=
P T
P S
T P S
= 1
P S S TT P
x y 1
= ;
y z x z
y,z) = 0
f (x,
Reciprocal relation
S

T P
x y z
= 1
y zz xx y
Cyclic Relation

S
T
=
P T
P S
T

P S
S V
=
T P T P
S

=V
P T T P
S
= VT / C P
T P
Step 3: Express result in

terms of and CP
Step 2: Use Maxwell Relation
in terms of and CP

Lecture 29: Phase Transitions I
Time: 2:35-3:25
Office Hours: 2-3MW
Rutherford 411

You may recall the Throttling process: a gas is forced through a
small valve or porous membrane between some initial pressure Pi
and final pressure Pf.
Pi
Pi, Ti
Pf<Pi
Pf, Tf
Pi
Pf<Pi
This process occurs at constant enthalpy (lecture 24)

final pressure
Tf
Tf5
Tf6
Tf4
Tf3
Ti2
Tf2
Tf1
Ti1
Pf

Temperature (K)

10
20
Inversion curve
Tf begins to fall)
30
Pressure (MPa)
40
50

In a throttling process, the key partial derivative is: T

(for example, on the inversion curve this derivative is 0) P H
= JK
As before we use cyclic relations to deal with the
requirement of holding H constant
Realize that
f (T,P, H) = 0
T P H
= 1
P H H T T P
T
1 H

=

C P P T
P H
H H
=
P H
P T T P
(we will deal with this partial
derivative on the next slide)

The enthalpy: dH = T dS+V dP
S
S
(Expanding dS in
dT +T +V dP
terms of dT and dP) = T
T P
P T

H
=
P T
T
S
1 H
1
= C = T +V
CP
P H
P P
P T
T
Maxwell relation
V
=
V
( T 1 )
CP
= = V
T P

JK
On the inversion
curve:
T
= 0
P H
= 1/T
T
= = V ( T 1 )
P H C P
=0
H
You will explore his more fully in

your HW using the VdW Eq of State

T

P S
in terms of and CP
Some reference information:

This might or might not be provided on the final!
S
1 V

CP T
T P
V T P
This will NOT be provided on the final:
f (x, y,z) = 0
x y 1
= ;
y z x z
Reciprocal relation
x y z
= 1
y zz xx y
Cyclic Relation

T

P S
in terms of and CP
Step 1: Apply Cyclic Relation:
S
T
=
P T
P S
T P S
= 1
P S S TT P
x y 1
= ;
y z x z
y,z) = 0
f (x,
Reciprocal relation
S

T P
x y z
= 1
y zz xx y
Cyclic Relation

S
T
=
P T
P S
T

P S
S V
=
T P T P
S

=V
P T T P
S
= VT / C P
T P
Step 3: Express result in

terms of and CP
Step 2: Use Maxwell Relation
in terms of and CP
PV diagram for H20
Showing fluid phase

as compression
continues
saturated
liquid
A
vapor
phase
(coexistance line)
vapor
liquid
B
liquid condensation
progresses
saturated
vapor
gas
vapor
liquid
vapor
vapor
distinction between
liquid
vapor
liquid

By taking system above critical point you can continuously transition from
vapor to liquid phase!
compress
gas
cool
liquid
heat
vapor
Equation-of-State: PT Diagram
P
PT Diagram for H20

No coexistence
regions on a PT
surface: these
collapse to a line
(Note slope negative: very

special property of water)
Liquid/vapor
coexistance occurs at
fixed pressure and
temperature of liquid/
vapor phases
boiling
1atm
(e.g. phases are

in thermal and
mechanical
equilibrium during
coexistance)
T
Equation-of-State:
Substance expands upon
Freezing (e.g. H2O)
f (P,V,T) = 0
P = g(T,V )
(negative
slope)

Equation-of-State:
Substance contracts upon
Freezing
(most other substances)
(positive
slope)

Equilibrium Condition for Two-Phases

We now know enough thermodynamics to move beyond a purely
qualitative, descriptive discussion of phase phenomena!
From our discussion of fluid phase transitions it appears that there
are two distinct types of phase transitions:
Type I (first order): e.g. crossing the liquid-vapor co-existance
boundary. In this case we transition between phases with different
densities and entropies (involves heat transfer/volume changes).
Type II (second order or continuous): e.g. passing through
the critical point. In this case there are continuous changes in the
fluid properties (entropy and density).
First Goal: we will develop an equation that will describe the
boundary between two phases involving a first order change: the
Clausius-Clapeyron equation.

Consider a system consisting of two phases of the same component
The two phases are in equilibrium at fixed pressure and temperature: the
correct equilibrium condition is then the minimization of the Gibbs potential
The two phases will have molecule numbers N1 and N2 with

corresponding molar Gibbs potentials g1 and g2.
G = n1 g1 +n2 g2
The molecule numbers satisfy n1 + n2 = n (with n fixed)
The total Gibbs potential is
Minimization of G implies that dG=0 with respect to interchange of

molecules between the phases
! !! !
dG = dn1 g1 +dn2 g2 = (g1 " g2 ) dn1 = 0
! ! != "dn
g =g
1

Recall from lecture 26 that the Gibbs free energy is related to the
chemical potential:
G = n
Thus the Gibbs potentials (per mole) are equal to the chemical potentials:
g1 = 1
g2 = 2
=
g1 = g2
1
2
and
This is simply another way to say that the phases are at equilibrium
with respect to molecule transfer between the phases
The Clausius-Clapeyron Equation

The Gibbs potentials of the phases are
equal along the phase boundary:
At point A:
g1 (T,P) = g2 (T,P)
Phase 1
At point B:
(T, P)
g1 (T + dT,P + dP) = g2 (T + dT,P + dP)
both sides of the equality:

Taylor expanding
g1
g1
g1 (T,P) +
dP =
dT +
P T
T P
g
g
g2 (T,P) + 2 dT + 2 dP
T P P T
= v2
= v1
= s 2
= s 1
g1 g2
g2 g1
dP

T
dT=
T
P T P T
P P
(T+dT, P+dP)
Phase 2
s1, s2: entropy per mole of

phase 1 and 2
v1, v2: volume per mole of
phase 1 and 2
dP s 2 s1
=
dT
v2 v1

The entropy difference between the phases implies that heat transfer
occurs during the first order change.
This heat change is known as the latent heat:
Latent Heat:
= T ( s 2 s1 )
This is the heat input required to transform one mole of the substance
in phase 1 into one mole of the substance in phase 2
The Gibbs energy difference between phases:
g=
h Ts = 0
= Ts = h
(the latent heat is equal to the molar enthalpy difference

between phases)
The latent heat is known as the heat of fusion for transitions from a
solid to liquid phase and the heat of vaporization for transitions from
a liquid to gas phase

dP 1
L 1
=
=
dT T v2 v1 T V2 V1
The Clausius-Clapeyron Eq determines the slope of the phase boundary
Generic
substance
vS < vL
dP / dT > 0
Water
vS > vL
dP / dT < 0
Example: Regelation
Example: Regelation
Two equal masses are hung from a rigid bar which is placed over an ice sheet.
The entire system is at atmospheric pressure and -2oC. What is the minimum
value of M for which the rod will pass through the ice by regelation?
Given Data:
Heat of fusion of water: 336J/g
Density of water: 1g/cm3
Ice cubes float with 4/5 of their

volume submerged!
Width of bar (w): w=2mm

Length of bar in contact with ice: a=2.5cm
Step 1: Calculate molar volumes of

liquid and water ice
g sVice = g l Vsubmerged
Vsubmerged /Vice = s / l 4 /5
vl = 18 / l = 18 cm 3 /mole
v =
3
5v
/
4
=
22.5
cm
/mole
s
l
M
M
Example: Regelation
Given Data:
Width of bar: 2mm
Step 2:

Apply Clausius-Clapeyron
Eq
dP 1
=
dT T vV vL
=
vl = 18 cm 3 /mole
vs = 22.5 cm 3 /mole
P
1 atm
(336 18) J/mole

1
6
3
271 K
(18 22.5) 10 m /mole
= 5 10 6 Pa/K
7
P = (5 10 6 Pa/K) (2K) = 10 Pa = 100 atm
-2oC 0oC
Example: Regelation
Given Data:
Width of bar: w=2mm
Step 3: Calculate Mass
vl = 18 cm 3 /mole
vs = 22.5 cm 3 /mole
2Mg 2Mg
P =
=
aw
A
aw
=
M=
P
2g
2
3
(2.5
10
m)(2
10
m)
10
Pa
2
2(9.81m/s
)
= 25kg
P = 10 7 Pa
M
M
Example: Phase Boundaries for Carbon

Entropy increase per mole upon
converting from graphite to diamond
Phase Diagram for Carbon
S = 3.4 J/K
Volume increase per mole upon
converting from graphite to diamond
v = 1.9cm 3
dP S 3.4J/K
=
=
dT v 1.9cm 3
Diamond
= 18bar/K
Graphite
The Vaporization Curve

We can use the Clausius-Clapeyron Eq and the ideal gas law to derive
an explicit equation for the vapor-liquid coexistence curve
1
dP
=
The Clausius-Clapeyron Eq:
T vV vL T
dT
V
RT
v
=
=
Ideal gas law: PV = nRT
V
n
P
dP
dT
dP
P
=
=
2
P R T2
dT RT

1
+constant
ln P =
R T

P and
T are reference pressures
and
o
o
ln(P / Po ) =
temperatures at a point on the vapor-liquid
coexistence curve (say Po =1atm and To =100oC)
1
(vV >> vL )
vV
1 1
To T
ln(P / Po ) =
R
1 1
To T
This equation tells us the pressure of vapor in equilibrium with

its liquid
phase at a given temperature
For a system subject to an external pressure Pext, boiling will occur
when the vapor pressure exceeds Pext
(for example, a pot of liquid on a stove top, Pext=Patm)
This equation is not exact, but is a decent first approximation

(for example, the latent heat varies slightly with temperature)
Stability of Thermodynamic Systems

First order phase transitions arise fundamentally from an
instability in the underlying thermodynamic potentials
What is meant by stability/instability in thermodynamics?
S
Consider dividing a system into

two identical sub-systems
Each sub-system has an
entropy S(U,V,N)
1
2
S(U + U )
[S(U U ) + S(U + U )]
Consider transferring an
energy U
between the two sub-systems.
Stability requires:
S(U + U,V,N ) +S(U U,V, N )
or equivalently
1
2
2S
0
2
U V ,N
S(U U )
System
unstable
2S(U,V,N )
[S(U U ) + S(U + U )] S(U,V,N )
U U
U + U
Subsystem 1 Subsystem 2
Otherwise, energy
transfer would be thermodynamically
favorable and the system would develop inhomogeneities
S(U,V.N)
S(U,V.N)
U

We can also consider the stability condition in differential form
1
2
[ S(U U,V, N ) +S(U + U,V, N ) ] S(U,V, N )
1 S(U + U ) S(U ) S(U ) S(U U )

0

2U
U
U 0
2S
0
2
V ,N
the
differential form
of the criterion is less
(note that
restrictive
than
the finite form which holds for all U)
The stability condition also applies to volume transfers V:

1
2
[ S(U,V V, N ) +S(U,V + V, N ) ] S(U,V, N )

2S
0
2
V U ,N

What if we have a system with an unstable S(U,V,N)?
S
Unstable locally
AND globally:
Stable
2S
0
2
U V ,N
Locally stable but globally

unstable
2S
0
2
U V ,N
Stable
1
2
BUT
[S(U U ) + S(U + U )] S(U,V,N )
We draw a family of tangent lines that lie above the curve:

the system will follow the thermodynamic relation given by the
envelope of these tangent lines

What if we have a system with an unstable S(U,V,N)?
S
Coexistance line
between phases at
A and B!
X
We draw a family of tangent lines that lie above the curve:
the system will follow the thermodynamic relation given by the

In general the system must be stable with respect to arbitrary
excursions U and V

Lecture 30: Phase Transitions II
Time: 2:35-3:25
Office Hours: 2-3MW
Rutherford 411

Type I (first order): e.g. crossing the liquid-vapor co-existence

1
s 2 - s1
dP
=
=
v2 v1
T v2 v1
dT
The Clausius-Clapeyron Eq determines the slope of the phase boundary
order
for a first

transition
= T ( s 2 s1 )
g = h Ts = 0
= Ts = h
, s : entropy per mole of
s
phase 1 and 2
v , v : volume per mole of

phase 1 and 2

Latent Heat:
P
Phase 1
P(T)
(g1,s1,h1)
Phase 2
(g2,s2,h2)

We can use the Clausius-Clapeyron Eq and the ideal gas law to derive
an explicit equation for the vapor-liquid coexistence curve
1
dP
=
The Clausius-Clapeyron Eq:
T vV vL T
dT
V
RT
v
=
=
Ideal gas law: PV = nRT
V
n
P
dP
dT
dP
P
=
=
2
P R T2
dT RT

1
+constant
ln P =
R T

P and
T are reference pressures
and
o
o
ln(P / Po ) =
temperatures at a point on the vapor-liquid
coexistence curve (say Po =1atm and To =100oC)
1
(vV >> vL )
vV
1 1
To T
ln(P / Po ) =
R
1 1
To T
This equation tells us the pressure of vapor in equilibrium with

its liquid
phase at a given temperature
For a system subject to an external pressure Pext, boiling will occur
when the vapor pressure exceeds Pext
(for example, a pot of liquid on a stove top, Pext=Patm)
This equation is not exact, but is a decent first approximation

(for example, the latent heat varies slightly with temperature)

First order phase transitions arise fundamentally from an
instability in the underlying thermodynamic potentials
What is meant by stability/instability in thermodynamics?
S
Consider dividing a system into

two identical sub-systems
Each sub-system has an
entropy S(U,V,N)
1
2
S(U + U )
[S(U U ) + S(U + U )]
Consider transferring an
energy U
between the two sub-systems.
Stability requires:
S(U + U,V,N ) +S(U U,V, N )
or equivalently
1
2
System
unstable
S(U U )
2S(U,V,N )
[S(U U ) + S(U + U )] S(U,V,N )
U U
U + U
Subsystem 1 Subsystem 2
Otherwise, energy
transfer would be thermodynamically
favorable and the system would develop inhomogeneities
S(U,V.N)
S(U,V.N)
U

We can also consider the stability condition in differential form
1
2
[ S(U U,V, N ) +S(U + U,V, N ) ] S(U,V, N )
1 S(U + U ) S(U ) S(U ) S(U U )

0

2U
U
U 0
2S
0
2
V ,N
the
differential form
of the criterion is less
(note that
restrictive
than
the finite form which holds for all U)
The stability condition also applies to volume transfers V:

1
2
[ S(U,V V, N ) +S(U,V + V, N ) ] S(U,V, N )

2S
0
2
V U ,N

How do we characterize a system with an unstable S(U,V,N)?
S
Draw a family of tangent lines that lie above the curve
The system will follow the modified thermodynamic relation given by the

S
Unstable locally
AND globally:
Stable
2S
0
2
U V ,N
Locally stable but globally

unstable
2S
0
2
U V ,N
Stable
1
2
BUT
[S(U U ) + S(U + U )] S(U,V,N )
Draw a family of tangent lines that lie above the curve

S
Coexistance line
between phases at
A and B!
X

S
Coexistance line
between phases at
A and B!
Thermodynamic relation
that will be adopted in
equilibrium

In general the system must be stable with respect to arbitrary
simaltaneous excursions of both U and V:
1
2
[ S(U U,V V,N) +S(U + U,V + V,N)] S(U,V,N)

2S
2S
0
0 ; 2
2
V ,N
U ,N
In addition, the following constraint must be satisfied:
2 S
2
U V ,N
2 S S 2
2
0
V U ,N VU
(This third condition prevents a surface from curving upwards along

directions between the U and V axis,e.g. along diagonals)

Stability criteria can also be recast in terms of the internal energy.
As the internal energy is minimized in equilibrium, we have:
1
2
[ U(S S,V V,N) +U(S + S,V + V,N ) ] U(S,V,N )

2U
2U
0 ; 2 0
2
V S,N
S V ,N
In addition, the following constraint must be satisfied:
2U
2
S V ,N
2
2U
U 0
2
V S,N VS

For the internal energy, the stable states corresponding to an
underlying unstable relation U(X) lie underneath the curve
U

Stable
Unstable locally
AND globally
B
Locally stable but
globally unstable
Stable
A
Coexistance line
between phases at
A and B!
Locally stable but
globally unstable

U
Thermodynamic relation that

will be adopted in equilibrium

Finally, we would like to know how to cast the stability criteria in
terms of the thermodynamic potentials (F, H, G)
2U
2S
2 F
2 = 2 T 2 0
V T ,N V T ,N V T ,N
0
potentials with respect

Second partials of the
thermodynamic
to extensive variables (S, V, N) satisfy the same criterion
respect to intensive variables?

partials with
What about second

What about second partials of the thermodynamic potentials with
respect to intensive variables?
For the free energy, recall that:
U
T = ; S =
S V ,N
F

T V ,N
2 F
S
= 2
T V ,N T V ,N
1
S
1
0
= 2
=
2
T V ,N (T /S)V .N ( U / S)V .N
2 F
The same is true for all partials of the
0 thermodynamic
potentials (F, H, G) with
2
T V ,N
respect to intensive variables, T, P,

Here is a summary of the stability criteria:
2U
0
2
S V ,N
2U
2 0
V S,N
Hemholtz
Free Energy:
2 F
0
2
T V ,N
2 F
0
2
V T ,N
Enthalpy:
2 H
0
2
S P,N
2 H
2 0
P S,N
Gibbs Free
Energy:
2 G
0
2
T P,N
2 G
0
2
P T ,N
Energy:

The stability criteria have two immediate physical consequences:
2U
T
T
=
=
2
S V ,N
T (S /T)V ,N
S V ,N
U
T=
S V ,N
2 F
P
1
= =
0
2
V
T ,N V T ,N V T
F
P =
V T ,N
T
0
CV
CV 0
T 0
C P = CV +TV 2 / T
C P CV 0
Stability and Phase Transitions

Instability in an underlying thermodynamic relation signals
the existence of a phase transition
Consider the isotherms of

the VdW fluid model
Over a portion of the subcritical isotherms:
2
Nk B T
N
P=
a 2
V Nb
V
Pressure
We mentioned that the VdW eqof-state is a toy model for a

system with a phase transition
TC
P
= V T 0
V T ,N
Instability!
Volume

Let us consider the behavior of the Gibbs Free Energy along the
unstable isotherms
Recall that the Gibbs Free Energy per mole:
g=
(: chemical
potential)
Recall the Gibbs-Duhem relation (see lecture 22):
d = sdT +vdP
(s and v: entropy and volume per mole)
Along an isotherm we then have:
g = vdP + (T)
(some function of
temperature)
Using this relation we can construct g(P) for a given isotherm

P
Consider a representative
sub-critical isotherm
K
J
F
I
E
D
C
A
B
H
A
D
E
Plot v versus P
For pressures greater than PB

three states become available
Construct g by direct integration:
g gA =
Assign arbitrary
value to g at point A
g gF =
vdP
PA
vdP
PF
g gH =
vdP
P
PH
Direct integration
G
H
AF
FH
D, I
F
J
B
A

P
K
J
F
I
E
D
C
A
B
H
A
D
E
Plot v versus P
F
Unstable
branch
Direct integration
Which state does the system select

between point B and I?
The branch FH is unstable: these
states can be ruled out
Unstable
branch G
H
C
D, I
F
J
B
A

P
K
J
F
I
E
D
C
A
B
H
A
D
E
Plot v versus P
Metastable
Metastable
Direct integration

The branch FH is unstable: these
states can be ruled out
The parts of the curve from DF and

HI are locally stable but not globally
stable: these regions are called
metastable
Metastable
H
C
B
A
D, I
F
J
Metastable
In equilibrium the
system selects the
lower branches

P
K
J
F
I
E
D
C
A
B
H
A
Metastable
F
Unstable
branch
Metastable
We can deduce the form of the

thermodynamically stable isotherm from
the selected free energy branches
D
E
Plot v versus P
P
Direct integration
D, I
B
A
In equilibrium the
system selects the
lower branches

P
K Liquid!
J
F
I
H
B
E
D
C
Vapor!
A
D
E
We can deduce the form of the

thermodynamically stable isotherm from
the selected free energy branches
P
g
Liquid!
D, I
Vapor!
C
B
A
In equilibrium the
system selects the
lower branches
Equal Area (Maxwell) Construction

How do we determine the points H and D?
Area I=Area II
Note that the value of the integral around the

loop connecting D and I must vanish:
vdP = 0
PD
PF
PG
PF
PH
P
G
PI
vdP + vdP = vdP vdP
P P P
P
P
P
P
P
vdP vdP =
vdP vdP
P
P
P
P
Area I
Area II
D
PG
D
E
vdP + vdP + vdP + vdP = 0

P
P
P P
g
D
Maxwell Construction
Area II
PI
PH
Area I
G
PI
D, I
C
B
F
J
Pressure

The Maxwell constructio justifies our
interpretation of the co-existence
region in the VdW equation of state
Stable isotherms obtained from

equal area construction
TC: critical isotherm
gas
vapor
liquid
coexistence region
Volume
Latent Heat of Phase Change

The change in molar volume between
phases is simply the difference
P
K
v = vD vI
J
I
What about the latent heat for the transition?
Latent Heat:
= T ( sD sI )
E
D
C
B
A
We wish to calculate the entropy difference

between the phases
s
P
= dv=
ds
v T ,N T v,N
P
s D s I = dv

IHGFD T v,N
Maxwell Relation!
Coexistance Region: Lever Rule

x: fraction of substance in vapor
phase (x=Nv/N)
vx: total molar volume when vapor

vD: molar volume at point D
vI: molar volume at point I

Vx = xn vV +(1 x)n vL
vI
Number of moles in Number of moles in

vapor phase
liquid phase

= xVB +(1 x)VC
solve for x
x=
vx
vB
Vx VC
VB VC

Lecture 31: Phase Transitions III
(Critical Behavior)
Time: 2:35-3:25
Office Hours: 2-3MW
Rutherford 411

Type I (first order): e.g. crossing the liquid-vapor co-existence
(Tuesday)
(Today)
Review: Stability and Phase Transitions

Instability in an underlying thermodynamic relation signals
the existence of a phase transition
Over a portion of the subcritical isotherms:
Pressure
Consider the isotherms of

the VdW fluid model
2
Nk B T
N
P=
a 2
V Nb
V
TC
1
P
0
=
V T ,N V T
Instability!
Volume

P
K
Unstable
J
F
I
E
D
C
Calculate g
B
A

gV = gL E
H
D, I
F
J
Liquid
K
B
Vapor
In equilibrium the
system selects the
lower branches

P
K Liquid!
J
F
I
H
Area II
E
D
C
Area I
Vapor!
A
Construct stable isotherm
The points I and D are determined

from the equal area construction:
Liquid!
g
D, I
Area I=Area II
Vapor!
In equilibrium the
system selects the
lower branches
Pressure

The Maxwell construction justifies our
interpretation of the co-existence
region in the VdW equation of state
Stable isotherms obtained from

equal area construction
gas
vapor
liquid
coexistence region
Volume
Latent Heat of Phase Change

The change in molar volume between
phases is simply the difference
P
K
v = vD vI
J
I
What about the latent heat for the transition?
Latent Heat:
= T ( sD sI )
E
D
C
B
A
We wish to calculate the entropy difference

between the phases
s
P
= dv= dv
ds
v T ,N T v,N
P
s D s I = dv

IHGFED T v,N
Maxwell Relation!
Coexistance Region: Lever Rule

x: fraction of substance in vapor
phase (x=Nv/N)
vx: total molar volume when vapor

vD: molar volume at point D
vI: molar volume at point I

Vx = xn vD +(1 x)n vI
vI
Number of moles in Number of moles in

vapor phase
liquid phase

= xVD +(1 x)VI
solve for x
x=
vx
vD
Vx VI
VD VI
v
Lever-Rule
gas
vapor
liquid
vapor
vapor
distinction between
liquid
vapor
liquid

Vapor-Liquid Density Near

Critical Point
Density (kg/m3)
No distinction between liquid and

gas phase above critical point!
Saturated
liquid density
Critical
point
saturated
vapor density
Temperature (K)
Density curves for liquid/vapor
phase H2O near critical point
Pressure
Critical Behavior for VdW Fluid

The VdW fluid Eq-of-State is a useful starting
point for investigating critical behavior
Two conditions define the critical point:
P
(1) The isotherms pass from
=0
being locally unstable to stable: V
T ,N
(2) The two extrema in coexistance
region must merge:
2
2 P
>0
2
T ,N
P
=0
2
V T ,N
2 P
<0
2
V T ,N
Volume
Critical Point for VdW Fluid

Write VdW Equation in terms of variables rescaled to
values at critical point:
Nk B T
N 2 ; P = 0 ; 2 P = 0
P=
a 2 V
2
T ,N
T ,N
V Nb
V
vC = 3b
PC = 27b 2
Problem Set I
8a
k B TC = 27b

8T
3
2
P =
3v 1 v
Rescale VdW Eq
v = v/vC
P = P / PC
T = T /TC
Law of Corresponding States

The VdW Eq-of-State does not
give good quantitative predictions,
but the rescaling procedure is
generally valid
Rescaled experimental data for

coexisting liquid and vapor phases
Experimental data for many fluid

systems collapses onto the same
curve when plotted in rescaled
coordinates
This is known as the Law of
Corresponding States
(from Zemansky/Dittman 7th Edition)
Critical Behavior of VdW Fluid

Let us use the rescaled VdW Equation to investigate fluid
behavior in the vicinity of the critical point
Expand the rescaled variable about the critical point:
v = 1 +
P = 1 + p
T = 1+ t
8T
3
2
P =
3v 1 v
=
p
8t ( 1 + 2 + )
(2 + 7 +8 2 +3 3 ) +3 3
Express VdW Eq. in

terms of p, and t
(this eq. is still the complete eq of state)
thecritical point along the co-existence line

We imagine approaching
Very
close to the critical
point
only the terms which
are first order in p,

and t will remain:

2p 8t
p 4t

Let us use the rescaled VdW Equation to investigate fluid behavior
in the vicinity of the critical point
Expand the rescaled variable about the critical point:
v = 1 +
VdW Eq:
p 4t
P = 1 + p ; T = 1 + t
8t ( 1 + 2 + 2 ) = p (2 + 7 +8 2 +3 3 ) +3 3
;
(only keeping terms to third order)
Solutions:
( +8t +4t) 0

=0 ; = + ; =

Below
Above
= 12 [8t 64t 2 16t ]
critical point critical point
1/ 2

The two roots correspond to

For
2 t
T<TC: t < 0
the molar
volumes of the
2
Very close to TC
coexisting liquid and gas

phases

Let us look at how the density difference between the liquid and
vapor phases scales with temperature close to the critical point:
1
1
1
1
c cL cV = 1/vL 1/vV =
vC 1 + vC 1 + +
4 1/ 2
T
(Taylor
=
t
1
1
[( ) (
+) ]
expand)
TC
vC

vC
1/ 2
Critical
exponent

What about the scaling of the isothermal compressibility near the critical point?
1 V
T =
V P
1
T
P
p
= V = PC
V
T
T1 72 p + 92 2 8t
1/ 2
: p 4t ; = 2 t
Approaching the critical pointfrom below TC
(approaching along
1 coexistance line)
1
T 14t18t 8t
T
12t
= 12t
To leading order in p, and t:
Full VDW Equation:
3
2
2
3
=
p
8t ( 1 + 2 + )
(2 + 7 +8 +3 ) +3

What about the scaling of the isothermal compressibility near the critical point?
1
T =
V
V

P
1
T
p
P
= V = PC
T
V
T1 72 p + 92 2 8t
Approaching the critical pointfrom above T

p 4t ; = 0
C:
1
1
T 6t T
6t
To leading order in , and :
Full VDW Equation:

2
(density at
critical density)
3
2
3
=
p
8t ( 1 + 2 + )
(2 + 7 +8 +3 ) +3
Summary of Critical Behavior for VdW

c 1
T
TC
1/ 2
Critical exponent: =1/2
1
T
T
1
12 TC
TC
1
(Approach TC from below)
1
T
1
T
TC
6
(Approach TC from above)
Critical exponent: =1
T1
P
= V 0
V
TC
No restoring force preventing

density fluctuations at critical point.
Density fluctuations grow very large
leading to critical opalescence

We can deduce two additional critical exponents:
P PC v
(Expand pressure in
terms of molar volume
along critical isotherm)
(at T=TC)
CV 1 T
TC
(CV constant in
VdW model)
Full VDW Equation:

2
3
2
3
=
p
8t ( 1 + 2 + )
(2 + 7 +8 +3 ) +3
Significance of Critical Exponents

What is the significance of the critical exponents?
(1) The critical exponents are straightforward to obtain
experimentally (log-log plot in the vicinity of the critical point)
For example, some critical data for CO2:
=0.340.015
=1.350.15
VdW
0
0
0.5
1
1
3
The VdW exponents do not agree with experiment!
Significance of Critical Exponents

What is the significance of the critical exponents?
(2) The critical exponents predicted by the VdW model, while
they do not agree with experiment, are typical of classical
thermodynamic theories of critical behavior
The quantitative failure of VdW exponents is ultimately systematic of a
more fundamental problem that all models based on mean-field
assumptions share
Mean Field: models that neglect effect of fluctuations around average fluid
densities: these fluctuations become significant near the critical point
(3) Wide classes of thermodynamic systems share the same

critical exponents (universality classes)
This has been demonstrated experimentally and can be predicted on
theoretical grounds based on symmetry considerations
The Order Parameter

How can we generalize the concept of critical
scaling beyond fluid systems?
Every phase transition can be characterized by a special
parameter called the order parameter (denote by )
The order parameter is zero in the high temperature phase
The order parameter is non-zero in the low temperature phase
(co-existing phases will have distinct values of the order parameter)
First Order Transition: Discontinuous change in order parameter

Second Order Transition: Continuous change in order parameter
The Order Parameter: Fluids

How do we define the order parameter for a fluid phase transition?
A natural choice is:
= C
(1) The order parameter will be zero immediately above the critical point
(2) Will take unique values in each co-existing phase
(3) Will vary continuously through the critical point:
T
TC
1/ 2
(according to VdW)
Let us now consider some other examples of systems exhibiting phase
systems
transitions and define an order parameter for these
In particular let us investigate phase transitions in magnetic systems
Introduction: Magnetic Systems

Molecules possess a magnetic
dipole moment*
(think: very small current loop or
bar magnet!)
m: magnetization (average magnetic

dipole moment per unit volume)
Randomly oriented in
absence of field: m=0
Dipoles will align in magnetic field net

leading to magnetization m
*arising from physics you will encounter in later courses (orbital motion of electrons, unpaired
electron/nuclear spins)
Magnetic Systems in Thermodynamics

From a thermodynamic point-of-view, one key equation needed
to describe magnetic systems
The magnetic work needed to increase the
magnetization of some material by dM:
dW = Bext dM
(see Finn Appendix C)
M: total magnetic moment along B (M=mV)

Bext: Magnetic field in absence of the sample
system is then:
The first law relation for a magnetic
dU = TdS PdV +Bext dM +dN

In particular, note:
Bext =
M S,V ,N
(we say
and M are thermodynamically
conjugate)
that B
ext
The Order Parameter: Magnetic Systems

Paramagnetic Phase: At high temperature, in the absence of a magnetic
field, spins will be randomly oriented (no net magnetization)
Ferromagnetic Phase: At sufficiently low temperature interactions between
neighboring spins can lead to net spin alignment in the absence of a
magnetic field, leading to an intrinsic magnetization
Magnetization
vector has to pick
an orientation!
This is known as
spontaneous symmetry
breaking!
Low Temperature Phase

(long-range ordering of
spins, M finite)
Lower
temperature
High Temperature Phase

(spins randomly oriented,
M=0)

What is the order parameter for a ferromagnetic phase transition?
=M
(net magnetization)
(1) The order parameter will be zero in the high temperature disordered phase
(2) The order parameter will take distinct non-zero values in the lowtemperature phases
(3) The order parameter varies continuously through the critical point
The order parameter is in general a vector-valued quantity, but in
the following we will restrict it to one dimension, e.g. the dipoles
can only point along one axis aligned with the field direction
(this type of model is known as an Ising model)
Magnetic Versus Fluid Phase Diagram

Be
Magnetic Phase Transition
Ferromagnetic
phase (=+M)
second order
first order
TC
Paramagnetic
T phase (=M=0)
Ferromagnetic
phase (=-M)
Fluid Phase Transition
We can directly compare

the magnetic and the fluid
phase transition!
Gas Phase (=0)

Liquid Phase
(=L-C)
second order
TC
first order
Vapor Phase
(=V-C)
Landau Theory
Using the concept of the order parameter we can develop a generic model
for second order transitions that, while not quantitatively correct, yields
immense physical insight
This theory is known as Landau theory: it yields predictions for the
exponents that are shared by all mean field theories
The starting point of Landau theory is to write the Gibbs potential near
the critical point as a power expansion in the order parameter:
GL (T,P, ) = GO (T,P) +G1 (T,P) +G2 (T,P)
+G3 (T,P) +G4 (T,P)
Important: the equilibrium value of the order parameter
GL(T,P,)!
o(T,P) is thatwhich minimizes
Values of away away from o at a given T and P correspond
states
to
non-equilibrium
Landau Theory
The Landau Free Energy:
GL (T,P, ) = GO (T,P) +G1 (T,P) +G2 (T,P)

0
+G3 (T,P) +G4 (T,P)
For a magnetic system the odd terms must disappear: there can be
no intrinsic difference between different spin orientations
What should the sign of the G2 and G4 terms be?
To ensure stability G4 >0
What about G2?
(the potential must be positive and increasing for very

large values of the order parameter)
Landau Theory
2
4
+G
(T,P)
=
G
(T,P)
GL (T,P, )
+G4 (T,P)
2
O
What about G2?

GL()
G2 <0
G4 >0
G2 >0
G4 >0
GL()
One minimum at =0
High temperature phase!
Two minima at o = G2 /2G4

Low temperature phase!
Landau Theory
2
4
+G
(T,P)
=
G
(T,P)
+G
(T,P)
GL (T,P, )
2
O
4
GL()
G2 >0
G4 >0
Pass below TC
GL()
G2 <0
G4 >0
One minimum at =0
As the system passes through the critical point the sign of G2 must change
the low to the high
from negative to positive as the system moves from
temperature phase
G2 (T,P) = (T
0
TC )G2
(to leading order)
Landau Theory
GL (T,P, ) =
TC ) +G4
2
G L
= 2G20 (T TC ) +4G4 3 = 0
= 0 (T>TC)
G20
1/ 2
(TC T)
=
(T<TC)
2G4
GO +G20 (T
We obtain the same critical exponent

that we did for the VdW model!
TC
Landau Theory:
Qualitative Picture of Phase Transition
Second Order Transition
Be
T
TC
Landau Theory:
First Order Transition
Be
Ferromagnetic
phase (=+M)
T
Ferromagnetic
phase (=-M)
TC
Paramagnetic phase
(=M=0)

Lecture 32: Multi-Component Systems
Time: 2:35-3:25
Office Hours: 2-3MW
Rutherford 411

1 T
1/ 2
TC
Critical exponent: =1/2
1
T
T
1
12 TC
TC
1
(Approach TC from below)
1
T
1
T
TC
6
(Approach TC from above)
T1
P
= V 0
V
TC
No restoring force preventing

density fluctuations at critical point.
Density fluctuations grow very large
leading to critical opalescence
The Order Parameter


The Order Parameter


The Order Parameter: Fluids

How do we define the order parameter for a fluid phase transition?
= C
(1) The order parameter will be zero immediately above the critical point
(2) Will take unique values in each co-existing phase
(3) Will vary continuously through the critical point:
T
TC
1/ 2
(according to VdW)
Let us now consider some other examples of systems exhibiting phase
systems
transitions and define an order parameter for these
In particular let us investigate phase transitions in magnetic systems
Introduction: Magnetic Systems

Molecules possess a magnetic
dipole moment*
(think: very small current loop or
bar magnet!)
m: magnetization (average magnetic

dipole moment per unit volume)
Randomly oriented in
absence of field: m=0
Dipoles will align in magnetic field net

leading to magnetization m
*arising from physics you will encounter in later courses (orbital motion of electrons, unpaired
electron/nuclear spins)

Paramagnetic Phase: At high temperature, in the absence of a magnetic
field, spins will be randomly oriented (no net magnetization)
Ferromagnetic Phase: At sufficiently low temperature interactions between
neighboring spins can lead to net spin alignment in the absence of a
magnetic field, leading to an intrinsic magnetization
Magnetization
vector has to pick
an orientation!
This is known as
spontaneous symmetry
breaking!
Low Temperature Phase

(long-range ordering of
spins, M finite)
Lower
temperature
High Temperature Phase

(spins randomly oriented,
M=0)

What is the order parameter for a ferromagnetic phase transition?
=M
(net magnetization)
(1) The order parameter will be zero in the high temperature disordered phase
(2) The order parameter will take distinct non-zero values in the lowtemperature phases
(3) The order parameter varies continuously through the critical point
The order parameter for magnetic systems is in general a vector-valued
quantity, but in the following we will restrict it to one dimension, e.g. the dipoles
can only point along one axis the axis aligned with the field direction
(this type of model is known as an Ising model)
Magnetic Versus Fluid Phase Diagram

Be
Magnetic Phase Transition
Ferromagnetic
phase (=+M)
second order
first order
TC
Paramagnetic
T phase (=M=0)
Ferromagnetic
phase (=-M)
Fluid Phase Transition
We can directly compare

the magnetic and the fluid
phase transition!
Gas Phase (=0)

Liquid Phase
(=L-C)
second order
TC
first order
Vapor Phase
(=V-C)
Landau Theory
Using the concept of the order parameter we can develop a generic model
for second order transitions that, while not quantitatively correct, yields
immense physical insight
This theory is known as Landau theory: it yields predictions for the
exponents that are shared by all mean field theories
The starting point of Landau theory is to write the Gibbs potential near
the critical point as a power expansion in the order parameter:
GL (T,P, ) = GO +G1 +G2 +G3 3 +G4 4

(The Gi can be functions of pressure and/or temperature)
Important: the equilibrium value of the order parameter

o(T,P) is that which minimizes GL(T,P,)!
Values of away away from o at a given T and P correspond

to non-equilibrium states
Landau Theory
0
4
GL (T,P, ) = GO +G1 +G2 +G3 3 +G4
For a magnetic system the odd terms must disappear: there can be no
intrinsic difference in the free energy between different spin orientations
For a fluid system we must keep the odd terms
(this complicates the argument but does not change the critical exponents)

What about G2?

Landau Theory
2
4
+G
+G
=
G
GL (T,P, )
2
4
O
What about G2?
GL()
G2 <0
G4 >0
G2 >0
G4 >0
GL()
One minimum at =0

Landau Theory
4
2
+G
=
G
+G4
GL (T,P, )
2
O
GL()
G2 >0
G4 >0
Pass below TC
G2 <0
G4 >0
GL()
One minimum at =0
As the system passes through the critical point the sign of G2 must change
the low to the high
from negative to positive as the system moves from
temperature phase
G2 = (T TC )G20
(to leading order)
Landau Theory
GL (T,P, ) =
TC ) +G4
2
G L
= 2G20 (T TC ) +4G4 3 = 0
= 0 (T>TC)
G20
1/ 2
(TC T)
=
(T<TC)
2G4
GO +G20 (T
We obtain the same critical exponent

that we did for the VdW model!
TC
Landau Theory:
Second Order Transition
Be
T
TC
Landau Theory:
First Order Transition
Be
Ferromagnetic
phase (=+M)
T
Ferromagnetic
phase (=-M)
TC
Paramagnetic phase
(=M=0)
Multi-Component Systems
So far we have investigated pure (single-component) substances
We will now generalize thermodynamics to multi-component systems
(that is systems containing more than one molecular species)
This will enable us to tackle a wide-range of interesting problems, ranging
from solution thermodynamics to phase transitions of fluid mixtures
Let the molecule species have molecule numbers N1, N2, . .
The first law becomes:
dU = TdS PdV + 1 dN 1 + 2 dN 2 + +
Chemical potentials for individual molecule species
Internal Energy: Multi-Component

U(S,V, N 1 , N 2 ,)
U
i
T =
S V ,N ,N
1
T(S,V, N 1 , N 2 ,)
U
U
P =
=
V S,N ,N
N i V ,S,N N
k
i (S,V, N 1 , N 2 ,)
P(S,V, N 1 , N 2 )
dU = TdS PdV + 1dN 1 + 2 dN 2 + +
Gibbs Free Energy: Multi-Component

G(T,P, N 1 , N 2 ,)
G
G
i =
S =
T P,N
N i T ,P,N
k
S(T,P, N 1 , N 2 ,)
(T,P, N 1 , N 2 ,)
G
V =
P
T ,N
N
i
V (T,P, N 1 , N 2 ,)
+ +
dG = SdT
+VdP + 1 dN
1 + 2 dN 2
Euler Relation: Multi-Component

The Euler relation for a multi-component system has the form:
U = TS PV + 1 N 1 + 2 N 2 + +
The Gibbs Free Energy:
G = U TS +PV
= (TS PV + 1 N 1 + 2 N 2 + + ) TS +PV
G
G = 1 N 1 + 2 N 2 + +
For a multi-component system:
Ideal Gas Multi-Component Systems

Consider a mixture of inert (non-reacting) ideal gases with molecular
species N1, N2, etc. . . at temperature T, pressure P and volume V
The ideal gas law implies:
PV = (N 1 + N 2 + + ) k B T
k BT
k T
=N
N 1 + B N 2 + +
V
V
(the pi are known as
pressures)
partial
=p1
= p2
Total
P = p1 + p2 + +
pressure
equals the some of
P=
the partial pressures:
Note that:
Daltons law of
k BT
P
pi =
N i = xi P
Ni =
partial pressures
N
V
= N /N
i
Gibbs Free Energy for Ideal Gas Mixtures

We wish to calculate the Gibbs Free Energy for a multicomponent system of ideal gases with molecules N1, N2. . .
Consider a series of gases at fixed T and P placed side-by-side but
initially separated by partitions impermeable to molecule flow
T, P
Gas 1
N1, G1
Gas 2
N2, G2
Gas 3
N3, G3
...
If we open the partitions and let the gases mix we expect:
G = TS Mixing= Nk B T ( x1 ln x1 +x 2 ln x 2 + + )
Ginitial = G1 + G2 + +
Gfinal = Ginitial + G

Let us calculate the Gibbs free energy for a single ideal gas component:
= Nk B T
G = U +PV TS
= CV T
gas entropy:
The ideal
S = CV lnT +Nk B ln(V / N ) + So

= Nk B T /P
= (CV + Nk B ) lnT Nk B ln P +So
= C P
G = C P T C PT lnT TS o +Nk BT ln P = NkBT ( (T) + ln P )
= (T)/ k
BT
( has nothing to do with order

parameter, just conventional notation for
the temperature part of G)

G = TS Mixing= Nk B T ( x1 ln x1 +x 2 ln x 2 + + )
Ginitial = G1 + G2 + +
(results from
(T)
=N
k B T (i
+ ln P
previous two slides)
G
)
i
i
Putting this together we find: G

(T) + ln P + ln xi )
i( i
final = k B T N

i
=
Gfinal = Ginitial + G
We can
obtain the same result for the chemical potentials using Daltons law:
i = k BT (i (T) +
ln pi ) =kB T
( i (T)+ ln P+ ln xi )
= xi P
0
The chemical potential is often denoted: i = i (T,Po ) +k B T ln(Pxi / Po )
(i0(P, T) is the chemical and Po the

pressure
for astandard state (say 1atm, 25oC))
Ideal Gas Reactions

We are now in a position to describe chemical reactions in ideal gas mixtures!
Consider the following reaction:
1 A1 + 2 A2 3 A3
We can read this as stating: 1 moles of gas A1 and 2 moles of

gas A2 are reacted to produce 3 moles of gas A3
Example:
N 2 +3H 2 2NH 3
fixation)
(nitrogen
Now, if I start with 1 moles of gas A1 and 2 moles of gas A2 you

might expect the reaction to proceed (assuming a G<0 and favorable
kinetics) until all the reactants are converted into products
In fact, if I could somehow keep the products and reactants separate,

this is exactly what would happen!
Yet I have to take the entropy of mixing between

reactants and products into account!
Extent of Reaction
1 A1 + 2 A2 3 A3
We wish to find the Gibbs free energy as a function of

how close the reaction is to completion
:
Introduce the extent ofreaction
=0: no products formed

n
=1: maximum amount of reactants
converted into products
How do we calculate the mole

fractions in terms of ?
Let us start with 1 moles of A1 and 2 moles of A2

At a certain point along the reaction 3 moles of gas A3 are produced
To do this 1 (1-) moles of A1 and 2 (1-) moles of A2 must be consumed
Extent of Reaction
1 A1 + 2 A2 3 A3
How do we calculate the mole fractions in terms of ?

Let us start with 1 moles of A1 and
2 moles of A2
At a certain point along the reaction 3 moles of gas A3 are produced

To do this 1 (1-) moles of A1 and n 2 (1-) moles of A2 must be consumed
Total number of moles:
n( ) = 1 (1 ) + 2 (1 ) + 3
Mole fractions:
1 (1 )
;
x1 =
n( )
(1 )
2
; x3 =
x 2 =
n( )
n( )
Gibbs Energy for Reaction

1 A1 + 2 A2 3 A3
Let us find the Gibbs Free Energy for this reaction
(for simplicity, let P=Po and 1=2=3=1)
G( ) =
0
(1 ) 1
+k B T (1 ) ln
0
1
+(1 ) 2 +k BT (1 ) ln + 30 +k BT
2

1 (1 )
x1 =
n( )
x2 =
2 (1 )
n( )
3
x3 =
n( )

ln
1 (1
) + 2 (1 ) + 3
n(
) =

G = 1n1 + 2n2 + +
i = i0 (T,Po ) +k BT ln(Pxi / Po )
Gibbs Energy for Reaction

Let us plot the Gibbs Free Energy as a function of the extent of reaction
1 A1 + 2 A2 3 A3
G()
3
= 0
0
2
G()
0
1
The reaction equilibrium is

driven to the right as G
decreases
No entropy of
mixing!
G=2
0
-1
-2
Entropy of
mixing included!
0
-3
1
-4
0
Equilibrium Condition
Let us investigate the reaction equilibrium
1 A1 + 2 A2 3 A3
In equilibrium:
dG
=0
d
The change in mole numbers:
dni = i d
dG = ( 3 3 2 2 3 3 ) d = 0
3 3 = 2 2+ 3 3
(equilibrium
condition)
G = 1n1
+ 2 n2 + +
Let us investigate the reaction equilibrium 1 A1 + 2 A2 3 A3
The equilibrium condition is:
3 3 = 2 2 + 3 3
Using the chemical potential of an ideal

we can write
the
gas
equilibrium condition in terms of the mole fractions and pressures:
0 + k T ln(Px / P )
3 30 + 3 k B T ln(Px
=
/
P
)
3 o
1 1
1 B
1 o
+ 2 20 + 2 k B T ln(Px 2 / Po )
Go =
k BT
3 30 1 10 2 20
=ln x1 x 2
x3
k BT

3
P

Po
+ 2 3
i = i0 (T,Po ) +k BT ln(Pxi / Po )
Go
=
k BT
3 30 1 10 2 20
k BT
x1 x 2
= ln
x3
3
P

Po

x1x 2 P Go
= exp
K

Po
k BT
For the example:
x
NH
xN
Po 2
=K
3
xH 2 P
3
+ 2 3
(equilibrium
constant)
N 2 +3H 2 2NH 3
This equation becomes:

Lecture 33: Multi-Component Systems
Time: 2:35-3:25
Office Hours: 2-3MW
Rutherford 411
Review: Gibbs Free Energy for Ideal Gas Mixtures

Key equations for thermodynamics of multi-component ideal gas systems
G = i ni
Gibbs Free Energy in terms of component chemical potentials:
Chemical potential of single

ideal gas component in mixture:
i = RT (i (T) + ln P + ln xi )
(T) + ln(xi P) )
= RT ( i
Let the chemical potential of the pure component (xi=1) be denoted by:
i0(T, P)

We can write the chemical potential
0
0
(T,P)
=
i (T,Po ) +RT ln(P / Po )
of the pure component: i
(Po: a reference pressure, e.g. 1atm)
The chemical potential of the same

component in a mixture:
= i0 (T,P
i (T,P)
o ) +RT ln(Pxi / Po )
Review: Ideal Gas Reactions

1 A1 + 2 A2 3 A3
We can read this as stating: 1 moles of gas A1 and 2 moles of

gas A2 are reacted to produce 3 moles of gas A3
We wish to find the Gibbs free energy as a function of

how close the reaction is to completion
Introduce the extent of reaction :
=0: no products formed
=1: maximum amount of reactants converted into products
The mole numbers of reactants and products can be expressed in
terms of the extent of reaction (last lecture)
In the last lecture we obtained G(), treating the reactants and products
as ideal gases, in the simple case where P=Po and 1=2=3=1
Review: Gibbs Energy for Reaction

Let us plot the Gibbs Free Energy as a function of the extent of reaction
1 A1 + 2 A2 3 A3
G()
3
= 0
0
2
G()
0
1
The reaction equilibrium is

driven to the right as G
decreases
No entropy of
mixing!
G=2
0
-1
-2
Entropy of
mixing included!
0
-3
1
Reaction will have

stable equilibrium!
-4
0
Let us investigate the reaction equilibrium
1 A1 + 2 A2 3 A3
In equilibrium:
dG
=0
d
The change in mole numbers:
dG = ( 3 3
dni = i d
1 1 2 2 ) d = 0
3 3 = 1 1 + 2 2
(equilibrium
condition)
G = 1n1
+ 2 n2 + +
Let us investigate the reaction equilibrium 1 A1 + 2 A2 3 A3
The equilibrium condition is:
3 3 = 1 1 + 2 2
Using the chemical potential of an ideal

we can write
the
gas
equilibrium condition in terms of the mole fractions and pressures:
0 + RT ln(Px / P )
3 30 + 3 RT ln(Px
=
/
P
)
1
3 o
1 1
1 o
+ 2 20 + 2 RT ln(Px 2 / Po )
Go =
RT
3 30 1 10 2 20
x1 x 2
= ln
RT
x3
P

Po
+ 2 3
i = i0 (T,Po ) +RT ln(Pxi / Po )
Go
=
RT
3 30 1 10 2 20
x1 x 2
= ln
x3
RT
3
P
x3

Po
x1 1 x 2
1 2
For the example:
Go K
= exp
RT
N 2 +3H 2 2NH 3
This
equation becomes:

P

Po
2
x NH
Po 2
3 = K
xN xH P
3
+ 2 3
Equilibrium
constant
Thermodynamics of Solutions
The concepts we have introduced for ideal gas mixtures can be
applied in a modified form to investigate the properties of solutions
Solutions consist of a solvent medium with a concentration
(usually small) of solute molecules
Ideal solution: no appreciable interaction energy contributed by
the addition of solute species. The thermodynamic properties of
an ideal solution are determined by the entropy of mixing of
solvent and solutes.
Solvent (SV):
mole number nSV
(generalization to
system with multiple
solute components
straightforward)
Solute (SL):
mole number nSL
The ideal solution Gibbs free energy:

0
Gideal = SV
nSV +nSL +TS mixing
=R
Chemical potential Energy cost of adding solute
molecules completely
of pure solvent
xSL, xSV: mole fractions of solvent

and solute components
nSV ln x SV +R nSL ln x SL
surrounded by solvent
approximately
behave
Solutions
ideally when the solute concentrations are very low
Chemical Potential of Solutions

0
Gideal = SV
nSV +nSL +RT ( nSV ln x SV +nSL ln x SL )
0
= nSV ( SV
+RT ln x SV ) +nSL ( +RT ln x SL )

0
SV
(T,P) +RT ln x SV
SV =

SL = (T,P) +RT ln x SL
G = ni i
i

For a dilute solution: nSL<<nSV and we can make some
simplifications to the formulas for the chemical potentials:
0
(T,P) +RT ln x SV
SV = SV
= nSV /n
0
SV
(T,P) +RT ln
SL
nSL
= (T,P) +RT
ln
]=
0
SV
n
SL
n
nSL
1 -
n
nSV
nSL
(T,P) RT
nSV
(n = nSL + nSV nSV )
nSL /V
=
= c/cSV
nSV /V

Let us consider a dilute solution with a solvent species (SV) and
a single solute species (SL): NSL<<NSV.
nSL
(T,P)RT
SV =
nSV
c
SL = (T,P) + RT ln
cSV
In practice the solute chemical potential is expressed in the

0
SV
(equivalent) form:
SL
= SL (T,P, co ) +RT
c
ln
co
co: the standard state

concentration (typically 1M)
Osmotic Pressure
no solute; just solvent
solute present (dilute limit)
P1
P2
At fixed
temperature T
semipermeable membrane
(permeable to solvent NOT solute)
Solvent chemical potential:
SV (T,P) =
0
SV
nSL
(T,P) RT
nSV
The solvent chemical potential will be lower on the side containing solute
Solvent molecules will spontaneously flow from the side containing pure solvent
into the side containing solution
(this flow is
called osmosis)
The osmotic flow will occur until the pressure drop P2-P1 across the membrane is
large enough to counteract the flow (the pressure drop is called osmotic pressure)
Osmotic Pressure
What is the pressure drop
required to prevent osmosis?
(this pressure is called the
osmotic pressure)
solute present
(dilute limit)
no solute;
just solvent
P1
P2
Equilibrium will be reached when the solvent chemical potentials across the
membrane are equalized:
SV (T,P1 ) = SV (T,P2 ) =
(pure solvent side)
0
SV
(side with solute)
nSL
(T,P2 )RT
nSV
Question: How do we relate the chemical potentials for the pure solvent
at pressures P1 and P2?
Osmotic Pressure
no solute;
just solvent
(this pressure is called the

osmotic pressure)
solute present
(dilute limit)
P1
P2
Answer: Use Gibbs-Duhem relation
Gibbs-Duhem relation (constant T):
0
d SV
= dP
P1
0
0
0
(P1 ,T) + (P2 P1 )
SV
(P2 ,T) = SV (P1 ,T) + dP SV
P2
(for liquid solvent molar volume
approximately constant)
Osmotic Pressure
no solute;
just solvent
solute present
(dilute limit)
P1
P2
(the osmotic pressure)
Now combine the equations:
SV (T,P1 ) =
0
SV
nSL
(T,P2 ) RT
nSV
0
SV
(P1 ,T) + (P2 P1 )
= Posmosis
nSL
(P2 P1 ) = RT
V Posmosis = nSL RT
nSV
= V /nSV
Osmotic Pressure of Cells

Osmotic pressure is a particularly important in biology in regards
to understanding cellular stability
Cells maintain a very high concentration of internal components
(e.g. proteins, inorganic ions such as K+)
Estimating a total solute concentration of ~100mM inside a typical cell:
nSL
Posmosis = RT
V
3
3
= (8.314 JK -1mol-1 ) (293K) (100mM) (10 L/m ) ~ 2atm
This high pressure is sufficient to lyse many cells types if they are
deposited in pure water (e.g. osmotic shock)
Evolution has devised numerous strategies for coping with the osmotic
pressure, including rigid cell walls (plants) and Na+-K+ pumps in animals
that maintain a high concentration of inorganic ions outside the cell
Vapor Pressure above Solutions

We can also use the ideal solution chemical potentials to calculate how
solutes shift the vapor pressures of pure substances.
Consider a liquid solvent in equilibrium with
its vapor phase; the liquid contains a small
concentration of solute molecules
The condition of chemical equilibrium implies:
Fixed Temperature T
Vapor
Liquid
(1) If there is no solute:
o
vapor
SV
(T,Po ) = SV (T,Po )
Chemical potential of
solvent in vapor phase
Chemical potential of
pure liquid solvent
Po: vapor pressure at temperature T

(2) If the
liquid is a dilute solution:
vapor
SV (T,P)
vapor phase
o
SV
(T,P)
nSL
RT
nSV
liquid solvent with solute
solute
We need to relate the chemical
potentials taken for zero solute
(at pressure Po) to the chemical
potentials with solute present
(at pressure Po)

We can also use the ideal solution chemical potentials to calculate how
solutes shift the vapor pressures of pure substances.
Fixed Temperature T
vapor
SV
(T,Po )
vapor phase
Vapor
o
SV
(T,Po )
pure liquid solvent
Liquid
(2) If the liquid is a dilute solution:
vapor
SV
(T,P)
vapor phase
For the liquid phase:
o
SV
(T,P)
nSL
RT
nSV
solute
0
0
SV
(T,P) SV
(T,Po ) + L (P Po )
(same argument
as slide 14)
vapor
(T,P)
= vapor (T,P ) + RT ln ( P / Po )
For the vapor phase:
o
SV
SV
vapor
P
vapor
SV
(T,Po ) +RT
ln 1 + PP SV
(T,Po ) + RT P
P P Po (assume small)
(treat as
ideal gas)

Combine equations from previous slide:
0
SV
(T,Po ) + (P Po )
vapor
SV (T,P)
o
SV
(T,P) RT
P
vapor
= SV
(T,Po ) + RT
Po
nSL
nSV
This term is small as L<< V=RT

(we will neglect it)
nSL
RT P = L (P
Po ) RT
Po
nSV
P
P
=
Po Po
n
1 = n SL
SV
Vapor pressure is reduced

by adding solute!
P
nSL
=1
nSV
Po
Raoults Law

Lecture 34: Solutions and Binary Mixing
Time: 2:35-3:25
Office Hours: 2-3MW
Rutherford 411
The concepts we have introduced for ideal gas mixtures can be
applied in a modified form to investigate the properties of solutions
Solutions consist of a solvent medium with a concentration
(usually small) of solute molecules
Ideal solution: no appreciable interaction energy contributed by
the addition of solute species. The thermodynamic properties of
an ideal solution are determined by the entropy of mixing of
solvent and solutes.
Solvent (SV):
mole number nSV
(generalization to
system with multiple
solute components
straightforward)
Solute (SL):
mole number nSL

0
Gideal = SV
nSV +nSL TS mixing
=R
Chemical potential Energy cost of adding solute
molecules completely
of pure solvent
xSL, xSV: mole fractions of solvent

and solute components
nSV ln x SV +R nSL ln x SL
surrounded by solvent
approximately
behave
Solutions
ideally when the solute concentrations are very low
Review: Solution Chemical Potential

Two key results for the dilute solution limit (NSL<<NSV):
Chemical Potential Solvent:
SV =
0
SV
nSL
(T,P)RT
nSV
co ) +RT ln
Chemical Potential Solute: SL = SL (T,P,
c
co: the standard state concentration (typically 1M)
Change of Boiling Temperature

Tuesday: we calculated shift in vapor pressure at fixed
temperature when solute added
If we assume the pressure is fixed, we can solve for the shift in
temperature needed to maintain equilibrium when solute is added
vapor
SV
(To ,P)
= SV (To ,P)
Fixed
Pressure P
pure liquid solvent
vapor phase
Vapor
vapor
(T,P)
SV
vapor phase
o
SV
(T,P)
nSL
RT
nSV
Liquid

We need to relate the chemical potentials at T to the chemical potentials
at To (for the pure solvent liquid and vapor phase):
o
For the liquid phase:
(To ,Po ) +(T To )
(T,P)
T P
o
Gibbs-Duhem (at constant P): d o = sdT
= s L
T P (molar entropy of
pure solvent
liquid phase)
For the vapor phase:
Vapor
vapor
vapor
SV (T,P) SV (To ,Po ) + (T To )
T P
0
SV
0
SV
= s V
(molar entropy of
pure solvent
vapor phase)

The final step is to combine the relations from the last two slides:
0
SV
(To ,P) s L (T To )
vapor
SV
(T,P)
o
SV
(To ,P) RT
nSL
nSV
vapor
= SV
(To ,P) s V (T T
o)
(1)
If there is no solute:
o
vapor
(To ,P)
SV
(To ,P) = SV
pure liquid solvent
vapor phase

0
0
(Po ,To ) (T To ) s L
SV
(P,T) SV
vapor
vapor
SV
(P,T) SV
(Po ,To ) (T To ) sV
vapor
SV
(T,P)
= SV (T,P) RT
vapor phase
nSL
nSV

The final step is to combine the relations from the last two slides:
nSL
s V (T To ) = s L (T To ) RT
nSV
2
n
nSL
RT
n
RTT
RT
SL
o
SL
o
T To =
=
sV s L nSV
nSV
nSV

=
/To
(latent heat)
2
RT
T T
o nSL
o
n
SV
Boiling temperature increases

with solute
0
(Po ,To ) (T To ) s L
SV (P,T) SV
vapor
vapor
SV
(P,T) SV
(Po ,To ) (T To ) sV
TTo To 2
vapor
o
(To ,P)
SV (To ,P) = SV
pure liquid solvent
vapor phase

vapor
SV
(T,P)
= SV (T,P) RT
vapor phase
nSL
nSV
Chemical Equilibrium in Dilute Solution

The equilibrium relation for reactions in dilute solution
is analogous to the result for ideal gas reactions
1 A1 + 2 A2 3 A3
We can read this as stating: 1 moles of solute A1 and 2 moles of

solute A2 are reacted to produce 3 moles of solute A3
As before we have the equilibrium condition: 1 1 + 2 2
= 3 3
The chemical potential for the ith solute constituent:
i
SL
i
SL
(T,P,
The equilibrium
condition:
ci
co ) +RT ln
co
c3
1
c1 c2
co: the standard state

concentration (typically 1M)
Go
= exp
K
RT
Go = 3 30 1 10 2 20
Beyond Ideal Solutions: Solution Lattice Model

What if we relax the assumption that the solution is ideal?
We can explore the effect of solvent-solute interactions via
the following lattice solution model:
+
Species A
Species B
Mixed system
Number of A-type particles: NA

Number of B-type particles: NB
+
Species A
Species B
Mixed system
We assume the total energy of the lattice model depends upon the
number of AA (mAA), BB (mBB) and AB (mAB) contacts that can be formed
wAA: energy of AA bond
wAB: energy of AB bond
wBB: energy of BB bond

The total internal energy:
U = m AA wAA +m BB wBB +m AB wAB

How many bonds of each type are formed?
Each lattice site has z sides (in 2D z=4)
zN A = 2m AA +m AB
Total number of sides
of type A particles
Mixed system
Two A-sides present per AA bond:

(mBB BB-bonds formed)
Two A-sides!
One A-sides present per AB bond:
+
One A-side!

(mAA AA-bonds formed)
wAB: energy of AB bond

(mAB AB-bonds formed)

How many bonds of each type are formed?
Each lattice site has z sides (in 2D z=4)
zN A = 2m AA +m AB
zN B = 2m BB +m AB
Solving these relations for
mAA and mBB:
Mixed system
(mAA AA-bonds formed)

zN A m AB
(mBB BB-bonds formed)
m AA=
2
energy of AB bond
zN B m AB w(mAB: AB-bonds
formed)
AB
m BB =
2
m AA wAA +m BB wBB +m AB wAB
U
=


The internal energy is then:

zN A m AB
zN B m AB
w
wBB +m AB wAB
=
AA+
2
2
zw zw

wAA + wBB
AA
BB
w
m
+
N
=
N
AB
AB
B
A

2
2

k BT
AB
AB : Exchange Parameter
z
zN A m AB
m AA =
m BB

2
m
= zN B AB
2
Exchange Parameter
The exchange parameter has a straightforward physical interpretation:
2 AB :
the energy change in units of kBT for exchanging a

molecule of type A embedded in pure B and a molecule
of type A embedded in pure B
Species A
AB
z
=
k BT
Species B
(w
AB
wAA +wBB
2
Exchange Parameter
2 AB :

Start with 4 AA
and 4 BB bonds
Species A
AB
z
=
k BT
Species B
(w
AB
wAA +wBB
2
Exchange Parameter
2 AB :

End with 8 AB
bonds
Species A
AB
z
=
k BT
Species B
(w
AB
wAA +wBB
2
Exchange Parameter
2 AB :

AB > 0 :
mixing of A and B disfavored
(phase separation possible!)
AB = 0 :
(only mixing entropy)
AB < 0 :
AB
ideal solution behavior
z
=
k BT
mixing of A and B favored
(w
AB
wAA +wBB
2

How can we count the number of AB contacts (mAB)?
There are many possible system configurations: some of
these configurations have many contacts, some have few
Many AB contacts
Few AB contacts

In order to calculate the number of AB bonds we will assume
that the Bs are randomly distributed throughout all sites
The probability that a given site is
occupied by B:
pB = N B / N = x B
The average number of AB contacts that a

single A-particle will experience is then:
The total number of AB contacts is then:
m AB
zpB
zN A N B
= N A zpB =
N

Recalling the expression for the internal energy:
zw AA
U =
NA
2
zw BB
k BT
AB
+
NB +
z
2
m AB
= zN A N B / N
zw AA
zw BB
NANB
+k
T
N
=
+
N A
B
B
AB
2
2
N
The mixing energy:
U
mixing = U(N
A , N
B ) U (0, N B ) U (N A ,0)
NANB
= k B T AB
N

The mixing energy:
U mixing = U(N A , N B ) U (0, N B ) U (N A ,0)

NANB
= k B T AB
N
The mixing free energy:
xA = N A / N x
Fmixing = U mixing TS mixing
x
=
1
x
B
Fmixing
= x ln x +(1 x) ln(1 x) + AB x(1 x)
Nk B T
model cannot
account for volumechanges uponmixing
The lattice
(the volume is fixed by the number of particles)
If these volume changes

are
Fmixing
(to good approximation)
small, however,
=Gmixing
Thermodynamics of Binary Mixtures

We can now model the phase behavior of binary mixtures!
Write the Gibbs Free energy:
G /n =
0
gB
x +gA0 (1 x) +gmixing
gmixing = RT [ x ln x +(1 x) ln(1 x) + AB x(1 x)]

For the case AB=0 only mixing entropy contributes
-TSmixing
G/n
Mixture stable for all x
gB0
No mixing
gA0
Ideal mixing
0
Pure A
1
B
Pure

0
0
g
G /n = B x +gA (1 x) +gmixing

For the case AB>0 competition between mixing energy and entropy
Umixing
G/n Region of
gB0
instability!
+
-TSmixing
0
Pure A
gA0
x
1
Pure
B

0
0
g
G /n = B x +gA (1 x) +gmixing

For the case AB>0 competition between mixing energy and entropy
The tangent line between points xA

G/n
and
x
for an
B gives
free energy
unmixed combination of the two
gB0
phases (with compositions xA and xB )

The phase separated system
has a lower free energy then
the mixture
Not possible to form mixtures with
compositions between xA and xB
Soluability Gap
gA0
Free energy of phase

separated system
0 xA
Pure A
xB 1
Pure B

Gibbs Free energy:
0
gB
G /n =
Assume mixing energy

independent
of temperature
High T: entropic mixing

components
dominates;
mix
G/n
Low T
z
w + wBB
wAB AA
2
RT
Low T: energetic mixing term

dominates; components segregate
gB0
gA0
High T

Gibbs Free energy:
0
gB
G /n =
xB
z
w + wBB
wAB AA
2
RT
Homogenous mixture
TC
T)
G(x,
T
Coexistence region
of two separated
phases
xA
T
x
0
Pure A
1
Pure B
Binodal versus Spinodal Curves

Recall that there is a distinction between local and global stability
Local stability:
2 G
2 0
x
(system has reached lowest free energy

accessible via only small fluctuations)
Global stability: curve lies on envelop of local tangent lines

(system has reached lowest possible free energy)
If the global condition is violated
but the
local stability condition is
satisfied the curve is metastable
G/n
gB0
unstable
If both the global and local conditions

are violated the system is unstable and
will inevitably phase separate
gA0
metastable
0
A system can remain in a supersaturated metastable state until a sufficiently large

the stable phase separated state
fluctuation occurs to drive it into

Local stability:
2 G
2 0
x


The coexistence curve (binodal) is the line along which global stability fails
The binodal
curve is determined from the condition that points xA and xB
have a common tangent
gB0
G/n
G
x
G
=
x
x= x
A
gmixing
x= x B
(I used this condition to calculate the coexistance curve in the plots on slide 27)
=0
gA0
common tangent
0 xA
xB 1

Local stability:
2 G
2 0
x


The curve along which
local stability
fails is called
the spinodal:
2 G
2 =0
x
For the binary system:
TC
2 G 1
1
2 AB = 0
2 = +
x x 1 x
Binodal
two phase
Spinodal
0
Pure A
1
Pure B
Critical Point for Binary Mixtures

The critical point for a binary mixture can be determined from two conditions:
2G
x 2
(1) Onset of local stability:
=0
x= xC
3G
(2) Merging of the phases requires:
x 3
(tricky: second partial
of G must vanish
=0
x= xC
in the neighborhood of the critical point)
3G
x 3
x= xC
1
1
=
(1 x c ) 2 x c2
x2
=
x= xC
TC
= 0
1
1
2
AB
+
xc 1 xc
two phase
Spinodal
c
AB
=2
= 4 2 AB = 0
x c = 1/2
Binodal
0
Pure A
1
Pure B

Lecture 35: The Third Law
Time: 2:35-3:25
Office Hours: 2-3MW
Rutherford 411
Defining Absolute Entropy. . .

The third law of thermodynamics is concerned with the
behavior of the entropy as absolute zero is approached
To introduce the third law, let us ask how we might assign an absolute
value to the entropy of some substance at 1 atm of pressure:
The absolute entropy of a gas at some
temperature T can be written:
T melt
S(T,1atm) = S(0 K,1 atm) +
T boil
H fusion
+
dT
T
T
T
T
gas
H
C
vap
+ P dT
+
T
T
T
S(0K)
S(T)
C Psolid
dT
T
C Pliquid
T P
Recalling C P = T
substance melts
S = H fusion /T
boil
But what is S(0K)?
substance
boils
S = H vap /T
melt
CP
dT
T
Third Law: Planck

But what is the entropy at absolute zero: S(0K)?
This is the question addressed by the Third Law
The entropy of every pure liquid or solid substance in
equilibrium at absolute zero is itself zero
Third Law: Modified Plank Statement
The Planck statement was originally formulated in terms of a perfect crystal,

but it holds as well for 4He and 3He which remain liquid to absolute zero!
Note the two key words, pure and equilibrium:
The substance must be chemically pure: a mixture of chemically
different species will always have a finite mixing entropy, even at T=0
The substance must be in equilibrium: if the substance is not in
equilibrium, i.e. does not occupy a minima of the appropriate potential at
T=0, it may have residual entropy
NOTE: a system that would be considered merely metastable at a high temperature
can be considered as an equilibrium state near T=0 (no thermal energy is available to
drive the system out of the local minima)
Third Law: Statistical Interpretation

Plancks form of the third law has a very simple statistical
interpretation
Recall:
S = k B ln
Number of microstates available (multiplicity)
At absolute zero then S=0 corresponds to a =1
Residual Entropy
The condition that the system be in a true equilibrium state
can be problematic for several reasons:
Orientational Entropy: If the molecules are asymmetric (e.g. H20) then
they can orient themselves in different ways within the crystal. In a carbon
monoxide crystal two different orientations are possible:
These orientational rearrangements can occur nearly randomly. While one

arrangement may lead to a net lower free energy, in practice equilibration
can take a very long time, effectively freezing in a residual entropy
Residual Entropy
The condition that the system be in a true equilibrium state
can be problematic for several reasons:
Isotope Mixing: We have to worry about the mixing of entropy created by
combining different nuclear isotopes in one sample!
Nuclear Spins: The nuclear spins can in addition lead to a multiplicity of
different alignment states. The spins will align either in a parallel or antiparallel fashion at T=0, but spin entropy can be significant even <1K
Nernst Statement of Third Law

There is a second statement of the third law due to Nernst:
The entropy change in a process, between a pair of equilibrium states,
associated with a change in the external parameters tends to zero as the
temperature approaches absolute zero
Nernst Statement of the Third Law
We could paraphrase this statement as:
S 0
as
T 0
(isothermal process)
The Nernst statement (formulated in terms of entropy changes) can

be deduced from the Planck statement (formulated in terms of
absolute entropies)
Thermodynamic Consequences
The third law has some immediate thermodynamic consequences
In particular, partial derivatives of the entropy at constant temperature
must vanish as T approaches absolute zero
Coefficient of thermal expansion:
1
=
V
V

T P
V S T 0
Maxwells relation tells us:
= 0
T P P T
What about heat capacities?

T
Recall:
Thus
S(T) =
CP
dT
T
The entropy approaches zero as T0.

We thus require that CP0 to ensure that
the integral remains finite

0
C P 0 and CV 0 If we can reach absolute zero we
will not be able to stay there!
as T 0
(only an infinitesimal amount of heat required to increase the temperature away from T=0!)
Thermodynamic Consequences
The third law has some immediate thermodynamic consequences
Clausius-Clapeyron:
dP s T 0
=
0
dT v
The slope of a phase coexistance boundary for a first order transition must
become parallel to the temperature axis as absolute zero is approached!
Unattainability of Absolute Zero

There is a final formulation of the third law related to the unattainability of
absolute zero:
No reversible adiabatic process starting at non-zero temperature can
possibly bring a system to absolute zero
The T=0 isotherm coincides
with the S=0 adiabat
(this is just the Nernst

statement of the third law!)
Thus, the T=0 isotherm can
not be intersected by any
other adiabat!
We cant cool more
efficiently than with a
reversible adiabatic process!
T=T
T=T
S=S
T=0
S=S1
S=0

Phys 253 Thermal Physics

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Phys 253 Thermal Physics

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Physics 253: Thermal Physics

Prof: Walter Reisner

Extremely general but empirical in character: thermodynamics provides

(Macroscale~1023 atoms, e.g. one moles worth)

What is long enough?

Much greater than characteristic time scale of atomic motions

1 mole of a gas (say Ar) ~ 1023 atoms

(Avagadros number NA=6.0221023)

Can be characterized by just four numbers:

Disordered highly rapid particle motions are blurred-out

The First Law

Energy can also be transferred via hidden DOF. . . this is HEAT!

The Second Law

The Second Law

The Second Law

Basic Problem of Classical Mechanics:

Q: Given force F(x,t) how do I deduce the particles motion?

Same idea also applies to: classical electrodynamics, quantum

Thermodynamics does NOT allow us to predict the time-course of

Thermodynamics does NOT require a detailed microscopic model,

Thermodynamics vs Statistical Mechanics

Statistical Mechanics: Directly calculate thermodynamic

For many real-world systems

Why Study Thermodynamics?

Why Study Thermodynamics?

Office Hours and TAs

Policy on Group Work

Solutions from Online Research

Error Treasure Hunt/Contest

In-Class Problem Tutorials

Physics 253: Thermal Physics

I use WebCT (My Courses)!

The System, Surrounding and Walls

(e.g. confined volume

The System, Surrounding and Walls

The System, Surrounding and Walls

Liquid in open pot on the stove

Living organisms like yourself. . .

The System, Surrounding and Walls

Isolated System: walls prohibit exchange of matter and energy

The System, Surrounding and Walls

The System, Surrounding and Walls

Answer: Mechanical energy is transferred to system from

Process that involve volume exchange

Many alternative units for pressure. . .

Useful to remember: 1 atm=760 torr=101325 Pa105 Pa=1 bar

The System, Surrounding and Walls

Examples: Good thermal

Examples: good thermal

The System, Surrounding and Walls

The planet earth

Of course, these systems are open on

The System, Surrounding and Walls

Alert! A common student confusion in thermodynamics is to

IMPORTANT: Always be aware of whether the system

Key properties of equilibrium states:

volume of system 2 increases. . .

until mechanical equilibrium is reached

and if systems B and C are also in mechanical equilibrium. . .

Then systems A and C will be in mechanical equilibrium!

Let systems A and B be connected by a

VA=VB; NA=NB; PA=PB

VA=VB; NA=NB; PA=PB

I push piston in: