Statistical Physics

African Virtual university
Universit Virtuelle Africaine

Universidade Virtual Africana
Physics Module
Statistical Physics

Prepared by Sisay SHEWAMARE
Alr|car v|rlua| ur|vers|ly 1
Notice
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Table of ConTenTs
I. StatisticalPhysics__________________________________________5
II. PrerequisiteCourseorKnowledge _____________________________5
III. Time ____________________________________________________5
IV. Materials_________________________________________________5
V. ModuleRationale __________________________________________5
VI. Content__________________________________________________5
6.1 Overview___________________________________________5
6.2 Outline _____________________________________________6
6.3 GraphicOrganizer_____________________________________7
VII. GeneralObjectives _________________________________________8
VIII. SpecificLearningObjective(s)_________________________________9
IX. Pre-assessment __________________________________________11
X. TeachingandLearningActivities______________________________18
XI. GlossaryofKeyConcepts__________________________________111
XII. ListofCompulsoryReadings _______________________________112
XIII. CompiledListof(Optional)MultimediaResources_______________113
XIV. CompiledlistofUsefullinks________________________________116
XV. SynthesisoftheModule___________________________________117
XVI. SummativeEvaluation_____________________________________118
XVII.References _____________________________________________124
XVIII.MainAuthoroftheModule________________________________125
XIX.FileStructure ___________________________________________125

Foreword
This module has four major sections
The frst one is the Introductory section that consists of fve parts viz:
Title:- The title of the module is clearly described
Pre-requisit Knowledge: In this section you are provided with information regarding
the specifc pre-requisite knowledge and skills you require starting the module. Ca-
refully look into the requirements as this will help you to decide whether you require
some revision work or not.
Time Required: It gives you the total time (in hours) you require to complete the
module. All self tests, activities and evaluations are to be fnished in this specifed
time.
Materials Required: Here you will fnd the list of materials you require to complete
the module. Some of the materials are parts of the course package you will receive in
a CD-Rom or access through the internet. Materials recommended to conduct some
experiments may be obtained from your host institution (Partner institution of the
AVU) or you may acquire borrow by some other means.
Module Rationale: In this section you will get the answer to questions like Why
should I study this module as pre-service teacher trainee? What is its relevance to
my career?
The second is the CONTENT section that consists of three parts:
Overview: The content of the module is briefy presented. In this section you will
fned a video fle (QuickTime, movie) where the author of this module is interviewed
about this module. The paragraph overview of the module is followed by an outline
of the content including the approximate time required to complete each section. A
graphic organization of the whole content is presented next to the outline. All these
three will assist you to picture how content is organized in the module.
General Objective(S): Clear informative, concise and understandable objectives are
provided to give you what knowledge skills and attitudes you are expected to attain
after studying the module.
Specifc Learning Objectives (Instructional Objectives): Each of the specifc
objectives, stated in this section, is at the heart of a teaching learning activity. Units,
elements and themes of the module are meant to achieve the specifc objectives and
any kind of assessment is based on the objectives intended to be achieved. You are
urged to pay maximum attention to the specifc objectives as they are vital to organize
your effort in the study of the module.
The third section is the bulk of the module. It is the section where you will spend
more time and is referred to as the Teaching Learning Activities. The gist of the
nine components is listed below:
Pre-assessment: A set of questions, that will quantitatively evaluate your level of
preparedness to the specifc objectives of this module, are presented in this section.
The pre-assessment questions help you to identify what you know and what you need
to know, so that your level of concern will be raised and you can judge your level
of mastery. Answer key is provided for the set of questions and some pedagogical
comments are provided at the end.
Key Concepts (Glossary): This section contains short, concise defnitions of terms
used in the module. It helps you with terms which you might not be familiar with
in the module.
Compulsory Readings: A minimum of three compulsory reading materials are
provided. It is mandatory to read the documents.
Compulsory Resources: A minimum of two video, audio with an abstract in text
form is provided in this section.
Useful Links: A list of at least ten websites is provided in this section. It will help
you to deal with the content in greater depth.
Teaching And Learning Activities: This is the heart of the module. You need to
follow the learning guidance in this section. Various types of activities are provided.
Go through each activity. At times you my not necessarily follow the order in which
the activities are presented. It is very important to note:
formative and summative evaluations are carried out thoroughly
all compulsory readings and resources are done
as many as possible useful links are visited
feedback is given to the author and communication is done
Enjoy your work on this module.
I. statistical Physics
By Sisay Shewamare Gebremichael Jimma University Ethiopia
II. Prerequisite Course or Knowledge
In order to successfully study this module, it is recommended that you need to have
either completed or to concurrently study the AVU Thermal Physics, Mathematical
Physics and Quantum Mechanics Teachers Training modules.
III. Time
This module can be completed in 120hrs.
IV. Materials
The materials in this module are different books, and from the soft copy available
on the internet.
V. Module Rationale
In this module we are focusing on the system of macroscopic particles and we study
the statistical description of systems in terms of probability and the behavior of the
density of state which help to measure the macroscopic parameters like heat, absolute
temperature and entropy. As a result of this discussion we will acquired some very
powerful tools for calculating the macroscopic properties of any system in equilibrium
from knowledge of its microscopic constitutes then we shall illustrate their useful-
ness by discussing the application of macroscopic thermodynamics and distribution
of systems of particles.
VI. Content
6.1 Overview
The central concepts of this module are the macroscopic systems of particles and
macroscopic measurement. The module begins with the study of statistical descrip-
tion of systems with statistical thermodynamics and measuring the macroscopic
parameters and its application.
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Activities are related to the interaction of the macroscopic systems of particle and
analyzing the distribution of macroscopic systems in terms of the mean energy, entropy
and pressure. The inter relation between the macroscopic parameter discussed in the
application of macroscopic thermodynamics and in the partition function.
6.2 Outline
1 Unit 1 Statistical description of systems of particle (25 hours)
Specifcation of the state of the system,
Statistical enesemble.
Probability,
Simple random walk problem in one dimenssion;
Binomial distribution.
Gaussian distribution.
Principles of equal priori probability
Relaxation time
The probability of the density of states.
2 Macroscopic measurements (25 hours)
Work and internal energy.
Absolut temperature,
Heat capacity and specifc heats.
Entropy
3 Statistical thermodynamics (30 hours)
Equilibrium condition and constraints,
Entropy of the combined system,
The approach to thermal equilibrium.
Heat reservoir.
Dependency of the density of states on the external parameters.
4 Some application of statistical and macroscopic thermodynamics (40 hours)
Thermodynamics potential and their relation with thermodynamical variables,
Enesembles systems,
Connection of canonical distribution with thermodynamics .
Partition function and their properties.
Gibs paradox.
Validity of the classical approximation.
The equi partition theorem
Kinetic theory of dilute gases in equilibrium
Distribution of systems of particles
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6.3 Graphic Organizer
6
Statistical
Physics
A. Statisti cal Description of
Systems of Particles
B. Macroscopic Measurements:
C. Statistical Thermodynami cs
D. Some Applications
Statistical Theories,
Specification of the state of the system,
Probability calculations,
Simple random walk problem in one dimenssion;
Principles of equal priori probability
Relaxation time
The probability of the density of states.
phase space
Accessi ble States,
Heat capacity and specific heats.
Entropy
Equilibrium condition and constraints,
Entropy of a combined system,
The approach to thermal equilibrium.
Heat reservoir.
Dependency of the density of states
on the external parameters.
Thermodynamic potentials
and their relation with thermodynamical variables,
Enesembles systems,
Connection of canonical distribution with thermodynamics .
Partition function and their properties.
Gibs paradox,
Validity of the classical approximation.
Kinetic theory of dilute gases in equilibrium
Distribution of systems of particles
Statistical
Physic
VII. General objective(s)
After completing this module you will be able to
Appreciate that the statistical distribution of systems of particle and their
solution at equilibrium
Understand the concept of temperature, heat and internal energy
Understand the underlying basis and the total statistical thermodynamics
law
Understand the macroscopic parameters and their measurements
Understand the basic generalized force and entropy
Understand the application of statistical and macroscopic thermodynamics
Understand the partition function
Derive the macroscopic measurements using the partition function
Derive the distribution of systems of particles
VIII. specifc learning objectives
(Instructional objectives)
Content Learning objectives

AfterCompletingthissectionyou
wouldbeableto:
1. Unit 1 Statistical
description of systems of
particle (25 hours)
Specifcation of the state of the
system,
Probability,
Simple random walk problem
in one dimenssion;
Principles of equal priori pro-
bability
Relaxation time
The probability of the den-
sity of states.
Deriving the statistical equation
Discussion on two state system to
apply random walk problem
Defne the relaxation time
Deriving the binomial distribu-
tion
Derive the Gaussian equation
2. Macroscopic
measurements (25 hours)
Heat capacity and specifc
heats
Entropy
Defne the work done and the
internal energy
Describe the absolute and en-
tropy relation
State the heat capacity at constant
V,P
Defne and derive the entropy
3. Statistical thermodynamics
(30 hours)
Equilibrium condition and
constraints,
Entropy of the combined system,
The approach to thermal equili-
brium.
Heat reservoir.
Dependency of the density of
states on the external parameters
.
Write the equilibrium conditions
Derive the entropy equation for
two systems
Solve problems related to entropy
Calculate the density of state at
equilibrium condition
4. Some application of
statistical and macroscopic
thermodynamics (40 hours)
Thermodynamics potential and
their relation with thermodyna-
mical variables,
Enesembles systems,
Connection of canonical distri-
bution with thermodynamics .
Partition function and their pro-
perties.
Gibs paradox.
Validity of the classical approxi-
mation.
Kinetic theory of dilute gases in
equilibrium.
Relates different thermodyna-
mics equation
Find thermodynamics quantity
relations using the thermodyna-
mics potentials
Defne the ensemble systems
Derive the partition function
Show the thermodynamics
quantities using the partition
function
Show the Gibbs paradox
Derive different distribution
IX. Pre-assessment
Are you ready for this module?

Figure 5: Ludwig Boltzmann (18441906)
Dear Learners
In this section, you will fnd self-evaluation questions that will help you test your
preparedness to complete this module. You should judge yourself sincerely and do
the recommended action after completion of the self-test. We encourage you to take
time and answer the questions.
Dear Instructors
The Pre-assessment questions placed here guide learners to decide whether they are
prepared to take the content presented in this module. It is strongly suggested to abide
by the recommendations made on the basis of the mark obtained by the learner. As
their instructor you should encourage learners to evaluate themselves by answering
all the questions provided below. Education research shows that this will help learners
be more prepared and help them articulate previous knowledge.
9.1 Self Evaluation Associated With Statistical Physics
Evaluate your preparedness to take the module on thermal physics. If you score
greater than or equal to 60 out of 75, you are ready to use this module. If you score
something between 40 and 60 you may need to revise your school physics on topics
of heat. A score less than 40 out of 75 indicates you need to physics.
1) How many calories of heat are required to raise the temperature of 3kg of
aluminum from 20
0
C to 55
0
C? Given specifc heat capacity of aluminum

C = 910J kg
-1
K
-1
and 4.2J=1 calorie
a. 13000
b. 22750
c. 35750
d. 95550
2) If 200g of water is contained in a 300g aluminum vessel at 10
0
C and an additional
100g of water at 100
0
C is poured into the container, what is the fnal equilibrium
temperature of the system? In degree Celsius
a. 77
b. 45
c. 35
d. 20
3) Two moles of an ideal gas ( =1.4) expand quasi-statically and adiabatic ally
from pressure of 5 atm. and a volume of 12 liters to fnal volume of 30 liters a.
What is the fnal pressure of the gas?
a. 1.4
b. 3.4
c. 3
d. 1
4) An ideal gas ( =1.4) expands quasi-statically and adiabatically. If the fnal
temperature is one third the initial temperature so by what factor does its volume
change?
a. 10
b. 20
c. 16
d. 12
5) Following question 4 above, by what factor does its pressure change?
a. 1
b. 1.2
c. 0.02
d. 2
6) One mole of an ideal gas does 3000J of work on the surroundings as it expands
isothermally to a fnal pressure of 1atm. and volume of 25l. Determine the tem-
perature of the gas
a. 200K
b. 100K
c. 400K
d. 300K
7) Following question 6 above, calculate initial volume of the gas.
a. 20l
b. 30l
c. 22l
d. 25l
8) Five moles of an ideal gas expands is isothermally at 127
0
C to four times its
initial volume. Find the work done by the gas
a. 30,000J
b. 40,000J
c. 50,000J
d. 32,012J
9) A gas is compressed at a constant pressure 0.8 atm from a volume of 9 liters
to a volume of 2 liters. If in the process 400J of heat energy fows out of the gas
what is the work done by the gas?
a. 57J
b. 37J
c. 50J
d. 400J
10) Using question 9 above, what is the internal energy lost by the system
a. 500J
b. 600J
c. 456J
d. 400J
11) There are two thermometers based on different thermometric properties of two
different materials. The two thermometers show identical readings because
a. each property changes uniformly with temperature.
b. the relation between the property and temperature is identical in the two ca-
ses
c. the property of one of increases with temperature and the property of the other
decreases at a uniform rate
d. the two thermometers have been calibrated with reference to a common stan-
dard.
12) In a Carnot cycle
a. work done during adiabatic expansion is less than work done during adiabatic
compression
b. work done by working substance during adiabatic expansion is greater than
work done during adiabatic compression.
c. work done during adiabatic expansion is equal to work done during adiabatic
compression
d. work done during adiabatic expansion is equal to the heat absorbed from the
source.
13) Which of the statements below is wrong about an ideal gas?
a. The total number of molecules is large
b. The molecules are in random motion
c. The molecules do not exert any appreciable force on one another or on the
walls
d. The volume of the molecule is negligibly small compared with the volume
occupied by the gas.
14) The mean free path in a gas is
a. the distance travelled by a molecule before hitting a wall
b. the average distance travelled by a molecule in one second
c. the root mean square velocity
d. the average distance travelled by molecules between any two successive
collisions
15) In adiabatic process work done
a. by working substance during adiabatic expansion is greater than work done
during adiabatic compression.
b. during adiabatic expansion is equal to work done during adiabatic compres-
sion
c. during adiabatic expansion is equal to the heat absorbed from the source.
d. by working substance during adiabatic expansion is equal to the heat that
enters.
16) Which of the following statements is wrong about a real gas?
a. The total number of molecules is large
b. The molecules are in random motion
c. The molecules exert negligible force on one another or on the walls
d. The volume of the molecule is appreciable compared with the volume occupied
by the gas.
17) The root mean square velocity of a gas
a. does not depend on the temperature but on the pressure of the gas.
b. increases with the density of the gas.
c. decreases with the volume of the gas.
d. depends on both the pressure and temperature of the gas.
18) The average molecular kinetic energy at a temperature

T
o
K is
a.

1
3
kT
b.

3
2
kT
c.

1
2
kT
d.

2
3
kT
9.2 Answer Key:
1. b
2. c
3. a
4. c
5. c
6. d
7. c
8. d
9. a
10. c
11. a
12. c
13. c
14. d
15. .b
16. c
17. d
18. b
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9.3 Pedagogical Comment For The Learner:
Physics, as a discipline that attempts to describe phenomena and processes in nature,
has succeeded in developing theoretical frameworks that describe processes and phe-
nomena ranging from subatomic particles to celestial bodies in galaxies. Theoretical
framework, suffcient enough to describe nonlinear systems such as the properties of
granular media, earthquakes, friction and many other systems, is still lacking.
Statistical physics gives a rational understanding of Thermodynamics in terms of
microscopic particles and their interactions. It allows calculation of macroscopic
properties from microscopic considerations. The tools and methods developed in
statistical physics are extensively used in frontier research areas to understand non-
linear systems.
The material presented in this module is highly sequential. You need to follow the
activities in the order they are presented in the module. If you dont understand
something go and refer to the compulsory materials and visit the useful links there
in; dont just write it down and hope that youll fgure it out later.
Extensive research in recent years has shown that the students who do best in physics
(and other subjects) are those who involve themselves actively in the learning process.
This involvement can take many forms: writing many questions in the margins of the
module; asking questions by email; discussing physics in the AVU discussion fora
doing exercises and self-assessments on schedule etc.
X. Teaching and learning activities
ACTIVITY 1: Statistical Description of System of Particles
You will require 25 hours to complete this activity. In this activity you are guided
with a series of readings, Multimedia clips, worked examples and self assessment
questions and problems. You are strongly advised to go through the activities and
consult all the compulsory materials and as many as possible of the useful links and
references.
Specific Teaching and Learning Objectives
Deriving the statistical equation
Discussion on two state system to apply random walk problem
Defne the relaxation time
Deriving the binomial Gaussian distribution
Summary of the Learning Activity
Description of a system of particles is an effort where theory is applied to a large
numbers of particles. We are not interested in all the details of the underlying mi-
croscopic dynamics of individual particles that constitute a large number of particles
like a given of mass of gas.
Instead, it is the systems macroscopic properties among which are the thermodyna-
mic functions that we wish to understand or to deduce, and these are gross averages
over the detailed dynamical states. That is the reason for the word statistical in the
name of our subject. Prominent feature in the landscape of statistical mechanics is
the Boltzmann distribution law, which tells us with what frequency the individual
microscopic states of a system of given temperature occur. An informal statement of
that law is given in the next section, where it is seen to be an obvious generalization
of two other well known distribution laws: the Maxwell velocity distribution and
the barometric distribution. We also need to note here that the exponential form
of the Boltzmann distribution law is consistent with indeed, is required by the
rule that the probability of occurrence of independent events is the product of the
separate probabilities.
List of Required Readings
Reading #1:.
Complete reference : Statistical Mechanics
From Cornell Universit
URL : http://pages.physics.cornell.edu/sethna/StatMech
Accessed on the 23
rd
September 2007
Abstract : Contents: Random Walks and Emergent Properties; Temperature and
Equilibrium; Entropy; Free Energies and Ensembles; Quantum Statistical Me-
chanics; Computational Stat Mech: Ising and Markov; Order Parameters, Broken
Symmetry, and Topology; Deriving New Laws; Correlations, Response, and Dissi-
pation; Abrupt Phase Transitions; Continuous Phase Transitions.
Rationale: This chapter covers most of the topics in the second and third activities
of the module...
List of Relevant MM Resources
Reference http://jersey.uoregon.edu/vlab/Piston/index.html
Date Consulted:-Nov 2006
Reference:-: http://lectureonline.cl.msu.edu/~mmp/kap10/cd283.htm.
Date Consulted:- August 2006 .
Reference http://en.wikipedia.org/wiki/Binomial_distribution
Reference:-: http://www.stat.yale.edu/Courses/1997-98/101/binom.htm.
Date Consulted:- August 2006
Reference: http://en.wikipedia.org/wiki/Normal_distribution
Date Consulted: Nov 2006
Complete Reference:- Computer calculation of Phase Diagrams.
List of Relevant Useful Links
Useful Link #1
Title: Exactly Solved Models in Statistical Mechanics
URL: http://tpsrv.anu.edu.au/Members/baxter/book
Screen Capture:
Description: Rodney Baxters classic book is offcially out of print. Contents: basic
statistical mechanics; the one-dimensional Ising model; the mean feld theory; Ising
model on the Bethe Lattice; The Spherical Model; Duality and Star Triangle Trans-
formations of Planar Ising Models; Square-Lattice Ising Model; Ice-Type Models;
Alternative Way of Solving the Ice-Type Models; Squared Lattice Eight-Vertex Mo-
del; Kagom Lattice Eight-Vertex Model; Potts and Ashkin-Teller Models; Corner
Transfer Matrices; Hard Hexagon and Related Models; Elliptic Functions. .
Rationale: This book can be downloaded and used for personal and non-commercial
use
Date Consulted: - Aug 2007
Useful Link #2
Title: STATISTICAL PHYSICS An Introductory Course
URL: http://www.worldscibooks.com/physics/3526.html
Screen Capture

By Daniel J Amit (Universita di Roma La Sapienza & The Hebrew University)
& Yosef Verbin (The Open University of Israel)
Description: This invaluable textbook is an introduction to statistical physics that
has been written primarily for self-study. It provides a comprehensive approach to
the main ideas of statistical physics at the level of an introductory course, starting
from the kinetic theory of gases and proceeding all the way to BoseEinstein and
FermiDirac statistics. Each idea is brought out with ample motivation and clear,
step-by-step, deductive exposition. The key points and methods are presented and
discussed on the basis of concrete representative systems, such as the paramagnet,
Einsteins solid, the diatomic gas, black body radiation, electric conductivity in met-
als and superfuidity.
The book is written in a stimulating style and is accompanied by a large number of
exercises appropriately placed within the text and by self-assessment problems at the
end of each chapter. Detailed solutions of all the exercises are provided.
Introduction to the Activity
Detailed Description of the Activity (Main Theoretical Elements)
Statistical description of systems of particles
Consideration of non interactive systems of particles to analyze the probability with
binomial and Gaussian distribution by consideration of the statistical approach and
with the density of systems of particles.
Statistical Description of Systems of Particles
Statistical Theories,
Ensemble
Accessible state
Probability calculation
Phase space
Specification of the state of the system
How do we determine the state of a many particle system? Well, let us, frst of all,
consider the simplest possible many particle system, which consists of a single
spinless particle moving classically in one dimension. Assuming that we know the
particles equation of motion, the state of the system is fully specifed once we si-
multaneously measure the particles position q and momentum p. In principle, if we
know q and p then we can calculate the state of the system at all subsequent times
using the equation of motion
Statistical ensemble
If we are informed about any of the initial conditions of a thrown up coin like its
position, the height of the throw and the corresponding velocity of the coin, we
would indeed predict the out come of the experiment by applying the law of classical
mechanics.
In an experiment that describes the outcome in terms of the probability of a single
coin, we consider an ensemble consisting of many such single experiments.
Probability
In this section we will discuss some of elementary aspect of probability theory. It is
important to keep in mind that whenever it is desired to described a situation from
a statistical point of view (i.e., in terms of probabilities), It is always necessary to
consider an assembly ( ensemble) consists of a very large number of similar prepared
systems.
Group discussion
Give some example which can be described by two states of systems of particles
Answer
a) In throwing a pair of dice, one gives a statistical description by considering
a very large number.
b) In the basic probability concept, it will be useful to keep in mind a specifc
simple but important, illustrative example the so called random walk pro-
blem
c) Magnetism: An atom has a spin

1
2
and a magnetic moment ; in accordance

with quantum mechanics, its spin can therefore point either up or down
with respect to a given direction. If both these possibilities are equally likely,
what is the net total magnetic moment of N such atoms?
d) Diffusion of a molecule in a gas: A given molecule travels in three dimensions
a mean distance l between collisions with other molecules. How far is it likely
to have gone after N collisions?
The simple random walk problem in one dimension
For the sake of simplicity we shall discuss the random walk problem in one dimension.
A particle performing successive steps, or displacements, in one dimension after a
total of N such steps, each of lengthl , the particle is located at
x = ml

Where mis an integer lying between N<m<N
The probability P
N
(m) of fnding the particle at the position x = ml after N such
steps.
W
N
(n
1
) =
N!
n
1
!n
2
!
p
n
1
q
n
2
Group discussion
Derive the probability W
N
(n
1
) for fnding the particle at position x=ml after N
steps
You can see the derivation as follow
The total number of steps N is simply
N = n
1
n
2

The net displacement where
m= n
1
n
2

m= n
1
n
2
= n
1
(N n
1
) = 2n
1
N
Our fundamental assumption was that successive steps are statistically independent
of each other. Thus one can assert simply that, irrespective of past history, each step
is characterized by the respective probabilities
P = probability that the step is to the right
q =1 p = probability that the step is to the left
Now, the probability of any one given sequence of n
1
steps to the right and n
2
steps
to the left is given simply by multiplying the respective probabilities, i.e., by

p
1
p
2
... p
n
q
1
q
2
...q
n
= p
n
1
q
n
2
The number of distinct possibilities is given by

N!
n
1
!n
2
!

The probability W
N
(n
1
) of taking n
1
steps to the right and n
2
= N - n
1
steps to the
left, in any order, is obtained by multiplying the probability of this sequence by the
number of possible sequences of such steps. This gives
W
N
(n
1
) =
N!
n
1
!n
2
!
p
n
1
q
n
2

Binomial Distribution
Indeed, we recall that the binomial expansion is given by the formula
(p + q)
N
=
n= 0
N
N!
n!(N n)!
p
n
q
N n
Read the binomial distribution in the fundamentals of thermodynamics book (Fede-
rick Reif) pp.7-23
Group discussion
Given that n
1
=
1
2
(N + m), n
2
=
1
2
(N m)
Show that

p
N
(m) =
N!
[(N + m) / 2]![(N m) / 2]!
1
2
N

In this discussion you may consider the probability P
N
(m) that the particle is found
at position m after N steps is the same as W
N
(n
1
) given by
P
N
(m) =W
N
(n
1
)

Mean Value
If f(u) is any function of u, then the mean value of f(u) is defned by

f (u)
p(u
i
) f (u
i
)
i =1
M
P(u
i
)
i =1
M

This expression can be simplifed. Since P(u
i
) is defned as a probability, the quan-
tity
African Virtual University 26
P(u
1
) + P(u
2
) + ... + P(u
M
) P(u
i
)
i =1
M
P(u
i
) = 1
i =1
M
Thisistheso-callednormalizationcondition
f (u) p(u
i
) f (u
i
)
i =1
M
Activity
Derivethesummationandtheproductofthemeanvalueofdifferentfunction
Solution
Iff(u)andg(u)areanytwofunctionsofu,then
f (u) _ g(u) = P(u
i
)[ f (u
i
i =1
M
) + g(u
i
)] = P(u
i
) f (u
i
) + P(u
i
)g(u
i
)
i =1
M
i =1
M
Or
f (u) + g(u) = f (u) + g(u)
Ifcisanyconstant,itisclearthat
cf (u) = cf (u)
Deviation dispersion and standard deviation
u = u udeviation
(u)
2
P(u
i
)(u
i
i 1
M
u)
2
0 secondmomentofuaboutitsmean,ormore
simplythedispersionofusince( (u)
2
0 canneverbenegative,
Thevarianceofuisproportionaltothesquareofthescatterofuarounditsmeanvalue.
Amoreusefulmeasureofthescatterisgivenbythesquarerootofthevariance,
( ) ( ) f u g u +

( ) [ ]
2
1
2
* u u =

which is usually called the standard deviation of u.
The Gaussian Distribution
( )
( )
2
1
2
1
1
* 2
exp
* 2
1
) (
n
n n
n
n P

This is the famous Gaussian distribution function. The Gaussian distribution is only
valid in the limits N>>1 and
1
n >>1
Activity
Using the Taylor expansion and derive the Gaussian distribution
Solution
Let us expand lnP around n =n
~
. Note that we expand the slowly varying function
lnP(n), instead of the rapidly varying function P(n), because the Taylor expansion of
P(n) does not converge suffciently rapidly in the vicinity of n = n
~
to be useful. We
can write

ln p % n+ n
( )
= ln p( % n) +
1
+

2
2

2
+ ...
where

B
k
=
d
k
ln P
dn
k
n=n
P n ( ) P n
1
( )
exp
n n
1
( )
2
2 *n
1
( )
2

The constant P(
1
n ) is most conveniently fxed by making use of the normalization
condition
For discrete case

P
N
(n
!
)
n
1
=0
N
= 1
For continues case

P
N
(n)dn
0
N
= 1
for a continuous distribution function. Since we only expect P (n) to be signifcant
when n lies in the relatively narrow range
1 1
*n n , the limits of integration in the
above expression can be replaced by with negligible error. Thus,
P n
( )
exp
n n
1
( )
2
2 *n
1
( )
2
dn = P n
1
( )
2*n
1
exp x
2
( )
dx
1
The principle of equal a priori probabilities
Activity
Take a bottle of gas which is isolated with the external environment.

Solution
In this situation, we would expect the probability of the system being found in one of
its accessible states to be independent of time.
This implies that the statistical ensemble does not evolve with time.
Individual systems in the ensemble will constantly change state; but the average number
of systems in any given state should remain constant.
Thus, all macroscopic parameters describing the system, such as the energy and the
volume, should also remain constant.
There is nothing in the laws of mechanics which would lead us to suppose that the
system will be found more often in one of its accessible states than in another. We
assume, therefore, that the system is equally likely to be found in any of its accessible
states. This is called the assumption of equal a priori probabilities, and lies at the very
heart of statistical mechanics.
The relaxation time
Activity
Take an isolated many particle systems will eventually reach equilibrium, irrespective
of its initial state.

Time
Number of particle
Relaxation Time Fluctuation Time
Solution
The typical time-scale for this process is called the relaxation time, and depends in
detail on the nature of the inter-particle interactions.
The principle of equal a priori probabilities is only valid for equilibrium states.
The relaxation time for the air in a typical classroom is very much less than one
second. This suggests that such air is probably in equilibrium most of the time, and
should, therefore, be governed by the principle of equal a priori probabilities.
Behavior of the density of states
A macroscopic system is one which has many degrees of freedom denote the energy
of the system by E. We shall denote by E ( ) the number of states whose energy
lies between E and E+dE in a system. Let E ( ) denote the total number of possible
quantum states of the system which are characterized by energies less than E. Clearly
E ( ) increase when E increases. The number of states E ( ) in the range between
E and E+dE is then

E ( ) = E +E ( ) + E ( ) =

E
E
Activity
Consider the case of a gas of N identical molecules enclosed in container of
volume V. The energy of the system can be written
E=K+U+E
int
Where
K=K(p
1
,p
2
,.p
N
)=
1
2m
p
i
2
i =1
N
, U=U(r
1
,r
2
,r
N
)

Considering the system for mono atomic ideal gas U=0, E
int
=0
Solution
The number of states (E, V) lying between the energies E and E+ E is simply
equal to the number of cells in phase-space contained between these energies.

E
E+dE
R
Px
Py
In other words, (E, V) is proportional to the volume of phase-space between
these two energies:

E ,V
( )
d
3
r
1
...d
3
r
N
d
3
p
1
...d
3
p
N
E
E + E

Here, the integrand is the element of volume of phase-space, with
d
3
r = dx
i
dy
i
dz
i
d
3
p = dp
i x
dp
i y
dp
i z
,
the number of states E ( ) lying spherical shell between energies E and E+dE is
given
= BV
N
E
3 N
2
In other words, the density of states varies like the extensive macroscopic parameters
of the system raised to the power of the number of degrees of freedom. An extensive
parameter is one which scales with the size of the system (e.g., the volume). Since
thermodynamic systems generally possess a very large number of degrees of freedom,
this result implies that the density of states is an exceptionally rapidly increasing

function of the energy and volume. This result, which turns out to be quite general,
is very useful in statistical thermodynamics.
Problem
1. A penny is tossed 400 times. Find the probability of getting 215 heads. (Sugges-
tion: use the Gaussian approximation)
Solution
A penny is tossed 400 times. Find the probability of getting 215 heads is given by the
Gaussian approximation

( )
( )
2
1
2
1
1
* 2
exp
* 2
1
) (
n
n n
n
n P
where
N=400, n
1
=251, p=1/2, q=1/2
n1 = Np *n
1
= Npq = 400x1/ 2x1/ 2 = 100 = 10

*n
1
( )
2
= 100 , n
1
= 200
Substituting in the Gaussian equation

P(251, 400) =
1
10 2
e
251 200 ( )
2
200

P(251, 400) 1.3x10
2
Problem
2. A particle of mass m is free to move in one dimension. Denote its position coor-
dinate by x and its momentum by p. Suppose that this particle is confned with
a box so as to be located between x=0 and x=L, and suppose that its energy is
known to lie between E and E+dE. Draw the classical phase space of this particle,
indicating the regions of this space which are accessible to the particle
Solution
Let us represent the particle motion in the coordinate of p, x

p
x 0 L
p
P+ dp
The particle with position x and momentum p position lies between x=0 and x=L,
energy lies between E and E+dE
The momentum of the particle is given by
E=p
2
/2m

p = 2mE
the accessible state in the phase space E ( ) =
d E ( )
dE
E the number of states
which have an energy E in phase space is given by E ( ) = p = 2mE
3. What is the probability of throwing a three or a six with one throw of die?
solution
the probability that the face exhibit either 3 or 6 is

1
6
+
1
6
=
1
3
ACTIVITY 2: Macroscopic Parameters and their Measurements
consult all the compulsory materials and use as many as possible useful links and
references.
Defne the work done and the internal energy
Describe the absolute and entropy relation
State the heat capacity at constant V,P
This activity defnes the relation between work done and internal energy of a system.
The concept of Entropy is derived for a combined system and problems related to
entropy and density of states for the equilibrium are treated.
Reading #2:.
Complete reference : From Classical Mechanics to Statistical Mechanics
From Draft chapters of Thermal and Statistical Physics
URL : http://stp.clarku.edu/notes/chap1.pdf
Accessed on the 23
rd
September 2007
Abstract : Thermal and Statistical Physics: From Classical Mechanics to Sta-
tistical Mechanics; thermodynamic Concepts and Processes; Concepts of
Probability;The Methodology of Statistical Mechanics; Magnetic Systems; Nonin-
teracting Particle Systems; Thermodynamic Relations and Processes; Theories of
Gases and Liquids; Critical Phenomena and the Renormalization Group; Introduc-
tion to Many-Body Perturbation Theory...
of the module...
List of Relevant Resources
Reference http://en.wikipedia.org/wiki/Absolute_zero
Description: - Absolute zero is the lowest possible temperature, occurring when
no heat energy remains in a substance. Absolute zero is the point at which parti-
cles have a minimum energy, determined by quantum mechanical effects, which is
called the zero-point energy. By international agreement, absolute zero is defned
as precisely 0 K on the Kelvin scale, which is a thermodynamic (absolute) temper-
ature scale, and -273.15C on the Celsius scale.
[1]
Absolute zero is also precisely
equivalent to 0 R on the Rankine scale (also a thermodynamic temperature scale),
and 459.67 F on the Fahrenheit scale
Reference:-: http://www.upscale.utoronto.ca/GeneralInterest/Harrison/Entropy/
Entropy.html
Date Consulted:- February 1999
Description:-
The entropy is a measure of the probability of a particular result.
The entropy is a measure of the disorder of a system.
The entropy measures the heat divided by the absolute temperature of a body.
The laws that govern the relationships between heat and work are studied in thermal
physics. Since heat is a form of energy and work is the mechanism by which energy
is transferred, these laws are based on the basic principles that govern the behaviour
of other types of energy such as the principle of conservation of energy.
In this activity you will be guided through a series of tasks to understand heat as a
form of energy and defne terms like heat capacity, heat of fusion and heat of vapo-
rization.

Figure: compression of gas molecules

Macroscopic Measurements:
Work and internal energy
Absolute temperature
Heat capacity and specifc heat capacity
Entropy
Work and internal energy
The macroscopic work done by a system is determined by the volume of a system if
changed quasi-statically from

V
i
to V
f
and throughout this process the mean pressure
of the system has the measurable value

p V
( )
.

W = pdV
V
i
V
f
If the system is isothermally insulated so it cant absorb any heat then Q=0
The internal energy

E = W
Activity
Consider a system that consists of the cylinder containing a gas. Supply the external
energy to the system by switching the circuit. What do you observe? Consider a
standard macrostate

i of volume

V
i
and mean pressure

p
i
, where

E = E
i
. How would one determined the mean energy

E
j
of any other macrostate

j of volume

V
j
and the mean pressure

p
j
?
Figure A system consists of cylinder containing gas.

The volume V of the gas is determined by the position of the piston. The resistance
can brings thermal contact to the system.
Solution
The microstate of the system can be specifed by the two parameters, volume

V
and internal
energy

E . Each macrostate can be represented by a point on

pV diagram.
As the gas expand from 1 to its fnal volume 3 the mean pressure decrease to some
value
3
p and the work done by the piston
13
W
To bring the pressure
3
p without changing the volume, work is done by the elec-
tric resistance by an amount
R
W and if the amount of energy consumed by the
resistance then the energy supplied by the external system is
R
W .
The total internal energy of the system in state in state 2 is then given by

( ) a
ac R
E E W W = +
The amount of heat absorbed from a macrostate 1 to a macrostate 2 is given by

2 2 1
12
( ) E E E W = +
Heat
The heat
ab
Q absorbed by the system in going from a macrostate a to another
macrostate is given by
( )
ab b a ab
Q E E W = +
Absolute temperature
Properties of absolute temperature
1. The absolute temperature provides one with a temperature parameter which
is completely independent of the nature of the particular thermometer used
to perform the temperature measurement.
2. The absolute temperature T is a parameter of fundamental signifcance which
enters all the theoretical equations. Hence all the theoretical predictions will
involve this particular temperature.
Activity
From the equation of state
pV = NKT
you can show equivalently where
,
a
pV RT
R N K
=
=

Heat capacity and specific heat
Consider a macroscopic system whose macrostate can be specifed by its absolute
temperature T and some other macroscopic parameter y (y might be volume or mean
pressure)
Activity
Take a macroscopic system at temperature T, an infnitesimal amount of heat
dQ is added to the system and the other parameters y kept fxed.
The resulting change dT in temperature of the system depends on the nature
of the system as well as on the parameters T and y specifying the macrostate
of the system
Result
The specifc heat capacity at constant y is defned by

y
y
dQ
C
dT

=

The specifc heat per mole or heat capacity per mole is thus defned by

1 1
y y
y
dQ
c C
dT

= =

Eventually the specifc heat per gram is defned as

1 1
'
y y
y
dQ
c C
m m dT

= =

Task
Take a gas or a liquid whose macrostate can be specifed by two parameters say the
temperature T and volume. Calculate the heat capacity at constant volume C
and
at constant pressure
p
C

Figure : Diagram illustrated specifc heat measurement of a gas kept at constant
volume or at constant pressure
To determine C

We clamp the piston in position that the volume of the system is kept fxed.
In this case the system cannot do any work, and the heat dQ added to the system
goes entirely to increase the internal energy of the system

dQ dE =
To determine
p
C
The piston left completely free to move the weight of the piston being equal to the
constant force per unit area (mean pressure) on the system
In this case the piston will move when heat dQis added to the system; as the result
the system does also mechanical work. Thus the heat dQis used both to increase the
internal energy of the system and to do mechanical work on the piston

dQ dE pdV = + which is the fundamental law of thermodynamics
From the result we expected
i). dE is increase by small amount( and hence the temperature T will also increase
by smaller amount) in the second case compared to the frst.
ii).

C
p
> C

Heat capacity using the second law of thermodynamics
The second law of thermodynamics is given by

dQ = TdS the heat capacity

C
y
= T
S
T
y
If all external parameters of the system kept constant, then the system dose no
macroscopic work,

dW = 0 then the frst law reduced to

dQ = dE

C
V
= T
S
T
V
=
E
T
V
Example
Let us consider heat measurements by the method of mixtures in terms of the specifc
heats of the substance involved. Consider that two substances A and B, of respec-
tive masses

m
A
and

m
B
, are brought into thermal contact under condition where the
pressure is kept constant. Assume that before the substance are brought into thermal
contact their respective equilibrium temperature are

T
A
and

T
B
respectively. Compute
the fnal temperature

T
f
Solution
Entropy
The entropy can readily be determined by using the second law

dQ = TdS for an
infnitesimal quasi-static process.
Given any macrostate b of the system, one can fnd the entropy difference between
this state and some standard state a to state b and calculating for this process

S
b
S
a
=
dQ
T
a
b
Suppose that the macrostate of a body is specifed by its temperature, since all its
other parameters are kept constant.

S T
b
( )
S T
a
( )
=
dQ
T
a
b
=
C
y
T '
( )
dT '
T '
T
a
T
b
then

S T
b
( )
S T
a
( )
= C
y
ln
T
b
T
a
Problem
Consider two system A and system B with constant specifc heat

C '
A
and

C '
B
and
originally at respective temperature

T
A
and

T
B
, are brought into thermal contact with
each other. After the system come to equilibrium, they reach a come fnal temperature

T
f
. What is the entropy change of the entire system in this process?

Isolated system
B,T
B
System
System A,T
A
Answer
To calculate the entropy change of system A, we can imagine that it is brought from
its initial temperature

T
A
to its fnal temperature

T
f
by a succession of infnitesimal
heat additions.

dQ = m
A
C '
A
dT

dS =
dQ
T
= S
A
(T
f
) S
A
(T
A
) =
m
A
C
A
' dT
T
T
A
T
f
= m
A
C '
A
ln
T
f
T
A
Similarly for the system B

dS =
dQ
T
= S
B
(T
f
) S
B
(T
B
) =
m
B
C
B
' dT
T
T
B
T
f
= m
B
C '
B
ln
T
f
T
B
The total entropy change

S
A
+ S
B
= m
A
C '
A
ln
T
f
T
A
+

m
B
C '
B
ln
T
f
T
B
Problems
(a) One kilogram of water at 0
0
C is brought into contact with a large heat reservoir at
100
0
C. When the water has reached 100
0
C, what has been the change in entropy
of the water? Of the heat reservoir? Of the entire system consisting of both
water and heat reservoir?
b) If the water had been heated from 0
0
C to 100
0
C by frst bringing it is contact
with a reservoir at 50
0
C and then with a reservoir at 100
0
C, what would have
been the change in entropy of the entire system?
C) Show how the water might be heated from 0
0
C to 100
0
C with no change in the
entropy of the entire system.
Answer
Entropy of water

dS
0 100
0
C
=
dQ
T
where dQ = mCdT
=
mCdT
T

S = mC
dT
T
273k
373k

S = mC ln
T
f
T
i

S
water
= mC ln
373
273
(where mass of water =1kg)
= 1310J/K
The entropy of reservoir
The amount of heat loss by the reservoir

Q
water
= Q
r eser voi r

Q
r eser voi r
= mC(T
f
T
i
)

S
r eser voi r
=
mC(T
f
T
i
)
water
T
373
=-1126J/K

Total entropy

S
total
= S
r eser voi r
+ S
water

S
total
=
mC(T
f
T
i
)
water
T
373
+ mC ln
373
273

S
total
= 184J/K

ACTIVITY 3: Statistical Thermodynamics
references.
Defne the work done and the internal energy
Describe the absolute and entropy relation
State the heat capacity at constant V,P
In this activity you will investigate the relationship between pressure, temperature,
volume, and the amount of gas occupying an enclosed chamber. This activity consists
of three sections. In section one amount of gas and the importance of Avogadros
number is discussed. In the second section the relationship between pressure and
volume will be covered. In part three the relationship between pressure and volume
as well the amount of gas present in a chamber will be determined. The results learnt
in these tasks will be used to derive the Ideal Gas Law.
Reading #2
Accessed on the 23
rd
September 2007
Abstract : Thermal and Statistical Physics: From Classical Mechanics to Statistical
Mechanics; thermodynamic Concepts and Processes; Concepts of Probability;The
Methodology of Statistical Mechanics; Magnetic Systems; Noninteracting Particle
Systems; Thermodynamic Relations and Processes; Theories of Gases and Liquids;
Critical Phenomena and the Renormalization Group; Introduction to Many-Body
Perturbation Theory...
of the module...
Reading 5
Complete reference: Introduction To Statistical Mechanics | Free eBooks Down-
load!
URL:http:// www.ebookee.com/Introduction-To-Statistical-Mechanics_139834.
html Accessed

Reading 6
Complete reference: Molecular Driving Forces: Statistical Thermodynamics in
Chemistry ...
URL http:// www.ebookee.com/Molecular-Driving-Forces-Statistical-Thermodyna-
mics-in-Chemistry-amp-Biology_145376.html
List of Relevant Readings for all activities
Reference:- Kittel C. and Kroemer H., (1980) Thermal Physics, 2
nd
ed., W. H.
Freeman and Co., San Francisco, CA..
Rationale: This classic reference on thermal physics is recommended for a serious
student of Physics. The contents have been treated in detail with adequate math-
ematical support.
Reference: Fundamentals of statistical and thermal physics: F. Reif (McGraw-Hill,
New York NY,1965).
Rationale: This reading provides easy sources of information. The contents have
been treated in lucid manner with adequate mathematical support.
Reference http://en.wikipedia.org/wiki/Entropy
Description: - This Java applet helps you understand the effect of temperature and
volume on the number of collisions of the gas molecules with the walls. In the ap-
plet, you can change the temperature and volume with the sliders on the left side.
You can also adjust the time for which the simulation runs. The applet counts all
collisions and displays the result after the run. By varying temperature and volume
and keeping track of the number of collisions, you can get a good feeling of what
the main result of kinetic theory will be.
Reference: video.google.com
Complete Reference: - Computer calculation of Phase Diagrams. http://video.
google.com/videoplay?docid=1397988176780135580&q=Thermodynamics&hl=en
Rationale: Thermodynamic models of solutions can be used together with data to
calculate phase diagrams. These diagrams reveal, for a given set of all parameters
(such as temperature, pressure, and magnetic feld), the phases which are thermo-
dynamically stable and in equilibrium, their volume fractions and their chemical
compositions...
Title: The P-V Diagram and Engine Cycles
URL: http://www.antonine-education.co.uk/Physics_A2/options/Module_7/Top-
ic_4/topic_4.htm
Abstract: This site contains a good summary on Representation of processes on p
V diagram, Estimation of work done in terms of area below the graph, Expres-
sions for work done are not required except for the constant pressure case, W = p
V , Extension to cyclic processes: work done per cycle = area of loop
Title: Avogadros Number
URL: http://njsas.org/projects/atoms/avogadro.php
Abstract: A historic as well as scientifc of the origin of Avogadros number is
presented on this page
The Ideal Gas Law describes the relationship between pressure, volume, the number of
atoms or molecules in a gas, and the temperature of a gas. This law is an idealization
because it assumes an ideal gas. An ideal gas consists of atoms or molecules that
do not interact and that occupy zero volume.
A real gas consists of atoms or molecules (or both) that have fnite volume and interact
by forces of attraction or repulsion due to the presence of charges. In many cases the
behaviour of real gases can be approximated quite well with the Ideal Gas Law. and
this activity focuses on the description of an ideal gas.
Introduction
Thermal relay switch and dispersion systems (Boltzmann and Gibbs factors, partition
and connection functions with thermodynamics
Equilibrium conditions and constraints
Consider an isolated system whose energy is specifed to lie in a narrow range. As
usually, we denote by then number of states accessible to this system. From the
fundamental postulate we know that in equilibrium such a system is equally likely
to be found in any one of these states. If a system has a constraint y
1
,y
2
,y
n
then the
accessible state given by = y
1
, y
2
,...y
n
( ) .
If some constraints of an isolated system are removed, the parameters of the system
tend to readjust themselves in such a way that = y
1
, y
2
,...y
n
( ) approaches a
maximum
f

i
Thermal interaction between macroscopic systems
Activity
Consider a purely thermal interaction between two macroscopic systems, A and A,

A A

Energy of the systems E and E, the external parameters are constant, so that A and
A cannot do work on one another and the systems are thermally contact heat will
exchange. Considering the energy width

E
Let us calculate the accessible state
The temperature at equilibrium
The entropy at equilibrium
Result
The number of microstates of A consistent with a macrostate in which the energy lies
in the range E to E + E is denoted (E). Likewise, the number of microstates of
A consistent with a macrostate in which the energy lies between E and E + E is
denoted (E ).
The combined system A
(0)
= A + A is assumed to be isolated (i.e., it neither does work
on nor exchanges heat with its surroundings). The number of accessible to the entire
system A
0
let us denote by
0
(E) when A has energy between E and E+dE.
The probability
P(E)=C
0
(E)
Total accessible state

0
E ( ) = E ( )' E
0
E
( )
Temperature at equilibrium
The probability of system A having the energy an energy near E is given by
P(E)=C E ( )' E
0
E
( )
To locate the maximum position of P(E) at E=E

lnP(E )
E
=
1
P
P
E
=0

lnP(E ) = lnC + ln E ( ) + ln' E ' ( )

lnP(E )
E
=
ln E ( )
E
+
ln' E ' ( )
E
=0

where E
0
=E+E which is dE=-dE then

ln E ( )
E

ln' E ' ( )
E
'
=0
Entropy of the combined system
Activity
where and denote the corresponding energies of A and A at the maximum,
and where we have introduced the defnition
E ( ) =
ln
E
kT
1
where k is some positive constant having the dimension of

energy and whose magnitude in some convenient arbitrary way.
The parameter T is then defned as kT =
S
E
Solution
Where we have introduced the defnition S kln this quantity S is given the name
of entropy
Total accessible state
0
E ( ) = E ( )' E
0
E
( )
and taking the logarithm

ln
0
E
( )
= ln E
( )
+ ln' E
0
E
( )

S
0 ( )
= S + S '
The condition of maximum probability is expressible as the condition that the total
entropy
S + S' = maximumentropy occurs when T=T
The approach to thermal equilibrium
If the two systems are subsequently placed in thermal contact, so that they are free to
exchange heat energy until the two systems attain fnal mean energies E f and E
f
'
which are

f
=
f
'

It follows from energy conservation that

E
f
+ E ' f = E
i
+E
i
'
The mean energy change in each system is simply the net heat absorbed, so that

Q E f E
i
; Q
'
E '
f
E
'
i
The conservation of energy then reduces to
Q+Q=0:
It is clear, that the parameter , defned

=
ln
E
Temperature
1. If two systems separately in equilibrium are characterized by the same value
of the parameter, then the systems will remain in equilibrium when brought
into thermal contact with each other.
2. If the systems are characterized by different values of the parameter, then they
will not remain in equilibrium when brought into thermal contact with each
other.
If two systems are n thermal equilibrium with a third system, then they must
be in thermal equilibrium with each other
Heat reservoir

A
A
If A is suffciently large compared to A so A is a reservoir.
Suppose the macroscopic system A has ' E ' ( ) accessible states and absorbs heat
Q' = E ' using Expanding

ln
'
E
'
,Q
'
( )
at E=Q

ln' E ',Q' ( ) ln' E ' ( ) =
ln'
E '
Q'+
1
2

2
ln'
E '
2
Q'
2
+ ...
using approximation

ln'
E '
Q' =
Q'
kT '
the higher order becomes zero

ln' E ',Q' ( ) ln' E ' ( ) =
Q'
kT '

k(ln' E ',Q'
( )
ln' E '
( )
) =

Q'
T '

S' =

Q'
T '
For a heat reservoir
Dependence of the density of states on the external parameter
Activity
Now that we have examined in detailed the thermal interaction between systems, let
us turn to the general case where mechanical interaction can also take place, i.e. where
the external parameters of the systems are also free to exchange. We begin, therefore,
by investigating how the density of states depends on the external parameters.
Solution

E
E+

Figur e shaded area indicate the energy range
occurred by states with a value of whose energy
changes from E to E+when the external
parameter is changed from x to x+dx
The number of states accessible to the system microstates accessible to the system
when the overall energy lies between E and E + E depends on the particular value
of x, so we can write

E , x ( ) .
The number of states (E, x) whose energy is changed from a value less than E to
a value greater than E when the parameter changes from x to x + dx is given by the
number of microstates per unit energy range multiplied by the average shift in energy
of the microstates, Hence

E , x ( ) =
E , x ( )
E
E
r
x
dx
where the mean value of Er/ x is taken over all accessible microstates (i.e., all
states where the energy lies between E and E + E and the external parameter takes
the value x). The above equation can also be written

E , x ( ) =
E , x ( )
E
Xdx
where
Figure shaded area indicate the energy
range occurred by states with a value
of whose energy changes from E to
E+when the external parameter is chan-
ged from x to x+dx
X E , x ( ) =
E
r
x
is the mean generalized force conjugate to the external parameter x.
Consider the total number of microstates between E and E + E. When the external
parameter changes from x to x + dx, the number of states in this energy range changes
by
dx . In symbols

E , x ( )
x
dx = E ( ) E +E ( )

E
E
which yields

x
=
X
( )
E

x
=
X
( )
E
=

E
X +
X
E
then

ln
x
=
ln
E
X +
X
E

ln
x
=
ln
E
X = X
Thus,

ln
x
= X

where X
is the mean generalized force conjugate to the parameter x
Infinitesimal quasi static process

Activity
Consider a quasi static process in which the system A, by virtue of its interaction with
systems A, is brought from an equilibrium state describe by

E and

x

= 1, 2,...n
( )
to an infnitesimally different, equilibrium state described by

E + dE and

x
+ dx
.
What is the resultant change in the number of states accessible to A?
Solution
The accessible state

= E ; x
1
,..., x
n
( )

dln =
ln
E
dE +
ln
x
=1
n
dx
Substituting the in the above equation =

ln
E
,
ln
x
= X

dln = dE + X
dx

dW = X
dx
Then

dln = dE + dW
( )
= dQ
The fundamental relation valid for any quasi-static infnitesimal process

dQ = TdS = dE + dW
( )
or equivalently

dS =
dQ
T
Adiabatic process

dQ = 0which asserts

dS = 0
Equilibrium
Consider the equilibrium between the systems A and A in the simple case the exter-
nal parameters are the volumes V and V of the two systems. The number of state
available to the combined system

A
0
is given by the simple product.

0
E ,V
( )
= E ,V
( )
' E ',V '
( )
Activity
Using the accessible state given for the combined system derive the equation that
guarantee for thermal and mechanical equilibrium.
Solution
For the combined system the accessible state given as

0
E ,V
( )
= E ,V
( )
' E ',V '
( )
Taking the logarithm

ln
0
E ,V
( )
= ln E ,V
( )
+ ln' E ',V '
( )
The total entropy of the system given by

S
0
= S + S '
At the maximum value the total accessible state

dln
0
= 0

dln
0
E ,V
( )
= dln E ,V
( )
+ dln' E ',V '
( )
= 0

dln =
ln E ,V
( )
V
dV +
ln E ,V
( )
E
dE +

ln' E ',V '
( )
V '
dV '+
ln' E ',V '
( )
E '
dE ' =0

where

p =
ln E ,V
( )
V
similarly

' p' =
ln' E ',V '
( )
V '

=
ln E ,V
( )
E
similarly

' =
ln' E ',V '
( )
E '
Substituting in the above equation

dln = pdV + dE +

' p' dV '+ ' dE ' =0
from the combined system

E + E ' = E
0

V +V ' = V
0
Then

dE = dE ',

dV = dV '
Substituting in the above equation

pdV + dE

' p' dV ' dE =0
Collecting terms

pdV

' p' dV =0

dE

' dE =0

dE

= ' dE
Then at thermal equilibrium

= '

pdV =

' p' dV
Then mechanical equilibrium

p=

p'
Thermodynamics laws and basic statistics relation
Summery of thermodynamic laws
Zero law: If two systems are in thermal in equilibrium with a third system,
they must be in thermal equilibrium with each other.
First law: an equilibrium macrostate of a system can be characterized by a
quantity

E (called internal energy) which has the property that for an isola-
ted

E =constant. If the system is allowed to interact and thus goes from one
macrostate to another, the resulting change in

E can be written in the form

E = W + Q
Second law: an equilibrium macrostate of a system can be characterized by
a quantity S (called entropy ) which has the property that
-In any process in which a thermally isolated system goes from
one macrostate to another, the entropy tends to increase

S 0
-If the system is not isolated and under goes a quasi-static infnitesi
mal process in which it absorbs heat

dQ,

then

dS =
dQ
T
Third law: The entropy S of a system has the limiting property that

T 0
+
,

S S
0
where

S
0
is a constant independent of all parameters of the particular
system
ACTIVITY 4: Some Application of Statistical and Macroscopic
Thermodynamics
references.
Calculate the thermodynamics relations
Derive the equation for the canonical distribution and kinetic theory of dilute
gasses in equilibrium
List of Required Readings (for the Learning Activity)
Useful Link # 1
Title : MACROSCOPIC AND STATISTICAL THERMODYNAMICS
URL: http://www.worldscibooks.com/physics/6031.html
Screen Capture

By Yi-Chen Cheng (National Taiwan University, Taiwan)

Description : This textbook addresses the key questions in both classical thermo-
dynamics and statistical thermodynamics: Why are the thermodynamic properties
of a nano-sized system different from those of a macroscopic system of the same
substance? Why and how is entropy defned in thermodynamics, and how is the
entropy change calculated when dissipative heat is involved? What is an ensemble
and why is its theory so successful?
They include the introduction of the grand canonical ensemble, the grand partition
function and its application to ideal quantum gases, a discussion of the mean feld
theory of the Ising model and the phenomenon of ferromagnetism, as well as a more
detailed discussion of ideal quantum gases near T = 0, for both Fermi and Bose
gases.
Reading 2
Complete reference: Fundamentals Of Statistical And Thermal physics
URL: http://www.ebookee.com/Reif-Fundamentals-Of-Statistical-And-Thermal-
Physics_
Reading 3
Complete reference: Maxwell Velocity Distribution simulation
URL: http://www.kfki.hu/physics/physedu/kinetic_gas_model/exp/veldistr.html
Abstract: A graph which show the Maxwell velocity distribution
Reading 4
http://colos1.fri.uni-lj.si/~colos/COLOS/TUTORIALS/JAVA/THERMODYNA-
MICS/THERMO_UK/HTML/Vel_Distri.html
Abstract: Distribution of particles in their energy leel
Partition function and their properties Ideal gas, validity of classical approxima-
tion, equipartition theory, harmonic oscillator at high temperature Distribution of
particles Maxwell Boltzmann, Bose Einstein and Fermi-Dirac statistics
The gas laws described in activity 3 were found by experimental observation, but
Boyles law and Charles law are not obeyed precisely at all pressures. A gas which
obeys the above laws perfectly at all pressures would be a perfect or ideal gas,
and the kinetic theory resulted from an attempt to devise a mechanical model of such
a gas based on Newtons laws of motion.
First Law of thermodynamics

dQ = dE + dW
If the process is quasi-static, the second law gives

dQ = TdS
The work done by the system when the volume is changed by an amount dV in the
process is given by

dW = pdV
Then the fundamental thermodynamics

TdS = dE + pdV
The equation of state of an ideal gas
Macroscopically, an ideal gas is described by the equation of state relating its pressure
p, volume V, and the absolute temperature T. For v moles of gas, this equation of state
is given by

pV = vRT
The internal energy of an ideal gas depends only on the temperature of the gas, and is
independent of the volume
E = E (T) independent of V.
Entropy
The entropy of an ideal gas can readily be computed from the fundamental thermo-
dynamic relation
TdS = dE + pdV

ds = vC
V
dT
T
+
vR
V
dV
Adiabatic expression or compression

pV
= cons tant

V
1
T = cons
Thermodynamic potentials and their relation with thermodynamic
variables
The thermodynamic state of a homogeneous system may be represented by means of
certain selected variables, such as pressure p, volume v, temperature T, and entropy
S. Out of these four variables , any two may vary independently and when known
enable the others to be determined. Thus there are only two independent variables
and the others may be considered as their function.
The frst and the second law of thermodynamics give the four thermodynamic va-
riables

dQ = dE + pdV the frst law of thermodynamics

dQ = TdS the second law of thermodynamics

dE = TdS pdV combined the two laws
Activity
For two independent variables S and V using the fundamental thermodynamics derive
the thermodynamics state of a homogeneous system.
Answer
The independent thermodynamic function

E = E S,V
( )
the internal energy
Differentiating the function

dE =
E
S
V
dS +
E
V
S
dV
From the fundamental thermodynamic equation

dE = TdS pdV
Comparing the two equations we can get

T =
E
S
V
p =
E
V
S
Using the second order differential and dE is a perfect differential. E must be inde-
pendent of the order of differentiation.

S
E
S
V
=
T
V
V
E
V
S
=
p
S
V

Then

T
V
S
=
p
S
V
Activity
For two independent variables S and p using the fundamental thermodynamics derive
Answer

dE = TdS pdV

dE = TdS d pV
( )
+Vdp

d E + pV
( )
= TdS +Vdp
let

H = E + pV which we call it enthalpy

H = H S, p
( )

dH = TdS +Vdp


dH =
H
S
p
dS +
H
p
S
dp
From the thermodynamic equation

dH = TdS +Vdp


T =
H
S
p

V =
H
p
S
Using the second order differential and

dH is a perfect differential.

H must be in-
dependent of the order of differentiation.

S
H
S
p
=
T
p
p
H
p
s
=
V
S
p

Then

T
p
S
=
V
S
p
Activity
For two independent variables T and V using the fundamental thermodynamics derive
Answer

dE = TdS pdV

dE = d TS
( )
SdT pdV

d E TS
( )
= SdT pdV
let

F = E TS which we call it Helmholtz free energy

F = F T ,V
( )

dF = SdT pdV

F = F T ,V
( )

dF =
F
T
V
dT +
F
V
T
dV


dF = SdT pdV
Alr|car v|rlua| ur|vers|ly

S =
F
T
V

p =
F
V
T


H must be in-

V
F
V
T
=
p
T
T
F
T
V
=
S
V
T

Then

p
T
V
=
S
V
T

Activity
For two independent variables

T and

pusing the fundamental thermodynamics derive
Answer

dE = TdS pdV

dE = d TS
( )
SdT

d pV
( )
+Vdp

d E TS + pV
( )
= SdT +Vdp
let

G = E TS + pV which we call it Gibbs free energy

G = G T , P
( )

dG = SdT +Vdp

G = G T , p
( )

dG =
G
T
p
dT +
G
p
T
dp

dG = SdT +Vdp

S =
G
T
p

V =
F
p
T



H must be in-

p
G
p
T
=
V
T
T
G
T
p
=
S
p
T

Then

V
T
p
=
S
p
T

Summary for the thermodynamics function
Maxwell relations
The entire discussion of the preceding section was based upon the fundamental
thermodynamics relation

dE = TdS pdV

T
V
s
=
P
S
v

T
p
s
=
V
S
p

S
V
T
=
p
T
v

S
p
T
=
V
T
p
Thermodynamics functions

E .............................E = E (S,V )
H E + pV............H = H (S, p)
F E TS..............F = F (T ,V )
G E TS + pV......G = G(T , p)
Next we summarize the thermodynamic relations satisfed by each of these func-
tion

dE = TdS pdV
dH = Tds +Vdp
dF = SdT pdV
dG = SdT +Vdp
Specifc heats
Consider any homogeneous substance whose volume V is the only relevant external
parameter.
The heat capacity at constant volume is given by
Solution for b
Considering the independent variable

S = S T , p
( )
and second law of thermo
dynamics

dQ = TdS = T
S
T
p
dT +
S
p
T
dp
it is possible to express dp in terms

of dT and dV

dQ = T
S
T
p
dT +
S
p
T
p
T
V
dT +
p
V
T
dV
where at
V=constant
dV=0

dQ = T
S
T
p
dT +
S
p
T
p
T
V
dT then

Q
T
p
= T
S
T
p
+
S
p
T
p
T
V

C
p
= C
V
+
S
p
T
p
T
V
from the Maxwell relation
S
p
T
=
V
T
p
The volume coeffcient of expansion of the substance

=
1
V
V
T
p
=-
1
V
S
p
T

S
p
T
=-V
we can express V in terms of T and P

dV =
V
T
p
dT +
V
p
T
dp=0 since V= constant
Alr|car v|rlua| ur|vers|ly Z0

p
T
V
=
V
T
p
V
p
T
from the isothermal compressibility of the substance

k =
1
V
V
p
T
, kV =
V
p
T

S
p
T
=-V

p
T
V
=

k
Substituting in the above equation which yields

C
p
= C
V
+
S
p
T
p
T
V
=C
V
+ -V

k
=C
V

2
V
k
Ensembles system -Canonical distribution
Isolated system
An isolated system consists of N number of particles in a specifed volume v, the
energy of the system being known to lie in some range between E and E + dE. The
fundamental statistical postulate asserts that in an equilibrium situation the system
is equally likely to be found in any of its accessible states. Thus, if the energy of the
system in state r is denoted by E
r
, the probability P
r
of fnding the system in state r
is given by

P
r
= C If E<E
r
<E+E

P
r
= 0 Other wise
P
r
= 1Normalized
An ensemble representing an isolated system in equilibrium consists then of sys-
tem distributed in the above expression. It is some times called a microcanonical
ensemble.
In contact with reservoir

A A T
We consider the case of a small system A in thermal interaction with a heat reservoir
A. What is the probability P
r
of fnding the system A in any one particular microstate
r of energy E
r
?
The combined system A
0
=A+A and from the conservation of energy E
0
=E
r
+E
When A has an energy E
r
, the reservoir A
must then have an energy near E=E

0
-E
r.

The number of state
'
(E
0
E
r
) accessible to A
The probability of occurrence in the ensemble of a situation where A in state r is simply
proportional the number of state accessible to A
0

P
r
= C
'
'
(E
'
)

P
r
r
= 1
Using

ln
'
(E
0
E
r
) ln
'
E
0
( )
ln
'
E
'
E
'
= E
0
E
r
+ ....

ln
'
(E
0
E
r
) ln
'
E
0
( )
E
r

' E ' ( ) ' E
0
( )
e
E
r
then

P
r
= C ' ' E
0
( )
e
E
r

P
r
= C ' '(E
0
)e
E
r
= 1

C ' =
1
' E
0
( )
e
E
r
r

P
r
=
e
E
r
e
E
r
r
The probability of the canonical distribution

Application of canonical ensemble
Activity
Spin system: paramagnetic particles which has N atoms in a system with spin
Answer
Considering a system which contains N atoms, spin particles interact with external
magnetic feld H with the magnetic moment
State Magnetic moment Energy
+

E
+
= H
_
-

E
= +H
The particles has two states + or the probability
P
+
= Ce
E
+
= Ce
H

P
= Ce
E
= Ce
H
from the normalization condition
P
+
+P
-
=1 then we get

C =
1
e
H
+ e
H

P
+
=
e
H
e
H
+ e
H

P
=
e
H
e
H
+ e
H
Molecule in ideal gas
Activity
Consider a monatomic gas at absolute temperature T confned in a container of vo-
lume V. The molecule can only be located somewhere inside the container. Derive
the canonical distribution for a monatomic non interacting gas
Solution
The energy of the monatomic gas in a system is given by purely kinetic
E=

1
2
mV
2
=
P
2
2m
If the molecules position lies in the range between r and r+dr and momen-
tum lies between P and P+dP then the volume in phase space is given by
d
3
rd
3
P=(dxdydz)dp
x
dp
y
dp
z
)
The probability that the molecule has position lying in the range between r
and r+dr and momentum in the range between p and p+dp
P(r,p)d
3
rd
3
p

d
3
rd
3
p
h
0
3
p
2
2m

The probability that P(p)d
3
p that a molecule has momentum lying in the range
between p and p+dp
P p ( )d
3
p = P r, p ( )d
3
rd
3
p = Ce

p
2
2 m
d
3
p
r ( )

where we have p=mv d
3
p=md
3
v
Then

P ' V
( )
= P p
( )
d
3
p = Ce
mV
2
/ 2
Generalized force
Activity
Using the canonical distribution write the generalized force
Solution
If the a system depends on the external parameter x, then E
r
=E
r
(x) and from the def-
nition of the generalized force we have that

X
r
=
E
r
x
the mean value of the generalized force we can write as

X =
e
E
r
E
r
x
e
E
r
r
then

X =
1
lnZ
x

the average work done

dW = Xdx
where the external parameter is V

dW =
1
lnZ
V
dV

p =
1
lnZ
V
Connection of canonical distribution with thermodynamics
Activity
One can write the thermodynamics function in terms of the partition function derive
the equation
Solution
The partition function given by

Z = e
E
r
x ( )
so it can be represented in terms of ,
x since E
r
=E
r
(x)
Z=Z ( , x) considering a small change

dlnz =
lnz
dx
dx +
lnZ
d

dlnZ = dW Ed
The last term can be written inn terms of the change in E rather than the change in
. Thus
dlnZ = dW d E
( )
+ dE
d lnZ + E
( )
= dW + dE
( )
dQ
using the second law of thermodynamics
dS =
dQ
T
therefore
( ) E Z k S + ln
TS kT lnZ + E
From Helmholtz free energy F= E TS
Thus lnZ is very simply related to Helmholtz free energy F
F= E TS =-kT ln Z
Partition function and their properties

Z = e
E
r
r
partition function
If a system can be treated in the classical approximation then its energy

E = E q
1
,...q
n
, p
1
,.. p
n
( )
depends on some

f generalized coordinates and

f
momenta.
The partition function in the phase space given by

Z = ... e
E (q
1
,...q
n
, p
1
,... p
n
)

dq
1
,...dq
n
, dp
1
,...dp
n
h
f
Activity
Consider the energy of the system is only defned by a function to which is an arbi-
trary additive constant. If one changes by a constant amount

0
the standard state r
the energy state becomes

E
r
= E
r
+
0
using the partition function
a. Show the corresponding mean energy shifting by the amount of

0
b. Show the entropy of the combined system will not change

S
= S
Solution
a. The mean value of the energy when shifting the system energy by

0
Partition function

Z
= e
( E
r
+
0
)
r
=

e
0
e
E
r
r
=

e
0
Z

lnZ
= lnZ
0
Alr|car v|rlua| ur|vers|ly ZZ
from the defnition

E =
lnZ
and

E
=
lnZ
lnZ
=
lnZ
+
0

E
= E +
0
The mean energy also shifted
b. The entropy
let the partition function in terms of the variables

Z
= Z
(, x)

dlnZ
=
lnZ
d +
lnZ
x
dx where

E
=
lnZ
and

dW =
lnZ
x
dx
Then we can fnd

dlnZ
= Ed + dW
using the relation

Ed = d E
( )
dE

dlnZ
=

d E
( )
+ dE +

dW

dlnZ
+

d E
( )
=

dE +

dW =

dQ

d(lnZ
+

E ) =

dQ =

dQ
kT

S
= k lnZ
*
+ E
( )
Since we can write

E
= E +
0
and

lnZ
= lnZ
0
substituting in the above equation

S
= k lnZ
*
+ E
( )
=

k (

lnZ
0
+

E +
0
) =k (

lnZ +

E )=S

S
= S the entropy keeping constant

Activity
The second remark concerns the decomposition of partition function for a system A
which consists of two parts A and A which interact weakly with each other, if the
states of A and A are labelled respectively by r and s fnd the partition function for
the total system
Solution
Part A state r corresponding energy

E
r
Part A state s corresponding energy

E
s
System A state r,s corresponding energy

E
rs
The partition function for the system A is given by Z

Z = e
( E
r
+ E
s
)
r ,s
where

E
r ,s
= E
r
+ E
s
then

Z = e
( E
r
+ E
s
)
r ,s
=

e
( E
r
)
r

e
( E
s
)
s

Z = Z ' Z ''

lnZ = lnZ '+ lnZ ''
Calculation of Thermodynamics quantities with partition function
Activity
Consider a gas consisting of N identical monatomic molecules of mass m enclosed
in a container of volume V. The position vector of the i
th
molecule denoted by r
i
, its momentum by p
i
the total energy given by

E =
P
i
2
2m
i =1
N
+U r
1
, r
2
,...r
N
( )
where
for
non-interacting monatomic ideal gas U=0 and write the partition function in phase
space
Solution
Taking a gas consisting of N identical monatomic molecules of mass m enclosed in
a container of volume V. The position vector of the i
th
molecule denoted by r
i
, its momentum by p
i
the total energy given by

E =
P
i
2
2m
i =1
N
+U r
1
, r
2
,...r
N
( )
where
for
non-interacting monatomic ideal gas U=0 therefore the partition function in phase
space can be given as follows

Z = exp
1
2m
p
1
2
+ ... + p
N
2
( )
+U r
1
,...r
N
( )
d
3
r
1
...d
3
r
N
dp
1
3
...dp
3
N
h
0
3N

Z =
1
h
0
3N
exp
1
2m
p
1
2
+ ... + p
N
2
( )
dp
1
3
...dp
N
3

exp U r
1
,...r
N
( )
{ }
d
3
1
...d
3
N

exp U r
1
,...r
N
( )
{ }
d
3
1
...d
3
N
=

V
N

Z =
V
N
h
0
3N
exp
1
2m
p
1
2
+ ... + p
N
2
( )
dp
1
3
...dp
N
3

where

p
2
1
= p
1x
2
+ p
1y
2
+ p
1z
2
,

dp
1
3
= dp
1x
dp
1y
dp
1z
so for the i
th
particle

=
V
h
0
3
exp
1
2m
p
2
( )
dp

Z =
N

e
p
1x
2
2m
dp
1x
=
2m
,

e
p
2
2m
dp
=
2m
3
2

=
V
h
0
3

2m
3
2
=

V

2m
h
2
0
3
2

Z =
N
=

V
2m
h
2
0
3
2
N

the thermodynamics quantities with the partition function
Taking the logarithm

2
0
3 2 3
ln ln ln ln
2 2
m
Z N V
h

= +

Activity
With the given partition function, fnd
i) The value for the mean pressure,
ii) The mean energy,
iii) The heat capacity,
iv) The entropy
Solution
i) The mean pressure

p =
1
lnZ
V
=
NkT
V

pV = NkT
ii) The total mean energy

E =
lnZ

E =
3
2
N
=
3
2
NkT

=
3
2
kT

E = N
iii) The heat capacity at constant volume

C
V
=
E
T
V
=
3
2
R
iv)The entropy

( ) E Z k S + ln , where

E =
3
2
N

2
0
3 2 3
ln ln ln ln
2 2
m
Z N V
h

= +

S = Nk lnV +
3
2
ln
2m
h
2
0

3
2
ln +
3
2

2
0
3 3 2
ln ln (ln 1)
2 2
m k
S Nk V T
h

= + + +

where

=
3
2
ln
2mk
h
2
0
+1

S = Nk lnV +
3
2
lnT +
Then the Mean Energy

i
=
e

i
+ E ' ( )
i
dp
1
,...dp
f
e

i
+ E ' ( )
dp
1
,...dp
f

i
=
e

i
dp
i
e
E '
dp
1
,...dp
f
e
i
dp
i
e
E '
dp
1
,...dp
f

i
=
e

i
dp
i
e
i
dp
i
considering that

i
=
p
2
2m
= bp
2
then

i
=

ln e
p
i
2
2mi
dp
i
let

i
=

ln
4m
i

,
2
i
K T
=

for one degree of freedom
For three degree of freedom
3
,
2
i
KT =
The Harmonic Oscillator at high thermal energy
Summery of harmonic oscillator
For a1D-harmonic oscillator which is in equilibrium with a heat reservoir at absolute
temperature T.

E =
P
2
2m
+
1
2
kx
2
the energy of the oscillator

E = n+
1
2
h
Is the energy of the oscillator in quantum mechanics the angular frequency

=
k
m
Activity
Using the partition function of the harmonic oscillator derive the mean energy of the
oscillator for

h <<1 and

h >>1
Solution
The mean energy for the harmonic oscillator given by

E =
e
E
n
E
n
n=0
e
E
n
n=0

E =
lnZ
where

Z = e
E
n
n=0
= e
n+
1
2
h
n=0

Z = e
h
2
e
nh
n=0

Z = e
h
2
1+ e
h
+ e
2h
.....
( )

Z = e
h
2
1 e
h
( )
1

E =

ln e
h
2
1 e
h
( )
1

E =

ln(e
h
2
) ln 1 e
h
( )

E =
h
2
+
e
h
h
1 e
h
i) Considering the case

h <<1
From the Taylor expansion

e
h
= 1+ h +
1
2
h
( )
2
+ ... neglecting the higher order since

h <<1
substituting in the equation

E = h
1
2
+
1
e
h
1

E h
1
2
+
1
h

h <<1,

1
2
+
1
h

1
h

E
1
=

kT
ii) Considering

h >>1
then

E = h
1
2
+
1
e
h
1

E h
1
2
+ e
h
which shows

T 0the ground state energy given by

E =
1
2
h
Kinetic theory of dilute gasses in equilibrium
Maxwell velocity distribution
Summery for Maxwell velocity distribution
Consider a molecule of mass m in a dilute gas the energy of the molecule is equal
to

=
P
2
2m
+
int

P
2
2m
due to the kinetic energy of the centre of mass motion

int
the molecule is not monatomic the internal energy due to rotation and vibration
of the atom with respect to the molecular centre of mass
The probability

P
s
r , p
( )
d
3
rd
3
pof fnding the molecule with centre-of mass varia-
bles in the ranges (r,dr) and (p,dp) and with internal state specifed by s the result

P
s
r , p
( )
d
3
rd
3
p e
p
2
2m
+
int
d
3
rd
3
p
where

e
int
contributes for the constant proportionality

P
s
r , p
( )
d
3
rd
3
p e
p
2
2m
d
3
rd
3
p

f r ,V
( )
d
3
rd
3
V = Ce
V
2
2m
d
3
rd
3
V
Activity
Using the normalization condition for N number of molecules in a system derive the
value of C and write the Maxwell velocity distribution
Solution

V

f r ,V
( )
d
3
rd
3
V = N

V

Ce
V
2
2m
d
3
rd
3
V = N

C d
3
r e
mV
2
x
2m
dV
x
3
= N
r

CV
2
m
3
= N

C =
N
V
m
2
3
2
, n =
N
V
total number of molecule per unit volume

f r ,V
( )
d
3
rd
3
V = n
m
2
3
2
e
V
2
2m
d
3
rd
3
V Maxwell velocity distribution
Activity
Derive the velocity distribution component
Solution
Let the number of molecule per unit volume with x-component of velocity in the
range between V
x
and V
x
+dV
x
, irrespective of the values of their other velocity is
given by

g(V
x
)dV
x
=
V
x
f V
( )
V
y
d
3
V

g(V
x
)dV
x
= n
m
2kT
3
2
e
m
2kT
( )
V
2
y
V
y
dV
y
e
m
2kT
( )
V
z
2
V
z
d
3
V
z

g(V
x
)dV
x
= n
m
2kT
3
2
e
m
2kT
( )
V
x
2
e
m
2kT
( )
V
y
2
dV
y
e
m
2kT
( )
V
z
2
dV
z

g(V
x
)dV
x
= n
m
2kT
3
2
m
2kT
1
e
m
2kT
( )
V
x
2
dV
x
The graph

g(V
x
) versus

V
x
Problem
Solve the value for

V
x
and

V
x
2
Formulation of the statistical Problems
Consider a gas of identical particles in a volume V in equilibrium at the temperature
T. We shall use the following notation
Label the possible quantum states of a single particle by r or s
Denote the energy of particles in state r by

r
Denote the number of particles in state r by

n
r
Label the possible quantum states of the whole gas by R
The total energy of the gas when it is in some state R where there are

n
1
particle r=1,

n
2
particles in state r=2 etc.,

E
R
= n
1
1
+ n
2
2
+ ... = n
r
r
r
The total number of the gas N is given by

n
r
r
= N
In order to calculate the thermodynamic function of the gas it is necessary to calculate
its partition function

Z = e
E
R
R

Z = e
n
1
1
+n
2
2
+... ( )
R
Activity
Derive the mean number of the particles in state s
Solution

n
s
=
n
s
e
n
1
1
+n
2
2
+... ( )
R
e
n
1
1
+n
2
2
+... ( )
R

n
s
=
1
lnZ
s
Problem
Calculate the dispersion
Solution
One can similarly write down an expression for the dispersion of the number of
particles in state s. One can use the general relation.

(n
s
)
2
= (n
s
n
s
)
2
= n
s
2
n
s
2
For the case

n
s
2

n
s
2
=
n
2
s
e
n
1
1
+n
2
2
+... ( )
R
e
n
1
1
+n
2
2
+... ( )
R

n
2
s
=
1
2
Z
2
lnZ
2
s

n
2
s
=
1
s
1
Z
Z
+
1
Z
2
Z

n
2
s
=
1
s
1
Z
Z
+
2
n
s
2

n
s
( )
2
=
1
s
1
Z
Z
=

1
2
lnZ
s
2

n
s
( )
2
=

n
s
s
the dispersion of the distribution of particles
Photon Statistics
The average numbers of particles in state s in case of photon statistics

n
s
=
n
s
e
n
s
e
n
s

n
s
=
s
e
n
s
e
n
s

n
s
=
1
s
ln e
n
s
Using the geometric series

e
n
s
s
n
s
=0
= 1+ e
s
+ e
2
s
+ ... =
1
1 e

n
s
=
1
s
ln

1
1 e
s

n
s
=
1
s
ln 1 e
s
( )

n
s
=
1
e
s
1

The average number of particles in Planks distribution
Fermi-Dirac Statistics
Activities
Consider particles in a system where the total number N of particles is fxed
1 2,....
, n n
such that 0
r
n = and 1
r
n = for each r, but these numbers must always satisfy,

n
r
r
= N

let us derive the average number of particles in a given system
Solution
Considering the above mentioned condition where the total number N of particles is
fxed
1 2,....
, n n such that 0
r
n = and 1
r
n = for each r, but these numbers must always
satisfy

n
r
r
= N

, to derive the average number of particles in a given system for
Fermi-Dirac Statistics we consider the partition function

z
s
N
( )
= e
n
1
1
+n
2
2
+... ( )
n
1
, n
2,...
s ( )

then

s ( )
n
r
r
= N

s state omitted

n
s
=
n
s
e
n
s
s
n
s
s ( )
e
n
1
1
+n
2
2
+... ( )
n
1
, n
2
,..
e
n
s
s
n
s
s ( )
e
n
1
1
+n
2
2
+... ( )
n
1
, n
2
,..
since n
s
=0 and 1

n
s
=
0 + e
s
s ( )
e
n
1
1
+n
2
2
+... ( )
n
1
, n
2
,..
s ( )
e
n
1
1
+n
2
2
+... ( )
+ e
s
e
n
1
1
+n
2
2
+... ( )
n
1
, n
2
s ( )
n
1
, n
2
,..

n
s
=
0 + e
s
Z
s
N 1
( )
Z
s
N
( )
+ e
s
Z
s
N 1
( )

taking the ratio of the equation

n
s
=
1
Z
s
N
( )
Z
s
N 1
( )
s
+1

taking the Taylor expansion of

lnZ
s
N N
( )
for

N << N

lnZ
s
N N
( )
= lnZ
s
N
( )
lnZ
s
Z
( )
N
N

ln
Z
s
N 1
( )
Z
s
N
( )

=-

N

where

=
lnZ
s
N
( )
N

Z
s
N N
( )
= Z
s
N
( )
e
N
if we approximate

N 1

Z
s
N 1
( )
= Z
s
N
( )
e
since we have

n
s
=
1
Z
s
N
( )
Z
s
N 1
( )
s
+1
and substituting

n
s
=
1
e
+
s
+1

which is Fermi-Dirac Distribution
Bose-Einstein Statistics
Activity
Derive the distribution of the particles in a system considering the case where the
total number N of particles is fxed
1 2,....
, n n such that 0
r
n = ,1,2,.but these numbers
must always satisfy

n
r
r
= N
Solution

z
s
N
( )
= e
n
1
1
+n
2
2
+... ( )
n
1
, n
2,...
s ( )

n
s
=
n
s
e
n
s
s
n
s
s ( )
e
n
1
1
+n
2
2
+... ( )
n
1
, n
2
,..
e
n
s
s
n
s
s ( )
e
n
1
1
+n
2
2
+... ( )
n
1
, n
2
,..


n
s
=
0 + e
s
Z
s
N 1
( )
+ 2e
2
s
Z
s
N 2
( )
+ ...
Z
s
N
( )
+ e
s
Z
s
N 1
( )
+ e
2
s
Z
s
N 2
( )
+ ...
where

Z
s
N 1
( )
= Z
s
N
( )
e
and

Z
s
N 2
( )
= Z
s
N
( )
e
2

n
s
=
Z
s
N
( )
0
(
+ e
s
e
+ 2e
2
s
e
2
+ ....
)
Z
s
N
( )
1
(
+ e
s
e
+ e
2
s
e
2
+ ....
)

n
s
=
0
(
+ e
s
e
+ 2e
2
s
e
2
+ ....
)
1
(
+ e
s
e
+ e
2
s
e
2
+ ....
)

n
s
=
n
s
e
+ (
s
)n
s
e

s
+ ( )n
s
considering

n
s
e

s
+ ( )n
s
=

e

s
+ ( )n
s

n
s
=
n
s
e
+ (
s
)n
s
e

s
+ ( )n
s
ln e

s
+ ( )n
s
n
s
=0
=
taking the expansion

e

s
+ ( )n
s
n
s
=0
= 1+ e

s
+ ( )
+ e
2
s
+ ( )
+ ... = 1 e

s
+ ( )
( )
1

e

s
+ ( )n
s
n
s
=0
= 1 e

s
+ ( )
( )
1

n
s
=

ln

1 e

s
+ ( )
( )
1

=
e

s
+ ( )
1 e

s
+ ( )

=
1
e
s
+ ( )
1

Bose-Einstein Distribution
Maxwell-Boltzmann statistics
Activity
With the help of the partition function is

z = e
n
1
1
+n
2
2
+... ( )
R
compute the Maxwell-

Boltzmann distribution distribution
Solution
Hence, the partition function is

z = e
n
1
1
+n
2
2
+... ( )
R
For N number of molecules there are, for given values of (n

1
,n
2
,)
1 2
!
! !..
N
n n
possible ways in which the particle can be put into the given single- particle

states, so that there are n
1
particles in state 1, n
2
particles in state 2, etc. By virtue of the
distinguishability of particles, each of these possible arrangements corresponds then
to a distinct state for the whole gas. Hence the partition function can be written

z =
N!
n
1
!n
2
!...
e
n
1
1
+n
2
2
+... ( )
n
1
, n
2
,..

where the sum overall values 0
r
n = ,1,2,.for each r, subject to the restriction

n
r
r
= N

z =
N!
n
1
!n
2
!...
e
(
1
)n
1
e

2
( )n
2
...
n
1
, n
2
,..
expanding the polynomial

z =
N!
n
1
!n
2
!...
e
(
1
)n
1
e

2
( )n
2
...
n
1
, n
2
,..

=

e
1
+ e
2
+ ...
( )
N

lnZ = N ln e
r
r
from the mean values of the distribution of the particle we have defned as

n
s
=
1
lnZ
s

=
1
N
e
s
e
r
r
where

e
r
r
= e
s
e
r
r =1
s

n
s
= N
e
s
e
r
r

this is called the Maxwell-Boltzmann distribution
Reference http://jersey.uoregon.edu/vlab/Balloon/
Description: This experiment is designed to further demonstrate the properties of
the ideal gas law. In addition, our balloon will also serve as a planetary atmosphere
for the second part of the experiment
Date Consulted: - August 2006
Description: - This Java applet helps you understand the effect of temperature and
volume on the number of collisions of the gas molecules with the walls. In the ap-
plet, you can change the temperature and volume with the sliders on the left side.
You can also adjust the time for which the simulation runs. The applet counts all
collisions and displays the result after the run. By varying temperature and volume
and keeping track of the number of collisions, you can get a good feeling of what
the main result of kinetic theory will be.
Reference: video.google.com
Complete Reference: - Computer calculation of Phase Diagrams. http://video.
google.com/videoplay?docid=1397988176780135580&q=Thermodynamics&hl=en
Rationale: Thermodynamic models of solutions can be used together with data to
calculate phase diagrams. These diagrams reveal, for a given set of all parameters
(such as temperature, pressure, and magnetic feld), the phases which are thermo-
dynamically stable and in equilibrium, their volume fractions and their chemical
compositions...
Title: Heat Engines
U R L : h t t p : / / e n . w i k i p e d i a . o r g / w i k i / H e a t _ e n g i n e s
Abstract: - The article in wikipedia presents an overview of heat engines, everyday
examples, examples of heat engines, effciency of heat engines etc. A good number
of external links are also provided
Title: Heat Engines and Refrigerators
URL: ht t p: / / t heory. phy. umi st . ac. uk/ ~j udi t h/ st at _t herm/ node15. ht ml
Abstract: In any heat engine, heat is extracted from a hot source (e.g. hot combustion
products in a car engine). The engine does work on its surroundings and waste heat is
rejected to a cool reservoir (such as the outside air). It is an experimental fact that the
waste heat cannot be eliminated, however desirable that might be. Indeed in practical
engines, more of the energy extracted from the hot source is wasted than is converted
into work. This web page presents a good comparison of different web pages.
Title: Second law of thermodynamics
URL: ht t p: / / en. wi ki pedi a. org/ wi ki / Second_l aw_of_t hermodynami cs

Title: Second law of thermodynamics
URL: http://hyperphysics. phy-astr. gsu. edu/hbase/thermo/seclaw. html
Abstract: The second law of thermodynamics is a general principle which places
constraints upon the direction of heat transfer and the attainable effciencies of heat
engines. In so doing, it goes beyond the limitations imposed by the frst law of thermo-
dynamics. This webpage presents a visualization in terms of the waterfall analogy.
Formative Evaluation 5
Optional Formative Evaluation 3
1. What is the probability of throwing three dice to obtain a total of score of 6 or
less?
Solution
Each dice have the numbers 1, 2, 3,4,5,6
When we throwing the dice the accessible state of the total sum 6 or less will be
1+1+1, 1+1+2, 1+1+3, 1+1+4, 1+2+1, 1+2+2, 1+2+3, 1+3+1,1+3+2 , 1+4+1, 2+1+1,
2+1+2, 2+1+3, 2+2+1, 2+2+2, 2+3+1, 3+1+1, 3+2+1, 3+1+2, 4+1+1
then state of the sum 6 or less is 20
the total number of accessible states is 6
3
=216
Then the probability of throwing three dice to obtain 6 points or less is
P x ( ) =
x ( )
total

=
20
216

=0.093
2. A penny is tossed 400 times. Find the probability of getting 215 heads. (Sugges-
tion: use the Gaussian approximation)
Solution
A penny is tossed 400 times. Find the probability of getting 215 heads is given by the
Gaussian approximation
( )
( )
2
1
2
1
1
* 2
exp
* 2
1
) (
n
n n
n
n P
where
N=400, n
1
=251, p=1/2, q=1/2
n1 = Np *n
1
= Npq = 400x1/ 2x1/ 2 = 100 = 10

*n
1
( )
2
= 100 , 200
1
= n
Substituting in the Gaussian equation


P(251, 400) =
1
10 2
e
251 200 ( )
2
200

P(251, 400) 1.3x10
2
3. A battery of total emf V is connected to a resistance R; as a result an amount
of power P=V
2
/R is dissipated in this resistor. The battery itself consists of N
individual cells connected in series so that V is just equal to the sum of the emfs
of all these cells. The battery is old, however, so that not all cells are imperfect
condition. Thus there is only a probability p that the emf of any individual cell
has its normal value v; and a probability 1-p that the emf of any individual cell
is zero because the cell has become internally short. The individual cells are
statistically independent of each other. Under these condition Calculate the mean
power P dissipated in the resistor, express the result in terms of N, v, and p
Solution
The total potential of the connection is given by V
And the total power is given by P=V
2
/R
From the connection n
1
number of the cells has emf each values v
The total potential is given by V=n
1
v
The mean value of the power is given by
R
V
P
2
= Where V=n
1
v ,v=constant
( )
R
v n
P
2
1
= =
R
n v
2
1
2
Using the binomial distribution equation we can solve
2
1
n
( )
2
1
n =

( )
( )
N
n
n N n
n q p
n N n
N
0
2
1
1 1 1
1 1
! !
!
and using from equation1.38 and equation 1.39 and rearranging the solution
2
1
n = N
2
p
2
1+
1 p
Np

the substituting in the above equation
( )
R
v n
P
2
1
= =
R
n v
2
1
2
=
N
2
v
2
R
p
2
1+
1 p
Np
4. Consider the random walk problem with p=q and let m=n
1
- n
2
denote the net
displacement to the right. after a total of n steps, calculate the following mean
values:

, m . , ,
4 3 2
m and m m
Solution
Where
a)

m= n
1
n
2
then m= n
1
n
2
where

1
n = W
N
n
1
( )
=
N!
n
1
!n
2
!
p
n
1
q
n
1
1
n
1
using the relation n
1
p
n
1
= p
p
n
1
p

n
1
= p

p
N!
n
1
!n
2
!
p
n
1
q
n
2
and us i ng t he bi nomi al di s t r i but i on

N!
n
1
!n
2
!
p
n
1
q
n
2

=( )
N
q p +
n
1
= p

p
p+ q ( )
N
= pN( p+ q)
N 1

where 1 = + q p then
n
1
= Np

Similarly you can fnd for
2
n =

Nq
Then from the above equation

m= N( p q)
b)

m
2
= n
1
n
2
( )
2
= n
1
2
+ n
2
2
2n
1
n
2

using the following relation
= p

p
2
p+ q ( )
N
= p

p
pN( p+ q)
N 1
( )

= pN( p+ q)
N 1
+ p
2
N(N 1)( p+ q)
N 2

consider (p+q)=1 then

2
1
n = pN + p
2
N(N 1)

similarly for
2
2
n can be calculated as
n
2
2
= qN + q
2
N(N 1)

Substituting in the equation given below

2
m = n
1
2
+ n
2
2
2n
1
n
2

= qN + q
2
N(N 1)

+ pN + p
2
N(N 1) - Np

Nq
.
5. An ideal gas has a temperature independent molar specifc heat
v
c at constant
volume. Let c
p
/ cv denote the ratio of its specifc heats. The gas is thermally
insulated and is allowed to expand quasi-statically from an initial volume V, at
temperature T
f
to a fnal volume V
f

a) Use the relation

pV

= constant to fnd the fnal temperature T
f
of this gas.
b) Use the fact that the entropy remains constant in this process to fnd the fnal
temperature T
f
.
Answer
We have given that pV
=cont.
from the ideal gas equation pV = nRT
then
V
nRT
p = which is
i
i
i
V
nRT
p = ,
f
f
f
V
nRT
p =
substituting in the above equation

p
i
V
i
= p
f
V
f

nRT
i
V
i
V
i
=
nRT
f
V
f
V
f
which is

T
i
V
i
1
= T
f
V
f
1
T
f
= T
i
V
i
V
f
1
b) Consider the entropy as a function of T, V
S=S(T,V)
dS =
S
T
V
dT +
S
V
T
dV = 0
If we evaluate for the value of
dT
dV

T
V
S
=
S
V
T
S
T
V
Using the second law of thermodynamics

dQ = TdS
T
S
T
V
=
dQ
dT
V

=
V
C
For monatomic deal gas the internal energy and molar heat capacity is given
C
V
=
E
T
V
=

T
3
2
RT
V

=
2
3R
Using one of the Maxwell relation

S
V
T
=
p
T
V

the pressure from the ideal gas equation p =
RT
V
then

p
T
=
R
V

using the above equation
T
V
S
=
S
V
T
S
T
V

T
V
S
=
R
V
3R
2T

3
2
=
S
V
T
T
V

lnT
lnV
=
2
3
which gives

TV
2
3
= cons tant
which is given as
2
3
= 1 =
5
3
1 for the ideal gas
6. The Molar specifc heat at constant volume of a monatomic ideal gas is known
to be
2
3
R. suppose that one mole of such a gas is subjected to a cyclic quasi-

static process which appears as a circle on the diagram of pressure p versus
volume V shown in the fgure below

B
A C
D
1 2
2
3
1
3
10
6
dynecm
-2
P
10
3
cm
3
V
Find the following quantities.
a) The net work (in joules) done by the gas in one cycle.
b) The internal energy difference (in joules) of the gas between state C and state
A.
c) The heat absorbed (in joules) by the gas in going from A to C via the path
ABC of the cycle.
Answer
a) The work done in one cycle

w= pdV
from the fgure we can write the value of v and p

V = (2 + cos)cm
3
10
3
p = (2 + sin)dyn / cm
2
10
6
dV = sincm
3
10
3
d
w= (2 + sin)sin10
9
2
0
d10
7
J

w= (2 + sin)sind10
2
J
0
2

w= 314J
b) The internal energy of the ideal gas is given by
T C E
V
=
nRT E
2
3
=
for ideal gas pV=nRT
then substituting in the above equation we will get

E =
3
2
pV
The internal energy of the gas along the path of ac

E
c
E
a
=
3
2
( p
c
V
c
p
a
V
a
)

=
3
2
(2x3 2x1)10
2
J

E
c
E
a
J 600 =
c) The heat energy from a to c along abc is given by

E = Q + w
compute for each value

w= pdV
w= (2 + sin)sind10
2
J

w= 100 (2sin + sin
2
)d
0
J

w= (4 +

2
)100J

w= 557.08

E
c
E
a
= 600J
Q = (E
c
E
a
) + w

Q = 600J + 557J
Q = 1157J
7. Compute the mean values of the magnetic moment
Answer

= P
r
r
r

= P
+
+
+ P
_
_

=
e
H
e
H
e
H
+ e
H

= tanh
H
kT
8. Compute the mean energy of the canonical distribution of mean energy
Answer
The system in the representatives statistical ensemble are distributed over their acces-
sible states in according with the canonical distribution
P
r
=
e
E
r
e
E
r
r
the mean energy given by

E =
e
E
r
E
r
r
e
E
r
r
where

e
E
r
r
e
E
r
( )
=

Z
r

where Z= e
E
r
r

the quantity Z defned the sum over state or partition function
E =
1
Z
Z

=
lnZ
9. Using the canonical distribution compute the dispersion of the energy

Answer
The canonical distribution implies a distribution of systems over possible energies;
the resulting dispersion of the energy is also readily computed

E ( )
2
= E E
( )
2
= E
2
E
2
here E
2
=
e
E
r
E
r
2
r
e
E
r
r
but e
E
r
E
r
2
e
E
r
E
r
r
2
e
E
r
r
then
E
2
=
1
Z
2
Z
2
using the following
1
Z
Z
1
Z
2
Z
2

+
1
Z
2
Z
E
( )
= -
2
E -

E
( )
2
E ( )
2
=
E
2
lnZ
2
10. The internal energy of the ideal gas is given by E=E(T) show that for the ideal
gas its internal energy does not depend on its volume
Answer
Let E=E(T,V)
Then we can write mathematically

dE =
E
T
v
dT +
E
V
T
dV
from the frst law

TdS = dQ = dE + dW
dS =
1
T
dE +
vR
V
dV

using the above equation for dE
dS =
1
T
E
T
V
dT +
1
T
E
V
T
+
vR
V
dV

the entropy as a function of T and V
S=S(T,V)
dS =
S
T
V
dT +
S
V
T
dV

Comparing the equation

S
T
V
=
1
T
E
T
V

S
V
T
=
1
T
E
V
T
+
vR
V

with the second order differential equation

2
S
VT
=

2
S
T V

T
S
T
V
=

V
T
1
T
E
T
=
1
T
2
E
VT
V
S
V
T
=

T
V
1
T
E
V
T
+
vR
V
=
1
T
2
E
V
+
1
T
2
E
T V

comparing the two equation
1
T
2
E
V
+
1
T
2
E
T V
=
1
T
2
E
VT

the right and the left equations are equal when

1
T
2
E
V
= 0

which implies E is independent of V

Figure : Maxwell-Boltzmann distribution
It is possible to demonstrate that the partitioning we have found is not just the most
probable but by far the most probable one. In other words, any noticeable devia-
tion from this distribution of particle velocities is extremely improbable (see above:
multinomial distribution.) This makes for the great practical importance of the MB
distribution: it is simply the distribution of velocities in a many particle system which
we may assume to hold, neglecting all other possible but improbable distributions.
Course material with JAVA applets
Franz J. Vesely
Computational Physics Group
Institute of Experimental Physics, University of Vienna,
Boltzmanngasse 5, A-1090 Vienna, Austria, Europe
Copyright F. Vesely 1996-2005
XI.CompiledListofAllKeyConcepts
(Glossary)
System of Particles
Source: http://www.answers.com/topic/coulomb-scattering
Boltzmanns Distribution
Source: http://hep.uchicago.edu/cdf/cdfglossary.html
Scattering cross section - The area of a circle of radius b, the impact parameter.
Phase Space
Source: http://en.wikipedia.org/wiki/Cross_section_(physics)
Ensemble
Source : http://en.wikipedia.org/wiki/Statistical_ensemble
http://srikant.org/core/node11.html
Macroscopic irreversibility from microscopically reversible laws of motion
Source: http://comp.uark.edu/~jgeabana/mol_dyn/
A University of Pennsylvania physical chemistry look at the Maxwell-Boltzmann
distribution, including applets..
Source: http://oobleck.chem.upenn.edu/~rappe/MB/MBmain.htm
XII.CompiledListofCompulsoryReadings
Reading 1
Complete reference : Statistical Mechanics
From Cornell Universit
URL : http://pages.physics.cornell.edu/sethna/StatMech
Accessed on the 23rd September 2007
Abstract : Contents: Random Walks and Emergent Properties; Temperature and
Equilibrium; Entropy; Free Energies and Ensembles; Quantum Statistical Me-
chanics; Computational Stat Mech: Ising and Markov; Order Parameters, Broken
Symmetry, and Topology; Deriving New Laws; Correlations, Response, and Dissi-
pation; Abrupt Phase Transitions; Continuous Phase Transitions.
of the module.
Reading 2
Abstract : Thermal and Statistical Physics: From Classical Mechanics to Sta-
tistical Mechanics; thermodynamic Concepts and Processes; Concepts of
Probability;The Methodology of Statistical Mechanics; Magnetic Systems; Nonin-
teracting Particle Systems; Thermodynamic Relations and Processes; Theories of
Gases and Liquids; Critical Phenomena and the Renormalization Group; Introduc-
tion to Many-Body Perturbation Theory...
of the module.
Reading #3
Complete reference : Lecture Notes in Statistical Mechanics
URL : http://www-f1.ijs.si/~vilfan/SM/
Abstract : This document has advanced theory of statistical mechanics..
Rationale: These Lecture Notes in Statistical Mechanics were written for the
students of the ICTP Diploma Course in Condensed Matter Physics at the Abdus
Salam ICTP in Trieste, Italy.
The lectures cover classical and quantum statistical mechanics, however, some
emphasis is put on classical spin systems. The author also gave an introduction
to Bose condensation and superfuidity but I do not discuss phenomena specifc to
Fermi particles, being covered by other lecturers.
XIII. CompiledListof(Optional)
MmResources
Resource #1
Title: Motion of Centre of Mass
URL: http://surendranath.tripod.com/Applets/Dynamics/CM/CMApplet.html
Description: Applet shows the motion of the centre of mass of a dumbbell shaped
object. The red and blue dots represent two masses and they are connected by a
mass less rod. The dumbbells projection velocity can be varied by using the velo-
city and angle sliders. The mass ratio slider allows shifting of centre of mass. Here
m1 is the mass of the blue object and m2 is the mass of red object. Check boxes
for path1 and path2 can be used to display or turn off the paths of the two masses.
Rationale: This applet depicts the motion of centre of mass of two balls (shown
in red and blue colour). The applets speed and angle of projection can be varied...
Resource #2
Title : Rotating Stool
URL:- http://hyperphysics.phy-astr.gsu.edu/hbase/rstoo.html#sm
Complete Reference:- Good animation graphics and applet to visualize the de-
pendence of moment of inertia on distribution of matter on an object..
Rationale: Strengthens what is already discussed in Activity 2.
Resource 3
Title : Hyper Physics
URL: http://hyperphysics.phy-astr.gsu.edu/hbase/vesc.html
Date Consulted:-April 2007
Description:- This Java applet helps you to do a series of virtual experiments, .
you can determine the escape and orbital velocities by varying different parameters
of the projectile.
Resource #1
Title: Statistical Mechanics (Advanced Texts in Physics)
by Franz Schwabl (Author), W.D. Brewer (Translator
URL: http://www.ebookee.com
Screen Cupture

Description : The completely revised new edition of the classical book on Statistical
Mechanics covers the basic concepts of equilibrium and non-equilibrium statistical
physics. In addition to a deductive approach to equilibrium statistics and thermody-
namics based on a single hypothesis - the form of the microcanonical density ma-
trix - this book treats the most important elements of non-equilibrium phenomena.
Intermediate calculations are presented in complete detail. Problems at the end of
each chapter help students to consolidate their understanding of the material. Beyond
the fundamentals, this text demonstrates the breadth of the feld and its great variety
of applications. Modern areas such as renormalization group theory, percolation,
stochastic equations of motion and their applications to critical dynamics, kinetic
theories, as well as fundamental considerations of irreversibility, are discussed. The
text will be useful for advanced students of physics and other natural sciences; a basic
knowledge of quantum mechanics is presumed.
Resource #2
Title: MACROSCOPIC AND STATISTICAL THERMODYNAMICS
by Yi-Chen Cheng (National Taiwan University, Taiwan)
URL: http://www.worldscibooks.com
Description: This textbook addresses the key questions in both classical
thermodynamics and statistical thermodynamics: Why are the thermodynamic
properties of a nano-sized system different from those of a macroscopic system
of the same substance? Why and how is entropy defned in thermodynamics,
and how is the entropy change calculated when dissipative heat is involved?
What is an ensemble and why is its theory so successful?
Boltzmanns Transport Equation
With his ``Kinetic Theory of Gases Boltzmann undertook to explain the proper-
ties of dilute gases by analysing the elementary collision processes between pairs
of molecules.
Applet BM: Start
We may understand this prescription as the rule of a game of fortune, and with the
aid of a computer we may actually play that game!
Applet LBRoulette: Start
XIV. CompiledListofUsefulLinks
Useful Link #1
Title: Classical Mechanics
URL: http://farside.ph.utexas.edu/teaching/301/lectures/
Description: Advanced description of the topics discussed in mechanics I and II of
the AVU Physics module.
Rationale: This site has comprehensive coverage of most of physics, in the me-
chanics courses. The learner can consult chapters 7, 8 and 9 of the book. The PDF
version is also available.
Statistical and thermal physics sites
http://oobleck.chem.upenn.edu/~rappe/MB/MBmain.html - A University of
Pennsylvania
The Maxwell-Boltzmann distribution, including applets
http://csep10.phys.utk.edu/guidry/java/wien/wien.html
Some applets related to black body radiation
http://history.hyperjeff.net/statmech.html
A statistical physics timeline, for history buffs
http://www.cstl.nist.gov/div836/836.05/thermometry/home.htm
The thermometry research group at NIST, actively trying to improve our
understanding and standards of temperature, particularly below 1 K
http://comp.uark.edu/~jgeabana/mol_dyn/
An applet that shows an example of macroscopic irreversibility from
microscopically reversible laws of motion in the presence of infnitesimal
perturbation
http://www.physics.buffalo.edu/gonsalves/Java/Percolation.html
An applet that shows the percolation phase transition
http://webphysics.davidson.edu/Applets/ising/intro.html
Another applet, this one showing a numerical approach to the 2d ising
model
Statistics websites
http://www.ruf.rice.edu/~lane/rvls.html -
The Rice University virtual statistics laboratory
http://www.stat.sc.edu/~west/javahtml/LetsMakeaDeal.html
An applet for demonstrating the Monty Hall problem
http://www.stat.sc.edu/~west/javahtml/CLT.html
An applet by the same author for demonstrating the Central Limit Theorem
http://www.math.uah.edu/stat/index.xhtml
A large number of statistics demo applets
XV. SynthesisOfTheModule
Statistical Physics
In this module you have learnt an important branch of physics namely Statistical
Physics. i.e. this module offered an introduction to probability, statistical mecha-
nics, and thermodynamics. Specifc topics in probability include random variables,
joint and conditional probability densities, and functions of a random variable.
Topics in statistical mechanics include macroscopic variables, thermodynamic
equilibrium, fundamental assumptions of statistical mechanics, and microcanonical
and canonical ensembles. Topics in thermodynamics include the frst, second, and
third laws of thermodynamics.
Prerequisites
Physics III: Vibrations and Waves (8.03), Differential Equations (18.03) and
Concurrent Enrollment in Quantum Physics I (8.04) is recommended. In Learning
Activity 2 of this module you have been guided through In Learning Activity 3,
you have been guided through the evolution of In Learning Activity 4, you have
been guided through the applications of
XVI.SummativeEvaluation
Short answer questions
1. The heat absorbed by a mole of ideal gas in a quasi-static process in which its tem-
perature T changes by dT and its volume V by dV is given by dQ = cdT + pdV
where c is its constant molar specific heat at constant volume and p is
its mean pressure, p =
RT
V
. Find an expression for the change of entropy
of this gas in quasi-static process which takes it from initial volume of temperature
T
i
and volume V
i
to fnal values T
f
and V
f
.
2. A 0.5kg of water had been heated from 7
0
c to 87
0
c by frst bringing it in contact
with a reservoir at 34
0
c and then with a reservoir at 87
0
c. When the water has
reach 87
0
c
i) What has been the change in entropy of water?
ii) What has been the change in entropy of the heat reservoir?
iii) What has been the change in entropy of the entire system consisting of both
water and heat reservoir?
3. Starting from the fundamental thermodynamic equation derive the general relation
which represent a necessary connection between the parameters T, S, P, V,
T
P
S
=
V
S
P
4. The molar specifc heat at constant volume of a monatomic ideal gas is known to
be
3
2
R . Suppose that one mole of such a gas is taken quasi-statically from state
A to state B along straight line on the diagram of pressure P versus volume V
shown in the fgure. Find the following quantities:
i) The internal energy difference (in joule) of the gas between state A and state B
ii) The net work done (joule) by the gas between state A and state B
iii) The heat absorbed (joule) by the gas between state A and state B

2 4
1
2
V
P
In 10
6
dynes cm
-2
10
3
cm
3
A
B
5. The ideal gas is thermally insulated and is allowed to expand quasi-statically from
an initial volume V
i
at temperature T
i
to a fnal volume V
f
. Using the relation
PV
=const to fnd the fnal temperature T

f
of this gas.
6. Derive the mean energy equation using the canonical distribution.
7. The mean energy E and the work dW are expressible in terms of lnZ considering
Z=Z ( , x) Consider Using the canonical distribution show that the Helmholtz
free energy equation given by
F E TS = kT lnZ
8. Consider an ideal gas of N molecules which is in equilibrium within a container
of volume V
0
.
Denote by n the number of molecules located within any sub volume V of this
container.
a) What is the mean number

nof molecules located within V? Express your
answer in terms of N,V
0
, and V
b) i) Find the standard deviation

n
( )
2
in the number of molecules located
within the sub volume V
ii) Calculate

n
n
, expressing your answer in terms of N,V
0
and V
9. Consider a system A consisting of 2 spins each having magnetic moment

2
0
, and another system A consisting of 4 spins each magnetic moment

0
. Both
systems are located in the same magnetic feld B. The systems are located in
contact with each other so that they are free to contact with each other so that
they are free to exchange energy. Suppose the total magnetic moment for the
combined system is M + M=

4
0
.
a) Count the total number of states accessible number to the combined system
A + A
b) Calculate the ratio of

p( M = 0)
p( M = 4
0
)
c) Calculate the mean value

i ) M

ii ) M
'
10. A simple harmonic one dimensional oscillator has energy level given by

E
n
= (n+
1
2
)h, where is the characteristic (angular) frequency of the
oscillator and where the quantum number n can assume the possible integral
value n=0,1,2,.. Suppose that such an oscillator is in thermal contact with a
heat reservoir at temperature T low enough so that

kT
h
=1
d) Find the ratio of the probability of the oscillator being in the 3
rd
excited state
to the probability of its being in the 2
nd
excited state.
e) Assuming that only the ground state and frst excited state are appreciably
occupied; fnd the mean energy of the oscillator as a function of the tempera-
ture T.
11. The heat absorbed in an infnitesimal process is given by the frst law islative
probability

dQ = dE + pdV
Considering te ideal gas equation at constant pressure. Show that

= 1+
R
C
V
, where =
C
p
C
V
12. Two states with energy difference4.83

4.8310
21
joule occur with relative
probability

e
2
. Calculate the temperature. Given

k = 1.38 10
23
joule/K
13. A system can take only three different energy state

1
= 0,
2
= 1.38 10
21
jou-
les,

3
= 2.76 10
21
joules. These three states can occur in 2, 5 and 4 different
ways respectively.
Find the probability that at temperature 100K the system may be
i) In one of the microstate of energy

3

ii) In the ground state

1
14. Let

V
x
,V
y
,V
z
represent the three Cartesian components of velocity of a mole-
cule in a gas. Using symmetry consideration and equipartition theorem deduced
expressions for the following mean values in terms of k, T and m
i)

V
x
ii)

V
x
V
z
iii)

V
2
x
iv)

(V
x
+ bV
z
)
2

Answer key
1.

S = C ln
T
f
T
i
+ R ln
V
f
V
i
2. i) 528J/K ii) -184J/K iii) 344J/K

4. i) 900J ii) 300J iii) 1200J
5.

T
f
= T
i
V
i
V
f
1

6.

E =
lnZ

7. Consider Z=Z ( , x)

( ) E Z k S + ln

TS kT lnZ + E
From Helmholtz free energy F= E TS
Thus lnZ is very simply related to Helmholtz free energy F
F= E TS =-kT ln Z
8. a)

n = N
V
V
0
, b)

NV
V
0
V
0
V
1
1
2
, c)

NV
V
0
V
0
V
1
1
2
9. a) 8 b) 2/3 C) i)

3
0
ii) 1
10. a)

p
3
p
2
=
1
e
h
b)

h
2
1+ 3e
h
1+ e
h
11. use

PV = RT at constant pressure

PdV = RdT ,

dE = C
v
dT
Hence

dQ = dE + PdV Substituting the above equation we can write

dQ
dT
p
= C
v
+ R = C
p
12.

p
3
p
2
= e
2
= e
E
2
+ E
3
( )
Comparing the two equations

2 =
E
2
E
3
( )
kT
=
4.83x10
21
1.38x10
23
T
, T=175
13.

p
1
= Ce

1
/ kT
= Ce
0
= C

p
2
= Ce
2
/ kT
= Ce
1.38 x10
21
1.38 x10
23
x100
= Ce
1

p
3
= Ce

3
/ kT
= Ce
2.76 x10
21
1.38 x10
23
x100
= Ce
2
and keeping in mind that 2,5,4
microstates can occur in the three energy state, the probabilities are

p
= 1 then

p
1
+ p
2
+ p
3
= 1,

2C + 5Ce
1
+ 4Ce
2
= 1

C =
1
4.38
=0.23
i) The probability for the system to be in one of the microstates energy

3
is

p
3

=
4C
e
2
=
4
4.38x(2.72)
2
=0.12
ii) The probability

p
1
= 2C = 0.45
14. i) 0 ii) 0 iii)

kT
m
iV)

1+ b
2
( )
kT
m

XVII. References
Reif, F. Fundamentals of Statistical and Thermal Physics. New York, NY: Mc-
Graw-Hill, June 1, 1965. ISBN: 0070518009.
Abstract: This standard textbook is an excellent treatment of Statistical
Physics. The chapter end exercises and the summary correlate very well
with the contents of the module.
Rationale: This reference on Fundamentals of statistical and thermal phys-
ics is recommended for undergraduate text book. The contents have been
treated in detail with adequate mathematical support.
Gupta and Kumar Elementary statistical mechanics 21 edition 2006. ISBN 81-
7556-988-
Rationale: This reading provides basic concept methods of ensemble
Distribution law
Zemansky, M., and R. Dittman. Heat and thermodynamics: an intermediate
textbook. 7th Ed. New York, NY: McGraw-Hill Companies, 1997. ISBN:
0070170592
Rationale: This reference may serve as an optional reading for this module.
Joel Keizer Statistical Thermodynamics of Nonequilibrium Processes
(Springer-Verlag) 1987.
Frank E. Beichelt, L. Paul Fatti Stochastic Processes and Their Applications
(Taylor & Francis) 1997.
V.G. Morozov, On the Langevin Formalism for NonLinear & NonEquilibrium
Hydrodynamic Fluctuations Physica 126A (1984) 443-460
Rationale: This reference may serve as an optional reading for this mod-
ule.
Ming Chen Wang, G.E. Uhlenbeck, On the Theory of the Brownian Motion
II Reviews of Modern Physics, Volume 17; 1945.
Abstract:
Walter Greiner, Ludwig Neise and Horst Stocker, Thermodynamics and Sta-
tistical Mechanics, English edition, translated from the German by Dirk
Rischke (Springer, New York, 2000) ISBN 0 387 94299 8
L. D. Landau and E. M. Lifshitz, Statistical Physics, 3rd Edition, Part I (Landau
and Lifshitz Course of Theoretical Physics, Volume 5)(Butterworth-Heine-
mann, Oxford, 1980)
ISBN 0 7506 3372 7
Chandler, D. 1987 Introduction to Modern Statistical Mechanics Oxford: Ox-
ford University Press.
XVIII.MainAuthoroftheModule
About the author of this module:
Sisay Shewamare
Title: Lecturer of Physics
Jimma University
P.O.Box 378
Jimma
Ethiopia.,
E-mail: Sisayshewa20@yahoo.com
Breif Biography
I am a Graduate from Addis Ababa University, Ethiopia where I did M.Sc in Phy-
sics in the Area of statistical Physics.
Currently Im lecturer in physics at Jimma University Ethiopia.
You are always welcome to communicate with the author regarding any question,
opinion, suggestions, etc this module.
IXX.FileStructure
Name of the module (WORD) fle :
Statistical Physics.doc
Name of all other fles (WORD, PDF, PPT, etc.) for the module.
Compulsory readings Statistical Physics.pdf

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African Virtual university

Universit Virtuelle Africaine

Alr|car v|rlua| ur|vers|ly 3

Alr|car v|rlua| ur|vers|ly 28

Alr|car v|rlua| ur|vers|ly 11

Alr|car v|rlua| ur|vers|ly 50

where k is some positive constant having the dimension of

is the mean generalized force conjugate to the parameter x

Infinitesimal quasi static process

Substituting the in the above equation =

it is possible to express dp in terms

must then have an energy near E=E

The probability of the canonical distribution

= S the entropy keeping constant

Alr|car v|rlua| ur|vers|ly 80

Then the Mean Energy

Alr|car v|rlua| ur|vers|ly 85

The total number of the gas N is given by

African Virtual University 91

Using the geometric series

compute the Maxwell-

For N number of molecules there are, for given values of (n

expanding the polynomial

and us i ng t he bi nomi al di s t r i but i on

from the fgure we can write the value of v and p

the mean energy given by

9. Using the canonical distribution compute the dispersion of the energy

African Virtual University 110

=const to fnd the fnal temperature T

African Virtual University 122

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