Singh RB - Thermal and Statistical Physics - 2ed

THERMAL AND SECOND EDITION
STATISTICAL PHYSICS
R B SINGH
Former Head
Department of Physics, UNPG College
Padrauna, DDU Gorakhpur University, Gorakhpur (UP)
ISBN : 978 81 943696 9 1

Price : 999.00
Pub Date : 2021
Format : Hardbound
Extent : 440 Pages
About the Book: Contents:
• This book is designed to meet the academic aspirations of inquisitive young minds of undergraduate students. The main objective of the book is to provide Part-1: Thermal Physics
students with clear and logical presentation of basic concepts and principles of thermal and statistical physics. The book has been divided into two parts. • Kinetic Theory of Gases
The first part deals with the kinetic theory of gases, transport phenomena, equation of state, laws of thermodynamics entropy, production of low temperature, • Transport Phenomena
thermal conduction and the nature of thermal radiation.
• Equation of State for Gases
• All the equations and thermodynamic relations have been expressed in terms of specific values of extensive variables and these variables have been denoted
• Zeroth Law of Thermodynamics:
by lower case letters (v, q, u, s, cv, cp ). The intensive variables have been denoted by upper case letters (P, T).
Preliminary Concepts
• A large number of solved examples have been provided to make the audience feel confident in applying the principles of thermodynamics to various
• First Law of Thermodynamics
phenomena.
• Heat Engines and Second Law of
Second Part of the book presents lucid and systematic exposition of the fundamental principles of the most fascinating, exciting, stimulating and challenging
Thermodynamics
subject – statistical physics. In this part of the book, attempts have been made to present most difficult concepts of statistical physics in most elementary form.
• Entropy
• It begins with the description of microscopic state of the system. Both quantum and classical methods of description of microscopic state have been discussed.
The classical description of a state requires the concept of phase space, μ – space, γ – space and density of states. All these concepts are developed here. • Thermodynamic Relations
• Chapter II is devoted to the development of the concept of ensemble formulation of statistical mechanics. The two fundamental postulates of statistical • Production of Low Temperature
mechanics - principle of equal a priori probability and ergodic hypothesis are discussed here. Then Livoulle’s theorem and the three kinds of ensembles - and Liquefaction of Gases
microcanonical, canonical and grand canonical ensembles are introduced. Canonical distribution function is derived in this section. • Conduction of Heat
• Chapter III gives a brief account of thermodynamic functions – energy, entropy, free energies and their connection with partition function. • Thermal Radiation
• Chapter IV describes the classical statistics. Maxwell-Boltzmann statistics for distinguishable particles and Maxwell’s speed distribution function are derived Part-2: Statistical Physics
first.
• The State of a Many Particle
• Chapter V deals with the consequences of indistinguishability of particles and the need for quantum statistics. Bose-Einstein and Fermi-Dirac statistics have System
been derived.
• Ensemble Formulation of
• Chapter VI is devoted to the study of some important applications of F-D statistics such a Sommerfeldʼs free electron theory of metals, electronic heat Statistical Mechanics
capacity, Richardson-Dushmann theory of thermionic emission, and B-E statistics to Ideal Bose gas and Planckʼs radiation law. This chapter ends with
• Thermodynamic Functions
discussion on validity criterion for classical regime and the comparison of M-B, B-E and F-D statistics.
• Maxwell-Boltzmann Statistics and
• Chapter VII and VIII present various types of partition functions and their applications to specific heat problems. Einstein and Debye models for calculation
Maxwell’s Speed Distribution
of specific heat are given in these chapters.
Formula
• Chapter IX discusses the well-known Random walk problem, Saha Thermal Ionization formula, Pauli-Paramagnetism of conduction electrons and the
• Quantum Statistics
concept of negative temperature.
• Applications of Quantum
About the Author: Statistics
R B Singh has served as Head of Physics Department, UNPG College, Padrauna (DDU Gorakhpur University, Gorakhpur). He obtained his graduate and postgraduate
• Partition Function
degrees from Allahabad University. He has a rich teaching experience of more than forty years. He has to his credit books: Introduction to Modern Physics Vol. I and II,
Thermal and Statistical Physics, A Primer of Quantum Mechanics, A Primer of Statistical Mechanics, Introduction to Mechanics and Fundamentals of Electricity and • Application of Partition Function
Magnetism (co-author). • Special Topics
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Preface to the
Second Edition
The subject matter of the first part of the book remains unchanged in the present edition. Keeping in
view of the feedback received from our learned readers, appropriate changes have been made in the
second part of the book. In addition to these changes, following topics have been added.
(i) Random Walk Problem
(ii) Saha Thermal Ionisation formula
(iii) Pauli-Paramagnetism of Conduction Electrons
(iv) Entropy of Two Level System and the Concept of Negative Temperature.
As far as possible every effort has been made to make the book user friendly and error free, I hope
the book in present form will be more useful. I do not claim that the book is complete in all respect,
the changes for further improvement are always there. I would appreciate any suggestion from our
readers for the improvement of the book. The untiring and cooperative efforts of the entire staff of
the publication division have made it possible to present the book in such a nice form.
R.B. Singh

Contents
Preface to the Second Edition (v)
Preface to the First Edition (vi)
PART–1 THERMAL PHYSICS
CHAPTER 1 Kinetic Theory of Gases 3

1.1 Introduction 3
1.2 Fundamental Assumptions of Kinetic Theory of Ideal Gases 3
1.3 Molecular Flux 4
1.4 Pressure of Gas 6
1.5 Interpretation of Temperature 7
1.6 Deduction of Gas Laws 7
1.7 Avogadro's Law 8
1.8 Dalton's Law 8
1.9 Graham's Law of Diffusion 8
1.10 Maxwell's Law of Distribution of Molecular Speeds 9
1.11 Shape of Curve Representing Speed Distribution Function 14
1.12 Effect of Temperature on Speed Distribution Function 15
1.13 Most Probable Speed, Average Speed and Root Mean Square Speed 15
1.14 Experimental Verification of Maxwell's Distribution Law 17
1.15 Maxwell-Boltzmann Energy Distribution 18
1.16 Degrees of Freedom 18
1.17 Theorem of Equipartition of Energy 19
1.18 Application of Theorem of Equipartition of Energy Specific Heat of Gases 20
1.19 Polyatomic Gas 21
Solved Examples 22
Questions and Problems 28

viii Contents
CHAPTER 2 Transport Phenomena 30

2.1 Mean Free Path 30
2.2 Survival Equation and Mean Free Path 32
2.3 Mean Distance Covered by a Molecule in a Given Direction
After Last Collision 33
2.4 Transport Phenomena 35
Solved Examples 41
CHAPTER 3 Equation of State for Gases 45
3.1 Introduction 45
3.2 Equation of an Ideal Gas 45
3.3 Behaviour of Real Gases 46
3.4 Andrews Experiment on Carbon Dioxide 48
3.5 Critical State 49
3.6 Two-Phase Region 50
3.7 Intermolecular Forces 51
3.8 van der Waals Equation of State 53
3.9 van der Waals Isotherms 55
3.10 Critical Constants 56
3.11 Alternative Derivation for Critical Constants 58
3.12 Limitations of van der Waals Equation 59
3.13 Law of Corresponding States 60
3.14 Determination of Critical Constants 60
3.15 Some Other Equations of State 61
3.16 Virial Equation of States — Kammerlingh Onnes Equation 63
3.17 Boyle Temperature of a van der Waals Gas 63
Solved Examples 64
CHAPTER 4 Zeroth Law of Thermodynamics: Preliminary Concepts 70
4.1 Introduction 70
4.2 Thermodynamic System and Surroundings 70
4.3 Thermodynamic Variables 71
4.4 Extensive and Intensive Variables 71
4.5 Thermal Equilibrium: Zeroth Law of Thermodynamics 72
4.6 Thermodynamic Equilibrium 74
4.7 Thermodynamic Process 75
4.8 Reversible and Irreversible Processes 75
4.9 Equation of State 76

Contents ix
4.10 Coefficient of Expansion (Expansivity) 77

4.11 Compressibility 77
4.12 Relation Between Partial Derivatives 78
Solved Examples 79
CHAPTER 5 First Law of Thermodynamics 82
5.1 Internal Energy 82
5.2 Heat 82
5.3 Work 82
5.4 Work Done in Some Other Processes 83
5.5 Work Depends on Path 84
5.6 Cyclic Process 85
5.7 First Law of Thermodynamics 85
5.8 Heat Capacity 86
5.9 Energy Equation and Difference of Heat Capacities 87
5.10 Adiabatic Transformation of an Ideal Gas 89
5.11 Work Done in Reversible Isothermal Expansion of Ideal Gas 91
5.12 Work Done in Reversible Adiabatic Expansion of an Ideal Gas 91
5.13 Work Done in Reversible Expansion of van der Waals Gas 92
5.14 Variation of Temperature With Height—Adiabatic Lapse Rate 92
5.15 Total (Exact or Perfect) Differential 94
Solved Examples 95
CHAPTER 6 Heat Engines and Second Law of Thermodynamics 98
6.1 Introduction 98
6.2 Heat Engine 99
6.3 Efficiency of Heat Engine 100
6.4 Carnot's Ideal Heat Engine 101
6.5 Reversibility of Carnot Engine 104
6.6 Carnot Refrigerator 104
6.7 Heat Pump 105
6.8 Carnot Theorem 106
6.9 Thermodynamic or Absolute Scale of Temperature 107
6.10 Clausius-Clapeyron Latent Heat Equation (First Latent Heat Equation) 110
6.11 Specific Heat of Saturated Vapour (Second Latent Heat Equation) 112
Solved Examples 114

x Contents
CHAPTER 7 Entropy 121

7.1 Definition 121
7.2 Principle of Entropy Increase 125
7.3 Entropy and Unavailable Energy 126
7.4 Change in Entropy in Heat Conduction or in Process of
Equalization of Temperature 127
7.5 Calculation of Change in Entropy of a System in Reversible Process 128
7.6 Increase in Entropy in Irreversible Processes 130
7.7 Efficiency of Carnot Cycle from T-S Diagram 131
7.8 Entropy of an Ideal Gas 132
7.9 Statistical Interpretation of Entropy—Entropy and Disorder 133
Solved Examples 135
CHAPTER 8 Thermodynamic Relations 145
8.1 Maxwell's Thermodynamic Relations 145
8.2 Tds Equations 148
8.3 Energy Equation 154
8.4 Heat Capacity Equations 156
8.5 Joule-Thomson or Joule-Kelvin Effect 162
8.6 Thermodynamics of Magnetic System Magneto-Caloric Effect 167
8.7 Thermodynamic Functions 169
8.8 Third Law of Thermodynamics Nernst's Heat Theorem 174
Solved Examples 175
CHAPTER 9 Production of Low Temperature and Liquefaction of Gases 185

9.1 Introduction 185
9.2 Techniques of Producing Low Temperature 185
9.3 Adiabatic Demagnetization 187
9.4 Liquefaction of Gases 191
9.5 Matter at Very Low Temperature 194
9.6 Superconductivity 197
Questions 198
CHAPTER 10 Conduction of Heat 199
10.2 Conduction and Conductivity 199

Contents xi
10.3 Variable and Steady State 200

10.4 Isothermal Surface 200
10.5 Coefficient of Thermal Conductivity 200
10.6 Thermal Resistance 201
10.7 Rectilinear Flow of Heat: Fourier Equation 202
10.8 Determination of Absolute Conductivity of a Metal Bar–Forbe's Method 205
10.9 Angstrom's Periodic Flow Method for Determination of Thermal
Conductivity 208
10.10 Three Dimensional Flow of Heat 209
10.11 Radial Flow of Heat: Determination of K of Bad Conductor 209
10.12 Radial Flow of Heat in Cylindrical Shell 213
10.13 Determination of Thermal Conductivity of Rubber Given
in the Form of Tube 214
10.14 Determination of K of Bad Conductor (Asbestos): Lee and
Charlton Method 215
10.15 Formation of Ice on the Surface of a Lake 217
10.16 Ingen Hausz Experiment 218
Solved Examples 219
CHAPTER 11 Thermal Radiation 223
11.2 Sources of Thermal Radiation 223
11.3 Radiation Detector – Thermopile 224
11.4 Nature of Thermal Radiation and Some of its Properties 225
11.5 Some Fundamental Definitions 226
11.6 Energy Flux, Intensity and Radiant Emittance 227
11.7 Radiation in a Hollow Enclosure 227
11.8 An Ideal (Perfect) Black Body 228
11.9 Fery's Black Body 228
11.10 Wien's Black Body 229
11.11 Kirchhoff's Law 229
11.12 Relation Between Radiant Emittance R of a Surface and Energy
È uc ˘
Density U : Í R = ˙ 230
Î 4˚
11.13 Radiation Pressure 231
11.14 Stefan-Boltzmann Law 234
11.15 Solar Constant (S0) 235

xii Contents
11.16 Temperature of Sun 236

11.17 Distribution of Energy in Black Body Radiation 237
11.18 Wien's Displacement Law 239
11.19 Normal Modes (Standing Waves) in a Box 242
11.20 Rayleigh-Jeans Law 244
11.21 Planck's Radiation Law 246
11.22 Deduction of Stefan's Law from Planck's Law 248
11.23 Deduction of Wien's Displacement Law 249
11.24 Energy and Momentum of Photon 250
Solved Examples 250
PART–2 STATISTICAL PHYSICS
CHAPTER 1 The State of a Many Particle System 259

1.2 Specification of the State of a System: Quantum Mechanical
Description of State 259
1.3 Density of States 261
1.4 N-Particle System 263
1.5 Macroscopic (Macro) State 263
1.6 Microscopic (Micro) State 264
1.7 Constraints and Accessible States 265
1.8 Phase Space: The Classical Description of State of a Many
Particle System 265
1.9 Density of States in Phase Space 268
1.10 Number of Quantum States of an N-particle System 270
CHAPTER 2 Ensemble Formulation of Statistical Mechanics 271
2.1 Ensemble 271
2.2 Density of Distribution (Phase Points) in g-Space 272
2.3 Principle of Equal a Priori Probability 272
2.4 Ergodic Hypothesis 273
2.5 Liouville’s Theorem 273
2.6 Statistical Equilibrium 276
2.7 Ensemble Formulation of Statistical Mechanics 277
2.8 Microcanonical Ensemble 277
2.9 Classical Ideal Gas in Microanonical Ensemble Formulation 279

Contents xiii
2.10 Canonical Ensemble and Canonical Distribution 280

2.11 The Equipartition Theorem 285
2.12 Grand Canonical Ensemble 286
CHAPTER 3 Thermodynamic Functions 288
3.1 Entropy 288
3.2 Statistical Interpretation of Second Law of Thermodynamics 289
3.3 Condition of Thermal Equilibrium: Statistical Definition of Temperature 289
3.4 Condition for Mechanical Equilibrium: Statistical Definition
of Pressure 293
3.5 Condition for Diffusive Equilibrium: Definition of Chemical Potential 294
3.6 Thermal, Mechanical and Diffusive Interaction 295
3.7 Free Energy 297
3.8 Thermodynamic Identities 299
CHAPTER 4 Maxwell-Boltzmann Statistics and Maxwell’s Speed Distribution Formula 302
4.1 Maxwell-Boltzmann Distribution 302
4.2 Maxwell’s Speed Distribution Formula 310
4.3 Velocity Distribution Formula 310
4.4 Maxwell Distribution for Velocity Component n(vx) 311
4.5 Average Speed <v> 314
4.6 Root Mean Square Speed vrms 314
4.7 Most Probable Speed vmp 314
4.8 Thermodynamic Properties of Monatomic Gas 315
4.9 Validity of Maxwell-Boltzmann Distribution 318
CHAPTER 5 Quantum Statistics 333
5.1 Indistinguishability of Particles and its Consequences 333
5.2 Bose–Einstein Quantum Statistics 334
5.3 Fermi Dirac (Quantum) Statistics 338
CHAPTER 6 Applications of Quantum Statistics 348
6.1 Sommerfeld’s Free Electron Theory of Metals 348
6.2 Electronic Heat Capacity 355
6.3 Thermionic Emission (Richardson-Dushmann Equation) 356
6.4 An Ideal Bose Gas 359
6.5 Degeneration of Ideal Bose Gas 362
6.6 Black Body Radiation: Planck’s Radiation Law 365
6.7 Validity Criterion for Classical Regime 366
6.8 Comparison of M-B, B-E And F-D Statistics 368

xiv Contents
CHAPTER 7 Partition Function 371

7.1 Canonical Partition Function 371
7.2 Classical Partition Function of a System Containing N Distinguishable
Particles 372
7.3 Thermodynamic Functions of Monatomic Gas 373
7.4 Gibbs Paradox 374
7.5 Indistinguishability of Particles and Symmetry of Wave Functions 377
7.6 Partition Function for Indistinguishable Particles 378
7.7 Molecular Partition Function 380
7.8 Partition Function and Thermodynamic Properties of Monatomic Ideal Gas
380
7.9 Helmholtz Free Energy F 382
7.10 Rotational Partition Function 383
7.11 Vibrational Partition Function 384
7.12 Grand Canonical Ensemble and Grand Partition Function 386
7.13 Statistical Properties of a Thermodynamic System in Terms of Grand
Partition Function 388
7.14 Grand Potential F 389
7.15 Ideal Gas from Grand Partition Function 389
7.16 Occupation Number of an Energy State from Grand Partition Function:
Fermi-Dirac and Bose-Einstein Distribution 390
CHAPTER 8 Application of Partition Function 393
8.1 Specific Heat of Solids 393
8.2 Phonon Concept 398
8.3 Planck’s Radiation Law: Partition Function Method 399
CHAPTER 9 Special Topics 402
9.1 Random Walk Problem 402
9.2 Saha Thermal Ionization Formula 404
9.3 Pauli-Paramagnetism of Conduction Electrons 407
9.4 Entropy of a Two-Level System: Concept of Negative Temperature 410
Appendices 414
Index 422

1
CHAPTER
Kinetic Theory of
Gases
1.1 INTRODUCTION
A vast number of experiments show that heat is a kind of energy associated with molecular motion. In
kinetic model, the matter is assumed to be made up of tiny particles called molecules. The molecules
move in all possible directions with varying speeds i.e., their motion is completely random. Their
speeds increase with rise in temperature of the substance. The molecular kinetic energy is a measure
of heat content in a body.
In solids, molecules are closely packed due to intermolecular forces. They cannot move bodily
from one place to another. However, they can vibrate about their mean position. For this reason,
solids have definite shape and size or volume. In liquids, molecules are at larger distances in
comparison to solids and the intermolecular forces are a bit smaller in magnitude. The molecules of
liquid cannot leave the liquid but move to anywhere inside it. Liquids have definite volume but not
size. In gases, the molecules are at larger distances from each other than those in liquids and the
intermolecular forces are very weak. The molecules are free to move anywhere and hence gases have
neither definite volume nor any shape. Because gases obey simple laws, the kinetic model of matter
was first applied to them. The work of Joule, Bernoulli, Clausius, Maxwell, Boltzmann, James Jean,
Lorentz, Rayleigh van der Waals, Planck, Helmholtz, Gibbs etc., laid the foundation of theory of
heat over which the modern theory of matter was erected. The present chapter is devoted to the study
of kinetic theory of gases.
1.2 FUNDAMENTAL ASSUMPTIONS OF KINETIC THEORY OF IDEAL GASES

The kinetic theory of gases is based on the following assumptions:
(1) A small sample of gas consists of a very large number of molecules. At standard conditions,
1 kilomol of an ideal gas occupies 22.4 m3 volume and contains NA = 6.023 × 1026 molecules
i.e., 1 cm3 of gas contains 3 × 1019 molecules.
(2) The molecules of a gas are like hard spheres and are perfectly elastic. The molecular diameter is
about 2 or 3 × 10– 10 m. The molecules are in continuous motion in all possible directions i.e., there
is no preferred direction of motion. Meaning thereby the molecular motion is chaotic in nature.
(3) Not all molecules have the same speed. Their speeds vary from a low value to a very high
value. The range of molecular speed is so large that no appreciable error is made in taking the
range from zero to infinity.

4 Thermal and Statistical Physics
(4) The collision between any two molecules and between molecule and the wall of the containing
vessel are perfectly elastic. When molecules strike the walls of the vessel, they transfer mo-
mentum to the wall. The rate of change of momentum suffered by molecules exerts force on
the wall. This is origin of pressure of the gas.
(5) The molecules exert no forces among themselves except when they collide. That is, intermo-
lecular forces are assumed to be absent.
(6) The molecules occupy negligible volume in comparison to the volume of the containing vessel.
(7) The duration of collision between the molecules is very small. Between two collisions molecules
move in straight lines and the average distance between two collisions is called mean free path.
1.3 MOLECULAR FLUX

Consider an ideal gas consisting of N molecules enclosed in a vessel volume V. The molecules move
chaotically in all possible directions with all possible speed from zero to infinity. Let us represent the
velocities of the molecules as vectors and call it velocity vectors. These vectors have all possible
magnitude and directions. Now transfer the tails of all velocity vectors to a common origin O and
imagine a sphere of arbitrary radius r with center at O such that all the velocity vectors intersect the
surface of the sphere. The number of points of intersection of velocity vectors with the sphere is equal
to the number N of molecules in the gas. The surface density of these points is N/(4pr 2). Now consider
an element of area dA on the sphere at point (r, q, f) as shown in the figure. This area is equal to
dA = r 2 sin q dq dj. The number of points on this represents the number of molecules with velocities
in the direction between q and q + dq, and j and j + dj. We denote this number by dNqj. Thus
FG N IJ dA = N F dA I = N dW N
4p H r K
dNqj = = . sin q dq dj ...(1.1)
H 4p r K
2
4p 2 qj
4p
where dWqj is the solid angle subtended by area dA at the origin O.
We are interested in finding the number of molecules arriving per second from one side at a unit
area of an imaginary surface within the gas. Let dNv denote the number of molecules whose velocities
have magnitude in the range v and v+dv irrespective of their direction of motion and dNθjv those
molecules moving with speeds between v and v+dv and directions in the angle intervals from θ to
θ+dθ and from j to j + dj. dNθjv is given by
d Ω θϕ sinθd θd ϕ
dN θϕv = dN v . = dN v . ...(1.2)
4π 4π
Let us first find the number of molecules arriving at an element of surface dS of the vessel towards
which dNqjv molecules are moving. To this end, we mentally construct a cylinder with area dS as
base and v dt as length. The volume of this cylinder is
dV = (dS cosq) (vdt)
dV
A fraction of dNqjv molecules will strike the surface dS and this number is
V

Kinetic Theory of Gases 5
Fig. 1.1.
dV Ê sin q d q d j ˆ Ê dS cos q ◊ v dt ˆ
dNqjv,dS = dNqjv = dNv Á ˜¯ ÁË ˜¯ ...(1.3)
V Ë 4p V
Fig. 1.2.
The number of molecules having speed in the range dv about v and striking unit area in unit time
in q-j direction is
dNqjv dS 1
dFqjv = = (vdNv) (sin q cos q dq) (dj) ...(1.4)
dS◊dt 4pV
The total number of molecules arriving at unit area in unit time from one side is obtained by
integrating dFqjv, within the limits of v from 0 to vmax, q from 0 to p/2, and j from 0 to 2p.
vmax p /2 2p
1
F=
4pV Ú v dN v Ú sin q cos q dq Ú dj
0 0 0
⎛ vmax
⎞
1
vmax
⎛ 1⎞ ⎜ ∫ vdN v ⎟
=
4 πV ∫ v dN v ⎜ ⎟ (2 π )
⎝ 2⎠ ⎜∵ v =
⎝
0 ⎟
⎠
0 N

1 N 1
Therefore, F= v = nv ...(1.5)
4 V 4
This is the expression for molecular flux. It also represents the number of collisions that the gas
molecules make with unit area of containing vessel in unit time.
1.4 PRESSURE OF GAS

When a molecule collides with the wall of the containing vessel, it suffers reflection with angle of
incidence equal to angle of reflection. The magnitude of velocity remains unchanged. This follows
from the assumption that the collision of molecule with wall is perfectly elastic. In such type of
collision, the tangential component of velocity remains the same but normal component of velocity
reverses its sign. If a molecule strikes the wall at angle q with the normal, the normal component of
momentum changes by amount 2mv cos q. The number of molecules incident on area dS in time dt
while moving with speed in the range dv about v in the direction q,j is
1
dNqjv,dS = vdNv sin q cos q dj◊dS◊dt
4pV
The change in momentum of these molecules is
1
dpqjv = (2mv cos q) dNqjv,dS = 2mv2 dNv◊cos2 q sin q dq dj◊dS◊dt
4pV
The change in momentum of striking molecules causes force on the surface in opposite direction.
The pressure, which is equal to the force per unit area, is nothing but the rate of change of momentum
per unit area due to all molecules striking the surface. Hence
Ú dp
z z z
v max p /2 2p
m 2 2
P= = v dN v cos q sin q dq dj
dS ◊ dt 2 pV
0 0 0
1 mN 2
P= v
3 V
z
v max
v 2 dN v
0
where v2 = , mean square velocity of molecules.
N
In terms of number density n = N/V of molecules the expression for pressure can be written as
1
P= mn v 2 ...(1.6)
3
The quantity mN/V is the density r of the gas. In terms of density the pressure of the gas is
1
P= ρ v2 ...(1.7)
3
Comparing Eq. (1.7) with ideal gas equation PV = NkT we have
1
mN v 2 = NkT
3

Kinetic Theory of Gases 7
3kT
whence v2 = vrms = ...(1.8)
m
Average kinetic energy per molecule is
1 3
e= m v 2 = kT ...(1.9)
2 2
The magnitude of average kinetic energy of gas molecules at temperature T = 300 K is
3 3 ¥ 1.38 ¥ 10 - 23 J K - 1 ¥ 300 K
e= kT = = 6.21 ¥ 10–21 J.
2 2
The root mean square velocity of oxygen molecule at 300 K is
3kT 3 × 1.38 × 10− 23 J K −1 × 300 K

vrms = v2 = = = 482 m/s
m 5.31 × 10− 26 kg
A STP the root mean square velocity of molecule of some gases is given in the table.
Table 1 R.M.S. Velocity of Molecule of Some Gases
Gas Molar mass vrms

kg/K mole m/s
H2 2.02 1920
He 4.0 1370
N2 28.0 517
O2 32.0 483
CO2 44.0 412
1.5 INTERPRETATION OF TEMPERATURE

The average kinetic energy of a molecule at temperature T is
3
e= kT
2
At absolute temperature T = 0 K, e = 0. Thus in kinetic model, the absolute 0 temperature is that
temperature at which average kinetic energy of molecule is zero and the average kinetic energy of
molecule is proportional to the absolute temperature T.
1.6 DEDUCTION OF GAS LAWS

From kinetic theory we have
1
PV = mN v 2
3
At constant temperature, the mean square velocity is constant, hence PV = constant. Thus for a
fixed mass of gas and at constant temperature, the pressure of a gas varies inversely with volume.

1.7 AVOGADRO'S LAW

For equal volume two gases taken at the same pressure and temperature we have
1 1 2
m1 N1 v12 (Since T1 = T2 , v1 = v2 )
2
PV = = m2 N 2 v 22
3 3
Therefore,
N1 = N2
Thus at constant temperature and pressure, equal volume of different gases contain equal number
of molecules.
1.8 DALTON'S LAW

When two or more non-reacting gases are mixed in a fixed volume, the total pressure is
1 1
P= ρ1 v12 + ρ2 v22 + ⋅⋅⋅⋅
3 3
= P1 + P2 +◊◊◊◊
where P1, P2, … are the partial pressures of the gases at the same in the same volume. Thus, if two or
more non-reacting gases are mixed in a vessel, the pressure of the mixture is equal to the sum of
partial pressures of the component gases.
1.9 GRAHAM'S LAW OF DIFFUSION

Consider two gases at the same temperature and pressure having densities r1 and r2 and root mean
square velocities v1,rms and v2,rms. At equal pressure we have
1 1
P= ρ1 v12 = ρ2 v 22
3 3
v12 r2
or =
v2
2
r1
Since the rate of diffusion of a gas is proportional to its root mean square velocity, we have
R v12
Rμ v12 or 1 =
R2 v22
R1 r2
Therefore, =
R2 r1
That is, at constant pressure and temperature, the rate of diffusion of a gas is inversely proportional
to the square root of its density.

THERMAL AND STATISTICAL PHYSICS
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Singh RB - Thermal and Statistical Physics - 2ed

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THERMAL AND SECOND EDITION

ISBN : 978 81 943696 9 1

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PART–1 THERMAL PHYSICS

CHAPTER 1 Kinetic Theory of Gases 3

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CHAPTER 2 Transport Phenomena 30

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4.10 Coefficient of Expansion (Expansivity) 77

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CHAPTER 7 Entropy 121

CHAPTER 9 Production of Low Temperature and Liquefaction of Gases 185

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10.3 Variable and Steady State 200

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11.16 Temperature of Sun 236

PART–2 STATISTICAL PHYSICS

CHAPTER 1 The State of a Many Particle System 259

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2.10 Canonical Ensemble and Canonical Distribution 280

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CHAPTER 7 Partition Function 371

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1.2 FUNDAMENTAL ASSUMPTIONS OF KINETIC THEORY OF IDEAL GASES

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1.3 MOLECULAR FLUX

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1.4 PRESSURE OF GAS

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3kT 3 × 1.38 × 10− 23 J K −1 × 300 K

Table 1 R.M.S. Velocity of Molecule of Some Gases

Gas Molar mass vrms

1.5 INTERPRETATION OF TEMPERATURE

1.6 DEDUCTION OF GAS LAWS

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1.7 AVOGADRO'S LAW

1.8 DALTON'S LAW

1.9 GRAHAM'S LAW OF DIFFUSION

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