# Statistical Mechanics

Dr Alfred Huan

Contents
1 What is Statistical Mechanics?
1.1 Key Ideas in the module . . . . . . . . . 1.2 Why do we study Statistical Mechanics? 1.3 De nitions . . . . . . . . . . . . . . . . . 1.3.1 Microstate . . . . . . . . . . . . . 1.3.2 Macrostate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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3 4 4 4 5

2 Distribution Law

2.1 Distribution Law & Ensemble Approaches . . . . . . . . . . 2.2 Computation of Most Probable Macrostate Distribution, nj . 2.3 Problems in Derivation of Maxwell-Boltzmann Distribution . 2.3.1 nj not being always large . . . . . . . . . . . . . . . . 2.3.2 What about the other macrostates? . . . . . . . . . . 2.3.3 What happens when we have many energy levels? . . 2.4 Time Evolution of system of microstates . . . . . . . . . . . 2.5 Alternative Derivation for Maxwell-Boltzmann Distribution . 2.6 Examples of Counting in Statistical Mechanics . . . . . . . . 3.1 3.2 3.3 3.4 4.1 4.2 4.3 4.4

6 7 11 11 11 14 15 16 17

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3 Indistinguishable Particles

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Bose-Einstein Distribution for Bosons . . . . . . . . . . . . . . . . . Fermi-Dirac Distribution for Fermions . . . . . . . . . . . . . . . . Alternative Derivation for Bose-Einstein and Fermi-Dirac Statistics First Law . . . . . . . . . . . . . . . . . . . . . Second Law . . . . . . . . . . . . . . . . . . . . Third Law . . . . . . . . . . . . . . . . . . . . . Calculation of Other Thermodynamic Variables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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20 21 23 24 26 27 29 30

4 Statistical Mechanics and Thermodynamic Laws

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5 Applications of Maxwell-Boltzmann Statistics 6 Paramagnetic Systems

5.1 Classical Perfect Gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33 5.2 Harmonic Oscillator . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39 5.3 Equipartition Theorem . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40 6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42 6.2 Spin 1 Quantum System . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43 2 6.3 Spin J Quantum System . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45 1

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CONTENTS

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6.4 Adiabatic Cooling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49

7 Applications of Fermi-Dirac Statistics

7.1 Fermi-Dirac Distribution . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51 7.2 Free Electron Model of Metals . . . . . . . . . . . . . . . . . . . . . . . . . 53 8.1 8.2 8.3 8.4 Introduction to Black Body Radiation Bose-Einstein Distribution . . . . . . . Planck's Radiation Formula . . . . . . Radiation emitted by blackbody . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

51 59

8 Applications of Bose-Einstein Statistics

59 60 61 63

9 The Classical Limit

9.1 The Classical Regime . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66 9.2 Monatomic Gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67 9.3 Gibbs Paradox . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69 10.1 10.2 10.3 10.4 10.5 Introduction . . . . . . . . . . . . . . . . Number of impacts on Area A of a wall . E usion of molecules . . . . . . . . . . . Mean Free Path,  . . . . . . . . . . . . Collision cross-section, . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

66 71

10 Kinetic Theory of Gases

71 73 74 75 76

external environment b particle within a system of many particles 6. We will deal with single particle states and no ensembles. Fermi-Dirac. and static macroscopic variables. Temperature 9. 5. 4. we shall restrict to equilibrium distributions. 1.Chapter 1 What is Statistical Mechanics? 1. Entropy : Disorder Number 7. Distributions : Maxwell-Boltzmann. 8. 2. 3.1 Key Ideas in the module We begin with the introduction of some important ideas which are fundamental in our understanding of statistical mechanics. 3 . The list of important terms are as follows : Microstate Macrostate Partition Function Derivation of Thermodynamic laws by Statistical Mechanics The idea of interaction a particle system . Bose-Einstein In the 3rd year course. weakly interacting particles and the behaviour for distinguishable degeneracies and indistinguishable particles. Equipartition Theorem : the energies are distributed equally in di erent degrees of freedom.

Classical Mechanics The position x. the possible energies for each particle is : ~2  2 E = 2m L2 n2 + n2 + n2  x y z For example in an ideal gas.. For example. So.2 Why do we study Statistical Mechanics? We apply statistical mechanics to solve for real systems a system for many particles. and there are many parameters for each state. 2. the solution will take the form : total = linear combination of a 1b 2c3::: where a means a particle in state a with an energy Ea . For many particles.e. how the particles are distributed over the energy levels.3 De nitions 1. V.. heat capacity. they do not a ect each other's energy levels. We have 2 perspectives to approach in looking at a microstate : 1. i. At T 0. whereas statistical mechanics gives a microscopic perspective of heat in terms of the structure of matter and provides a way of evaluating the thermal properties of matter. . the system possesses a total energy. We can easily solve the Schrodinger's equation for 1 particle atom molecule. Quantum Mechanics The energy levels and the state of particles in terms of quantum numbers are used to specify the parameters of a microstate. how is E distributed among the particles? Another question would be.y.g.1 Microstate A Microstate is de ned as a state of the system where all the parameters of the constituents particles are speci ed Many microstates exist for each state of the system speci ed in macroscopic variables E.3.z and momentum Px. for e..E. we consider particles con ned in a cubic box of length L. Pz  will give 6N degrees of freedom and this is put in a phase space representation. We apply statistical mechanics to provide the answer and thermodynamics demands that the entropy be maximum at equilibrium. Py . N. WHAT IS STATISTICAL MECHANICS? 4 1. We assume that the molecules are non-interacting. Thermodynamics is concerned about heat and the direction of heat ow. Each particle contains a certain energy. 1.CHAPTER 1. . From quantum mechanics.

CHAPTER 1. It contains many microstates. for an ideal gas.g. We adopt the a priori assumption which states the macrostate that is the most stable contains the overwhelming majority of microstates. the equilibrium tends towards a macrostate which is the most stable. However. the magnetization.N.. V : Volume. In statistical mechanics.V. PV = NkT We also have examples of other systems like magnetic systems where we include M. we only need to specify 3 macroscopic variables P. N : Number of particles and E : Energy.3. .V. In the equilibrium thermodynamic state. The stability of the macrostate depends on the perspective of microstates.V. The equation of state for the system relates the 3 variables to a fourth.T or P. The macrostate includes what are the di erent energy levels and the number of particles having particular energies. for e.2 Macrostate A Macrostate is de ned as a state of the system where the distribution of particles over the energy levels is speci ed. This also gives the probabilistic approach in physics. where P : pressure. WHAT IS STATISTICAL MECHANICS? 5 1. T : Temperature.N or E. the equilibrium macrostate is unknown from thermodynamics.

3. non-localised. which is maximum at equilibrium. Mutual interaction exist only for energy exchange during collisions. 2. is de ned as the number of microstates available to a macrostate.g. the volume V. energy E and total number of particles. The disorder number. N are xed. Each level j has energy "j . we need to decide whether the particles are distinguishable or indistinguishable. the sites being distinguishable e. i. 1. Distinguishability : small and identical particles cannot be distinguished during col- 6 . Microcanonical Ensemble : Isolated system with xed energy. in a paramagnetic solid. degeneracy gj . with energy levels xed and the particles don't in uence each other's occupation. every microstate is a macrostate. The disorder number is related to entropy. Grand Canonical Ensemble : Nothing is xed. Let us now consider independent particles. If they are indistinguishable. N.1 Distribution Law & Ensemble Approaches The distribution law is dependent on how we de ne the system.Chapter 2 Distribution Law 2. However. The energy levels are xed by each particle's interaction with its surroundings but not particle-particle interactions. E and number of particles. For an isolated system. and occupation nj . To enumerate .at constant temperature with xed N. and is very large for the equilibrium macrostate.e. localised particles are distinguishable because they are xed in space. Canonical Ensemble : The system is in a heat bath. There are three approaches in de ning the system and we adopt the three ensemble approaches. lisions.

! The number of ways to assign n2 particles = n !N . nj To nd the nj at equilibrium. i.e. n ! 2. For the rst level. nn1.1 1 1 For the second level. Considering the case for distinguishable particles : 1. N! The number of ways to assign n1 particles = n !N .2 2 1 2 . N. DISTRIBUTION LAW X N = nj Xj Total E = nj "j j 7 The A Priori assumption states that all microstates of a given E are equally probable thus the equilibrium macrostate must have overwhelming . n ! 2. We distribute N particles over the energy levels: For example. we must nd the most probable macrostate distribution.CHAPTER 2. Ω Equilibrium state Macrostates The disorder number is proportional to thermodynamic probability.2 Computation of Most Probable Macrostate Distribution. Enumerate .e. 2. i. how probable for a particular macrostate to be the one corresponding to equilibrium.

CHAPTER 2. n1 ! 2 1 2 N! = n1 !n2!::::nj !::::: = QN ! n! j j 2. it means that the energy levels. N.6 Y j gjnj Y gjnj Total = N ! n ! j j 2. Maximise subject to X nj = N and At maximum.7 2. N 2. Number of ways = 2. X nj "j = E 2.nn1.10 .3 Level j has degeneracy gj so any of the nj particles can enter into any of the gj levels.9 By Stirling's approximation for large N : ln N ! = N ln N .4 2. Number of ways = gjnj For all levels. These constraints are introduced through Lagrange multipliers.5 2. Maximise by keeping xed E. X j ln nj ! 2. DISTRIBUTION LAW Number of ways = 8 N! N !  n !N ."j are unchanged.. n !  :::::: n1 !N . For a xed V.8 d =0  dln  = 1 d =0 Hence we can choose to maximise ln instead of ln = ln N ! + X j nj ln gj .

nj lnnj  g nj ln nj  j by assuming large nj also. N + 1 N ln n + N ln N d n  1 N N N 1 2. DISTRIBUTION LAW Proof : ln N ! = = N X 9 Z1 N 1 ln n ln ndn 2. X g dln  = ln nj dnj . n N 1 = N ln N .11 = n ln n . ln N = N ln N . x 1N + N ln N 1 .14 X dnj = 0 for xed N X j "j dnj = 0 for xed E Note "j does not vary. N  1 = .12 n where 4n = d N  = dx. dnj  = 0 j j It is subjected to the constraints : j 2. N + 1 Or N X 1 ln n 4 n = Z 1 = N x ln x . which is not always true. Therefore X j g ln nj dnj = 0 j 2.N + ln N + 1 + N ln N . nj ln nj + nj  2. Now we come back to ln ln  N ln N .13 nj ln gj .15 . N + = N ln N + = N ln N + X j X X j j nj ln gj .CHAPTER 2.

then T " "  e. kT . Since "2 "1. For T 0. For "j "i. population inversion leads to negative temperature. "1 T T 2 1 2.18 1 We will prove later that is equal to kT where k is the Boltzmann constant k = 1:38  10.1  and T is the temperature.e. kT "1 n1 g1e. "j = P Ngj.19 Otherwise. so we get We choose and such that X j j dnj = 0 "j dnj = 0 2. "j Maxwell-Boltzmann Distribution Z where z is the partition function g ln nj  + . kT . "1 e kT " 2. except for n1. nj = 0.17 X j g ln nj  + . all the particles are at ground state. kT 1 = . In lasers. the upper levels get piled by particles provided 4"  kT 2. DISTRIBUTION LAW Now we introduce the constraints : 10 X .CHAPTER 2.20 for g1 = g2 .21 0 . "j dnj = 0 j The equilibrium macrostate becomes : nj = gj e e.16 2. kT e.1 mol. kT "2 "1 . kT "2 e. the population of upper levels remain small. "j = 0 j 2. "j j gj e = Ngj e. because k 0. we get nj ni for gj = gi and T 0 For T = 0. 2 n2 = g2e. "2 .23JK . "j e. i.

nj  X j X j nj ln nj 2. Note that 0! = 1! = 1. However. the higher levels contribute very negligibly to ln nj ! so that we can apP proximate again by nj ln nj .24 nj ln nj . 2. What are their s? Are they small enough to be neglected? The equilibrium distribution nj should be weighted against of all possible macrostates ~ i."j  gj e kT ." 2. If many levels exist. P 2. nj = nj + nj  Since ln nj  = N ln N .3 Problems in Derivation of Maxwell-Boltzmann Distribution There are 2 inherent problems present in the derivation of Maxwell-Boltzmann distribution : 1. then every level j has many particles so that for large nj .3. Many of the higher levels will give ln nj !  0. so The most probable nj Maxwell-Boltzmann Distribution  P j n n  nj = P j in j ~ j i j Ngj e kTj nj = P . The other macrostates of the same xed energy E.22 2. the lower levels will have large nj but higher levels will have small nj . DISTRIBUTION LAW 11 2. nj  because many of the lower levels have large nj . 2. Stirling's approximation can be used.3.23 2. nj is not always large.1 nj not being always large P If the total number of levels j 1 is small and T is large enough.25 . N .2 What about the other macrostates? How does the change when we consider other macrostates? Consider the changes from the most probable macrostate nj to another distribution  nj .CHAPTER 2. = N ln N .

. if  nj  1020. nj ln nj + nj + nj ln nj + 1   nj   + :::    2 n j j X X 1X n 2 = ln nj  . 1   nj   + ::::    2 n j j j 2 X = N ln N . e. 1  nj  + ::::::  2 j j nj  = nj e 2  1 X 2. nj + nj ln nj + n j . DISTRIBUTION LAW Expand about nj . ln N  nj + kT "j nj . X j ln nj  = ln nj  . kT  . 2  nj  + :::: j j j j where 2. minor uctuations will not matter very much. nj = N e kT  Z ."j X j nj = 0 nj "j = 0 and Thus. so the uctuation is minor.  ln nj  = N ln N .  P  nj 2 nj  2. nj ln nj ..27 It follows that nj  will be small.26 neglecting gj for the purpose of simplifying the discusion.CHAPTER 2. Now as before.28 Since nj are large. = N ln N . 2  nj  + ::: Z j j j X X n 2 1 X = ln nj  .  nj .g. Ultimately. by comparison. nj . Thus nj nj . the uctuations allowed are very small. 1010 for nj  to be large. in deriving properties of the system.  "j 1 X n 2 nj ln N . if nj  pnj . 1  nj  + ::: Z j 2 j j j X n 2 = ln nj  . 12 X X j nj + nj  lnnj + nj    nj + nj ln nj + ln1 + nj    nj j 2 X n = N ln N .

n X  nj 2 X 2  nj = j nj  j = 2N Hence nj  = nj e. n2 2 n2 d n2 ::::::: nj  1  2 2.31 N so nj needs to be small in order for nj  to be signi cantly large. i.32 . 2 N  which is small unless 2 1 . DISTRIBUTION LAW Ω 13 (i) (ii) (ii) Macrostates where i represents nj nj and ii nj large. Then. n2 1 n1 Y j d n1 e Z . we see that nj  will be small when the uctuation nj is large Now we come back to the total number of macrostates : The total number of macrostates consistent with constraints : n j nj j .e.30 1 2. 2. N . and we assume is the same for all j.CHAPTER 2.29 2. Alternatively. pj X  nj  e  = nj   Z . In either case. we can also argue the problem out by the choice of a fractional deviation 2 = j njj  j .

6= nj .."j e kT .e.37 . then we have many energy levels G macrostates look roughly the same. G . X 2 2.3 What happens when we have many energy levels? If nj  1 for most levels. Hence Stirling's approximation is invalid in this case."j  i gi e kT . then nj  N and j = 1. G is very much less than N. 2.36 ln nj   N ln N  X  ln nj   so the most probable microstate has overwhelming . ~ We resort to the following trick : Energy levels are closely spaced in groups because G is large.3.  Ngie kTi mi = P .CHAPTER 2. This means that all  P The total number of microstates are not mainly due to the maximum term nj .35 2..2. i. They are grouped into bunches of gi with mi occupation. i=1 first bundle 1 of g1 bundles The energy levels are so closely spaced such that they are grouped into bundles of g i levels i=2 2nd bundle of g2 bundles Using the previous derivation by counting mi energy states.34 2. G lnG  2 2 ln N ln G 2.33  nj  N  G  G ln Now so ln X  ln nj  + G ln N . N .. DISTRIBUTION LAW Stopping the product when nj = 1  14 If total number of energy levels. G." Ngi e kTi = P . gi and mi can be made large in this case.." 2..

Hence. We 2 also x E and T for a xed macrostate i. So we need a statistical assumption that what we observe corresponds to the real average over all microstates.e.CHAPTER 2. X k :Bk E f T  k . The typical time for spin ip is 10. The treatment tries to obtain the average ni over  many di erent but similar macrostates.each atom The change in microstates will mean that the spin energy of the electron is exchanged between neighbouring atoms so the atoms interchange energy levels. k .1 Now. nj .12s. we consider paramagnetic system where the atomic spins interact with the external magnetic eld .4 Time Evolution of system of microstates How many microstates does the system explore within the time for the experiment? For example. The particles inside this system = 1023 particles are assumed to be non-interacting. the energy levels are discretized.40 By grouping closely spaced levels.Zeeman E ect. So for 1023 electrons : The Transition Speed = 1012  1023 = 1035s. After a series of attack on our fundamental assumptions.e. one can only explore a small proportion of microstates. the time-averaged variations are small and the Maxwell-Boltzmann distribution describes nj very well.  mi = mi  g i . we come to establish the basis of statistical mechanics : All macrostates of signi cant probability i.38 Ne kTj = P . the  variation at each j level appears large. 2. Otherwise with nj  1. and each electron have a spin of  1 . for every experiment. DISTRIBUTION LAW 15 We take the time average value of nj over a large number of di erent macrostates."j j e kT mi  = N !  ln nj  = ln  2. the number of microstates :  eN ln N e1035 o 1035 So it takes forever to go through all the microstates. Note in Quantum Mechanics." 2.39  have roughly the same properties and distribution close to the MaxwellBoltzmann distribution ignoring minor changes. large Y gimi i mi ! X 2.

j E l k E i Both the transitions from j to l or i to k requires the same amount of energy. We need a transition from i to k to be accompanied by another transition from j to l. Therefore. keeping E. the rate Rij!kl = Ni Nj Tij!kl where Tij!kl is the transition probability. which is true for almost all transitions.CHAPTER 2. Suppose we change from 1 macrostate to another macrostate. V and N xed. Tkl!ij = Tij!kl 2.k.k.44 2.43 Ri out = Ri in Therefore it follows that : 2.41 Ri out = Ni The total rate in to level i : X j.42 Ri in = At equilibrium.k. DISTRIBUTION LAW 16 2. X j.5 Alternative Derivation for Maxwell-Boltzmann Distribution We present an alternative method to derive Maxwell-Boltzmann distribution from the perspective of equilibrium.l Nj Tij!kl = X j.l Nk Nl Tkl!ij Now we invoke the time-reversal invariance.k.45 Ni X j. The total rate out from level i : 2.l Nk Nl Tkl!ij 2.l Nj Tij!kl 2.46 .

"i 2. k and l.CHAPTER 2.6.48 2.51 Ni = e e. First of all.3. we present a diagramatic scheme of the problem : g2 = 5 g1 = 2 6 particles We also note importantly that there are no equilibrium macrostate in this problem because all the macrostates have di erent total energies. j.5 and 0. 3.49 2.4. 5. DISTRIBUTION LAW Thus for every combination i. There are 7 macrostates namely : 6. We want to calculate the number of macrostates and microstates in this system. both equations will lead to ln Ni = .0 macrostate. Now we come to calculate the microstates : For 6.0. which is the Maxwell-Boltzmann Distribution.6 Examples of Counting in Statistical Mechanics Problem 1 : Given 6 distinguishable particles. 1. 2 energy levels one with a degeneracy of 2 and the other degeneracy of 5. Since Ni N "i. we require NiNj = Nk Nl Principle of Detailed Balancing or ln Ni + ln Nj = ln Nk + ln Nl and "i + "j = "k + "l is required for energy conservation.47 2.1. 4.50 2. "i + 17 2.2. = 26 ways . 2.

Hence we can talk about a xed macrostate.0. n1 = 5  6 + 4  15 ~ 6 + 15 90 = 21 .0. We consider the particles to be weakly interacting. each separated by E .52 j i Therefore. they exchange energy but do not a ect each other's energy levels.e. DISTRIBUTION LAW For 5. In this case. we can calculate for the remaining macrostates.1 macrostate.0.0. 1 =6 C5 1 C0 1 C1 0 C0 0 C0 = 6 ways =6 C4 2 C2 0 C0 0 C0 0 C0 = 15 ways 2 At equilibrium. Macrostate 4.0. i.2. Now we try to calculate Now we consider the schematic picture of this problem : E E E E Macrostate 5. Let us look at the rst 3 levels : i a particle moves from the 3rd level down to the 2nd level and ii a particle moves from 1st level to the 2nd level. 18 ! n n = n Nn ! g1 1 g2 2 1! 2 6!  25  5 ways = 5!1! Subsequently. Problem 2 : Given 5 energy levels.1.0. P P n = nj i nj  ~ 2. because the number of microstates in either macrostate is not overwhelming enough. we apply the weighted average for microstates. using the example above.CHAPTER 2. the change in energy is balanced by exchange of particles for the 2 processes.

DISTRIBUTION LAW n2 = 0  6 + 2  15 ~ 6 + 15 30 = 21 n3 = 1  6 + 0  15 ~ 6 + 15 6 = 21 n4 = 0 ~ n5 = 0 ~ Note : 19 X which is the same as P j nj = 6 ~ nj for any macrostate. .CHAPTER 2.

For example. and they are non-localised. for 3 particles. There are two physically meaningful solutions. Antisymmetric  a = X p . N  20 3. Symmetric  : s = E.1 Introduction Why are particles indistinguishable? This is a quantum mechanical e ect. we get six possibilities : a 2b1c3::::: a 2b3c1::::: a 1b3c2::::: etc. 1. The exchange of quantum particles cannot be detected.g. 2.2 .1 s = a 1b2c3 + a 2b1c3 + a 3b 2c1 + a 1b3c2 + a 2b3c1 + a 3b1c2 2. and so are all linear combination of the permutations. 2. for three particle permutations. All particles are identical so all permutations are solutions to Schrodinger's equations.Chapter 3 Indistinguishable Particles 3. The 's of the individual particles combine to form a total . :::::. ::::.1pP 1. we get X p P 1. N  3. We can write a many particle wavefunction as a linear combination of a 1b2:::::: plus all the possible permutations.

Macrostates Microstates Unless g 1 for some levels. by arranging mi identical particles and gi. then a 2. a 3b2c1 .3 3. 2. We can then count microstates  1 because the states in i are distinguishable. 1! mi !gi . Note that = 1 for all macrostates because of the indistinguishability of particles. Bosons : Symmetric wavefunctions with integral spins. E. To put mi particles in gi states. total  is zero. by the clumping of levels together to make gi large. a 2b1c3 .. 1. INDISTINGUISHABLE PARTICLES 21 where P is the permutation operator. 3 = .a 1. and hence we obtain Pauli's Exclusion Principle.2 Bose-Einstein Distribution for Bosons There is no limit to the occupation number at each level of quantum state. imagine arranging mi particles into gi states. Note when 2 fermions are in the same state. + .1P means . for 3 particles. = mi + gi . 3 There are two kinds of quantum particles in nature: 1. 2. etc. for example.4 X i X i mi = N mi"i = E . For example. a = b . we get s = a 1b 2c3 . Fermions : Anti-symmetric wavefunctions with half-integral spins. a 1b3c2 + a 2b3c1 + a 3b1c2 If we exchange 1 and 2.CHAPTER 3.1 identical barriers on a straight line. . 1! The number of ways = mi !ggi. 3.1 every time we exchange two particle states. 1! mi i Therefore. meaning all permutations cancel in pairs. 1! To maximise subject to the constraints : 3. the more the better. In fact.g.

1 . 1 lngi . 1 mi + gi lnmi + gi . 1! . mi dln  = X i dmi lnmi + gi + dmi .5 1   for gi. 1 where = kT to be proved later. gi ln gi 3. gi . Therefore. INDISTINGUISHABLE PARTICLES Therefore. ln = 22 X i X i X i lnmi + gi . ln mi! . Two systems at thermodynamic equilibrium have the same temperature T. mi ln mi . 3. eg"ii . 1 lnmi + gi . mi + gi = e. 1 Averaging over the gi levels in each clump.11  We will nd later that = kT where  is the chemical potential. lngi .9 3. e mi "i 3.7 X mi + gi ln m dmi = 0 i i Add in : X . 1 . nj = e.8 X i ln mi + gi  + . e 1"j . dmi ln mi .CHAPTER 3. mi ln mi + mi . "idmi = 0 mi Then. mi + gi . So X i i dmi = 0 "idmi = 0 3.10 mi = e. 1 . 1 which is the Bose-Einstein Distribution. The systems at chemical particle number equilibrium have the same . dmi = 0 3. gi . 1! mi + gi .6 3. .

"idmi = 0 m i .. mi! mi = N gi To maximise subject to the constraints : X i X i mi"i = E 3. mi ln mi .15 Now we add in : X .16 X i ln gi . ln  where gi X i gi ln gi . mi = ln dm =0 i X mi i 3. etc.CHAPTER 3.13 = Y i mi!gi . Now we clump the energy levels to produce gi states and mi  gi. Therefore i Number of ways to ll mi boxes out of gi = m !g g. mi mi 1 d ln = .3 Fermi-Dirac Distribution for Fermions In this case.14 Therefore. So X i i dmi = 0 "idmi = 0 3. mi  + . gi .. mi lngi . m ! i i i 3. INDISTINGUISHABLE PARTICLES 23 3.12 3.dmi lnmi . dmi + dmi lngi . we allow 0 or 1 particle to each quantum state. Either there is a particle or no particle in each quantum state. mi  + dmi i X gi .

24 gi .18 3.17 3. P 3.l X 3.k.22 3. Suppose the rate depends on the occupation at k and l. Ni X j.20 Nk Nl Tkl!ij 1  Ni 1  Nj  j. .k.CHAPTER 3.l Nk Nl Tkl!ij 1  Nj  3.23 Applying time-reversal invariance.k. Note : 1 The positive sign in Fermi-Dirac distribution implies that nj  1 which is Pauli  Exclusion principle which states that no 2 fermions can share the same quantum state. eg"ii + 1 Averaging over the gi levels in each clump.4 Alternative Derivation for Bose-Einstein and FermiDirac Statistics For equilibrium consideration.l X = 1  Ni  Nk Nl Tkl!ij 1  Nj  j. INDISTINGUISHABLE PARTICLES Then. For isolated systems with xed N. Tij!kl is the transition rate from i ! k accompanied by j ! l to maintain energy conservation. Therefore. mi = e. nj = e.21 At equilibrium. e mi "i 3.k. e 1"j + 1 which is the Fermi-Dirac Distribution. 2 If nj = N is not a constraint.  has a value. Riout = Ni Riin = X j.19 mi = e.l Nj Tij!kl1  Nk 1  Nl  3.l Nj Tij!kl1  Nk 1  Nl  = 1  Ni  Tij!kl = Tkl!ij X j.k.  is zero and this is true for open systems.

k.CHAPTER 3. e 1"i .e. e 1"i  1 So starting with the positive + sign.30 3. 1 Bose-Einstein Distribution 3. Therefore N ln 1  iN = .28 Ni Nj = Nk Nl 1  Ni 1  Nj 1  Nk 1  Nl N N N N ln 1  iN + ln 1  jN = ln 1  k + ln 1  lN Nk i j l with "i + "j = "k + "l which is the conservation of energy. . Nl . i. the more you receive. l. the rate Riout 1 + Nk 1 . the more likely the transition. Nl  which demostrates Pauli's Exclusion Principle. we need 25 NiNj 1  Nk 1  Nl  = Nk Nl 1  Ni1  Nj  So 3. INDISTINGUISHABLE PARTICLES Then for every combination i.31 Ni = e. j. we obtain Ni = e.27 3. 3. Ni = e e. we obtain Ni = e.33 For fermions. the more particles in k and l.32 and with the negative - sign. the rate Riout 1 . "i i then. e 1"i + 1 Fermi-Dirac Distribution 3. The more you have. Nk 1 . "i 1  Ni 3.24 3.29 "i Ni  Nie e.25 3. and for bosons.26 3. "i = e e.

6 4.2 4. When the boundary conditions change. M.4 4.7 0H = .1 First Law The First law of Thermodynamics : dU = dQ + dW In Statistical Mechanics : Total Energy. etc.5 dW = X j nj d"j .3 dU = X j "j dnj + X j nj d"j Now. For example : particle in a box Hence So. 2 2  "j = ~2m 12 n2 + n2 + n2  V3 x y z 4. we have dW = . e.P = or X @"j nj @V j X @"j nj @m j 26 4.PdV or 0Hdm etc. This occurs when there is a change in the boundary conditions V. E = U = Therefore 4.Chapter 4 Statistical Mechanics and Thermodynamic Laws 4.g. the energy levels change.1 X j nj "j 4.

STATISTICAL MECHANICS AND THERMODYNAMIC LAWS 27 dW Original dQ Then dQ= P "j dnj which takes place by rearrangement in the distribution. The total of the Universe also increases because the equilibrium macrostate must be the maximum . dS = 0 i.2 Second Law We now search for a microscopic explanation for S in terms of .11 4. the particles may collide with the chamber walls and acquire more energy where the walls are hotter with more heat added. N  4. S is constant. dN 4. N  4.12 4. Now f  1 2 = f  1 + f  2 .CHAPTER 4. Now we consider 2 systems with entropy S1 and S2 and disorder number Total entropy. In kinetic theory. 4. During irreversible changes. 4.13 4.Also dnj = 0 so is also constant.8 so S f E. the total S in the Universe increases.e.10 Note : In adiabatic changes.14 S f  so S1 = f  1  and S2 = f  2. We start from the TdS equation : TdS = dU + PdV .9 Also gE. volume increase with no heat added dQ = 0. V. for example. V.S = S1 + S2 Total = Now 1 2 1 and 2 .

1 So S1 = f  1  = k ln S2 = f  2  = k ln S = k ln 1 + k ln = S1 + S2 which implies that C = 0.23 Hence we have a microscopic meaning of entropy.21 4.22 2 2 S = k ln R where k is the Boltzmann constant NA . From the formula which we obtained for the relation of entropy with .19  = @f   @ = @f  2  @ 2 Then 1 @f  1  = 1 @f  2  2 @ 1 1 @ 2 @f  1  = @f  2  = k 2 @ 1 @ 2 where k is a constant by separation of variables. Therefore 1 +C +C +C 4.20 4.CHAPTER 4.17 4. STATISTICAL MECHANICS AND THERMODYNAMIC LAWS Then 28 @f  @ So Also 1 1 2  = @f  @ 1 1  2 2 2 = @f  1  @ 1 4. .18 4. The lesser the knowledge about a system. we are unable to deduce the value of k.15 @f   @ @f  @ 1 2 2 2 = @f  1  @ 1 1 4. When more microstates are availiable 1 so S 0. To be proven later 4.16 4. The system is perfectly ordered when = 1 and S = k ln = 0. the more disordered it gets. The value of k comes out from the ideal gas equation.

When the macrostate has only one microstate. In order to make T = 0. Note that it is meaningless to talk about the exchange of particles in the same state because they do not exchange their positions. it implies that there are no further permutations for the Maxwell-Boltzmann distribution. If kT "int. Hence we can only say S ! S0 as T ! 0 where S0 is the entropy associated with the remaining small interactions for which "int kT and independent of all the entropy for all the other interactions degrees of freedom. The atoms occupying in the ground state are placed in fixed position in a lattice like this. However. made up of magnetic moments. quadrapole moments and octapole moments etc. Now we come to the formulation of the third law : The Third Law of Thermodynamics states that as the temperature T ! 0. From the third law. nuclear paramagnetism may lift the ground state degeneracy. some small interactions e. the entropy S ! 0.CHAPTER 4. The third law of thermodynamics can also be understood in a quantum mechanical . but it is an impossibility. When all the particles take the ground state. the magnetic moments are required to point in the same direction. STATISTICAL MECHANICS AND THERMODYNAMIC LAWS 29 4. Why is this so? The answer : There exists very small interactions in the nucleus. experimentally. it is approaching ground state as UT also approaches 0. this is not achievable. We know from the 2nd law of thermodynamics that heat passes from hot high temperature to cold low temperature if no work is done. the contribution to the entropy S from the system components also tend to zero. The internal energy UT increases when T increases. S = k log E0  = 0 Practically.3 Third Law As the temperature T tends to zero. T=0 is a theoretically correct statement.g. then S 6= 0 at a given T. E0  = 1.  that the disorder number tends to 1.

N Z@ j X 4. S as a combination of entropies of many sub-systems : S = Stotal 1 + Stotal 2 + Stotal 3 4. when 2 systems are in thermal equilibrium. X j gj e kT . U or E U= nj "j X = N gj e. STATISTICAL MECHANICS AND THERMODYNAMIC LAWS perspective as the freezing out of interactions. where will be the same." g e.N j j j where which is proven in tutorial. = 1 kT "j 4.24 Now we try to nd the relation between P and T. 2~m @ + V   = H @x2 2 2 The V  consists of many interaction terms."j 4. N @Z jV. Now we proceed to calculate the other thermodynamic variables. The depends on the nature of the particles and volume V etc.26 Since. For the system of same identical particles. By the Schrodinger equation : 30 . @ V. @Z j = X .4 Calculation of Other Thermodynamic Variables From chapter 2.CHAPTER 4. Hence we can approach the total entropy.25 We also de ne the internal energy. free exchange of particles will allow to reach the same value. the Partition function Z is de ned as : Z= where j represents all levels. "j "j Z j = . 1 dT kT 2 . d =.

CHAPTER 4. STATISTICAL MECHANICS AND THERMODYNAMIC LAWS and therefore. PdV 4.30 4. TdS .N @ @ Z jV.28 Therefore The Helmholtz free energy.29 4. SdT = . SdT = TdS . 1 @Z = @ ln Z  Z ln U = . TdS . ln nj ! = N ln N .31 Since dF = dU .27 We know that nj = N gj e.N 31 4. N + j X Xj = N ln N +  nj "j  + N ln Z . Z "j g Z  nj = N e "j j Then we work out ln .N ln = NkT 2 @ @TZ jV.32 . TS F = . N ln N = U + N ln Z g nj ln nj  + nj  j 4. F is de ned as : Therefore S = k ln = k U + Nk ln Z = U + Nk ln Z T F = U . PdV . ln = N ln N ! + X j nj ln gj .NkT ln Z 4.SdT .

CHAPTER 4.35 @T .33 Entropy : 4. we can calculate : Pressure : 32 @F dF =  @V T dV +  @F V dT @T @F P = . @F V @T 4. STATISTICAL MECHANICS AND THERMODYNAMIC LAWS From the chain rule Therefore. @V T = NkT  @ ln Z T @V S = .34 = Nk ln Z + NkT @Z Z @T = Nk ln Z + U T Then we can use the results above to compute the heat capacity at constant volume : Cv =  @U V 4.

e. 2 2 "j = 2~  2 n2 + n2 + n2  mL x y z for V = L3 and where nx. From quantum mechanics. The atoms are pointlike . There is no interaction with external elds.e. 6. i. no excited electronic states and the paricles are treated as single particles. magnetic elds. ny and nz are integers. e.occupying no volume.1 Classical Perfect Gas To apply the Maxwell-Boltzmann Statistics to the classical perfect gas. The energy is quantized as in the case of particle in a box in QM. 5. we require a few conditions : 1. " kT which is the classical limit. The gas is monatomic. There is no internal structure for the particles. The discrete levels can be replaced by a continuous one if the spacing is small as compared to T. 33 . 4.Chapter 5 Applications of Maxwell-Boltzmann Statistics 5. 3. but there is no interference on each other's "j . i. 2. 7.only for exchanging energy between particles and establishing thermal equilibrium.g. hence we consider only the translational kinetic energy KE. There is a weak mutual interaction . gravity.

x2 dx =  = Z 1 1 e.~2 22 n2 X .1 e.~2 2 n2 1 .2 where .~2 2 z 2mkTL2 x 2mkTL2 y = dnxe dny e dnz e 2mkTL2 n2 = XXX j ~2 2 5. 2mkTL2 n2 +n2 +n2  nx ny nz X . because all the states are summed over.1 2mkT  1 Z 1 e.1 Z 1 .CHAPTER 5.1 0 0 0 To evaluate the integral : Z 0 1 2mL2 kT  1 1 Z 1 e. Z and in this case gj = 1.1 2 Z 1 2 =  rdr d.~2 2 n2 1 .~ 2  2 nx mL kT 5. X "j Z = e.x2 dx e 2mL2 kT dnx =  ~22 2 2 .x2 +y2 dxdy 2 Z.~2 22 n2 X .~2 22 n2 = e 2mkTL x e 2mkTL y e 2mkTL z ny nz Znx1 Z Z . APPLICATIONS OF MAXWELL-BOLTZMANN STATISTICS 34 Now we compute the partition function.x2 dx = L h2 2 ~2 2 n2 x 2 2 1 Let x =  2.1 . kT x y z e.

1 Z 1 e.e.y2 dy 21 5.5 So. ln Z = lnV + 3 ln T + 3 ln 2mk 2 2 h2 ln P = NkT  @@VZ T = NkT V 5.3 Therefore 2 Z = L3  2mkT  3 h2 3 = V  2mkT  2 2 h 5.6 .r2  1 0 0 1 =  1 2 2 2 p = Z.x2 dx 1 Z 1 .4 5.1 e.

Also the entropy is given by : S = U + Nk ln Z T 3 Nk + 3 Nk ln 2mk  + Nkln V + 3 ln T  = 2 2 h2 2 Therefore.7 = NA molecules per mole ln U = NkT 2  @ @TZ V 1 = NkT 2 3 T 2 3 NkT =2  U = 3 kT 2 5. d" To calculate the density of states. ny and nz making up the grid points with each grid point representing one state. The number of particles having energies between " and " + " : .9 5. ny and nz states."j nj = N e kT Z Nh3 e . APPLICATIONS OF MAXWELL-BOLTZMANN STATISTICS i. . we consider the quantum numbers nx. PV = NkT since 35 PV = nRT Nk = nR n k = NR R k=N A because N n 5.10 5.e degeneracy dn ".CHAPTER 5.8 For each atom."j kT = 3 V 2mkT  2 where j represent all nx. Nh3 e kT" dn " n = 3 V 2mkT  2 d" where dn d" 5. i.e. the distribution becomes : .11 is the density of states.

we use : and 2 " = 2pm d" = p dp m . APPLICATIONS OF MAXWELL-BOLTZMANN STATISTICS By writing 36 R2 = n2 + n2 + n2 x y z 4 The number of points states with energy up to "R lie within a sphere of volume 3 R3. 2m 1 = 2V h3  " 2 " 3 2 " 3 V Nh3 e. " N" 2 kT = p  e 3 " 2 4 kT  5.13 Therefore. Therefore. kT 2v 2m 2 " 2 " 1 n = 3 3 h 2mkT  2 1 . dn " = 1 4R2R d" 8 = 1 4R2 dR " 8 d" 2 2 " = 2~  2 R2 mL 5.12 d" = ~22 R dR mL2 dn " =  R mL2 " d" 2 ~232 2 3 1 =  2m3L " 2 " 4 ~3 5. Only positive n's are allowed so we take the positive octant.CHAPTER 5. The number of states lying between energy " and " + " will become : Using we obtain.14 For the momentum distribution.

APPLICATIONS OF MAXWELL-BOLTZMANN STATISTICS So. 2mkT p2p = 2 2mkT  3 Note that 37 5.CHAPTER 5. 2mkT dp p 2 2m 4 kT  p2 N 4e.15 ZZZ all p space dpxdpy dpz = = Z 2 Z0 1 0 d Z p 2  0 sin . the number of particles have momentum between p and p + p is : p2 d" n = p  N 3 pp e.

pd.

p

Z

1

0

p2dp

4p dp

5.16

Therefore we can also express in px, py and pz as p2 N e, 2mkT p p p n = x y z 3 2mkT  2 x p2 + z y N e, p2 2+mkT p2 p p p = x y z 3 2mkT  2 p2 p2 p2 y N e, 2mkT p e, 2mkT p e, 2mkT p z x = x y z 3 2mkT  2 For velocity distribution, we use p = mv, n = f vx; vy ; vz dvxdvy dvz 2 2 2 3 mvx +vy +vz  = Nm 3 e, 2kT vxvy vz 2mkT  2 = gvdv 3 mv2  = Nm 4 3 e, 2kT v2dv 2mkT  2 which are the Maxwell distribution laws for velocities and speeds. We invoke a few integral identities :

5.17

5.18

In =

Z

1

I0 = 2 I1 = 1 2 I2 = 1 I0 2 I3 = I1 I4 = 3 I2 2

0 p

e,x2 xndx

CHAPTER 5. APPLICATIONS OF MAXWELL-BOLTZMANN STATISTICS
So,

38

Z
0

1

Nm3 4  2kT  3 Z 1 e,x2 x2dx 2 gvdv = 2 2mkT  3 m 0 =N
1 Z 1 vgvdv v=N  0 m34  2kT 2 Z 1 e,x2 x3 dx = 3 2mkT  2 m 0 r = 8kT m 1 v2 = N

5.19

The mean speed, v 

5.20

and mean square speed is

v2gvdv 0 m34 Z 1 e,x2 x4 dx = 5 2mkT  2 0 = 3kT m

Z

1

5.21

Average energy, 1 mv2 = 3 kT 2 2 Root mean square RMS speed, v2 = The most probable speed :
3 dgv = 0  2v e ,2mv2 , mvp e ,2mv2 = 0 kT kT p dv r kT kT  vp = 2m

5.22

p

r

3kT m

v 

5.23

5.24

CHAPTER 5. APPLICATIONS OF MAXWELL-BOLTZMANN STATISTICS
Maxwell Distribution of Molecular Speeds V

39

Vp

V

V2

T

vp v 

p

v2

5.2 Harmonic Oscillator
We now consider the simple 1-D harmonic oscillator in equilibrium at T, with the 2 Hamiltonian, H = 2pm + 1 k0x2 2 where j = 0,1,2,.....

"j = j + 1 ~! 2

! = k0 m Assume the oscillators are independent and distinguishable, ,"j nj = N e kT Z Z=
1 X
j =0

r

e,

j + 1 ~! 2

kT

! = e, 2~kT ! = e, 2~kT

1 X
j =0

e, kT

j ~!

1 ~! 1 , e, kT ~! 1 = e, 2 1 , e, ~!

5.25

3 Equipartition Theorem ... e. ar2. ~! e 1+ 1 = N ~! 2 e ~! . 1 1 U = N ~! 2 + ~! 1 + kT + ::: . U  1 N~!. 1 At low T. 1 X n=0 40 a arn = 1 .N @lnZ @ 1 = 2 N ~! + 1 . Quantization is not important for kT ~!  "= The Equipartition theorem states that all terms in the Hamiltonian with squared coordinates x or px etc will contribute  1 kT to the average energy. ar.. ln1 . N. APPLICATIONS OF MAXWELL-BOLTZMANN STATISTICS Note : for a series of a. ~! ~!e. r 5.. provided quantization 2 is not important.28 which is the classical result. 2 At high T. H = kinetic energy only p2 + p2 + p2 y z x = 2m 2m 2m Therefore U = 3 kT  N atoms 2 = 3 NkT 2 5. 1 = N ~! 1 + ~! 1 2 e kT .CHAPTER 5.27 5.. 1 ~! . Example 1 : Ideal Gas.. The high energy states are occupied. This is re ected in the classical regime at high T where kT "int. 1 = N ~! 1 + kT 2 ~! = NkT 5.. ~!  2 U = .26 ln Z = . it means that the oscillators are in ground state.

~!vib kT. i. For vibrational motion.e. the total internal energy. the experimental 2 results show that U = 5 NkT. the Hamiltonian is frozen out and the contribution is not 1 kT.CHAPTER 5. i. For rotational motion. Therefore. p0z2 + 1 k z0 2 Hvib = 2m 2 0 where z' is the relative coordinate between the 2 atoms. Total H = Hvib + Htrans + Hrot 5. 41 Therefore H = Kinetic energy + Potential energy p2 x = 2m + 1 k0x2 2 U = kT  N atoms = NkT With quantization setting in at low T.29 . However. the atoms are in ground state. p2 + p2 + p2 y z x Htrans = 2m 2m 2m 2 1 L2 Hrot = 1 Lx + 2 I y 2I x y neglecting rotation about z-axis. So in terms of Hvib . 2 Example 3 : Diatomic gas. U should be 7 NkT.e. APPLICATIONS OF MAXWELL-BOLTZMANN STATISTICS Example 2 : 1-D Harmonic Oscillator. For translational motion. atoms don't appear to vibrate much at normal temperature. 2 The reason is because the vibrational motion is frozen out.

S .Chapter 6 Paramagnetic Systems 6. so magnetism arises from their S. particularly 3d. the orbital quenching occurs.1 6. the atoms have unpaired electrons or partially lled ~ orbitals. Note that the excited electronic states are unoccupied at room temperature because " kT . L and spin. 42 . the outer electrons are involved in valency for chemical bonds. Hence in the ground electronic state of 3d elements. It also acts like the magnetic moment. L and J. In many solids of transition elements 3d. Note that J = S. B = 2e~ Bohr Magneton mc In a solid.~  B  ~ ~ ~ = gJ B B  J = gJ B Bz Jz Quantization 6. which are ultimately paired up so that the net J of outer electrons is zero. H = .2 The Jz and J are observed from atomic physics. Hamiltonian.1 Introduction For a paramagnetic spin system. The inner core. there is a degeneracy of 2S + 1 states.gJ B J When the system interacts with an external magnetic eld. J = . so that the net L = 0 for atoms in the ground electronic state. 4d and 4f orbitals of many elements are not involved in valency. The net angular momentum J for each atom is equal to both the linear orbital ~ ~ angular momentum.

 = .spin-phonon interaction. and determines the relaxation time . 2 The magnetic moment.4 6. S = 3/2 system 43 3 2 1 2 -1 2 -3 2 B 0 Hamiltonian.CHAPTER 6. This is important in spin resonance experiments such as electron spin resonance and nuclear magnetic resonance. H = gsB BSz and gs  2 for electron spin.eld to a spin 3 system : 2 For example. .gsB Sz =  1 gsB 2 The Zeeman interaction with external eld gives energy levels gsB Bz Sz =  1 gsB B 2 where gs  2 and B is the Bohr magneton.5 The  energies correspond to spin   antiparallel to B or spin "  parallel to B. A mechanism must exist for TS and TL to establish thermal equilibrium .3 The distribution in the spin states is associated with the spin temperature TS which may not be the same as the lattice temperature TL . 6. PARAMAGNETIC SYSTEMS Applying B. 6.2 Spin 1 Quantum System 2 We consider the system of N magnetic atoms of spin 1 due to 1 unpaired electron. 6.

the total energy.12 6. Z 2kT 6. 2kT  Z 2 2 Ngs B B sinh gsB B  =. 2kT Z B B Z = e+ 2kT + e.11 S = U + Nk ln Z T = . Z 2kT Ngs B B tanh gsB B  =. 2 gsB e. BV 6. gs B B n" = N e+ 2kT Z gs B B n = N e.CHAPTER 6.7 6. E : The entropy S : gs B B gs B B E = N . 1 gsB B 2 1g  B " = + 2 s B Using the Maxwell-Boltzmann distribution. 2kT Z2 N g  sinh gsB B  = VZ s B 2kT 1 N g  tanh gsB B  = 2V s B 2kT E = .13 where " = B . 2kT = 2 cosh gs2B B  kT gs  B gs  B 44 So 6.8 6. PARAMAGNETIC SYSTEMS "" = . NgsB B tanh gsB B  + Nk ln2 cosh gsB B  T 2kT 2kT The magnetization M : 1X M = V nj j j X + j B kT = VN Z j e gs B B gs B B 1 = VN 1 gsB e 2kT . 1 gsB Be+ 2kT + 1 gsB Be.6 6.10 where Therefore.9 6.

1.J + 1 y = 1y 1y e 2 .J.3 Spin J Quantum System Now we consider a system with total angular momentum J in an external B.P sum = ar .CHAPTER 6. +J +(J-1) 0 -(J-1) -J B=0 B mJ = . = e.yJ 2J X rn . G. 1.yJ  e ey . 11  6. 1 2 2 eJ + 1 y . e. e. Let y = gJ B B Therefore. 1 1 eJ +1y . ::::. PARAMAGNETIC SYSTEMS 45 6.J 6. J .J J X mJ =.Jy = ey .J . J Therefore there are 2J + 1 states. 2 = e. 1. "J = gJ B BmJ where gJ is the Lande g-factor an experimental quantity.15 = sinhJ + 1 y 2 sinh y 2 . the partition function.14 eymJ eymJ mJ =0 2J +1y .eld. 0. e. J X gJ B B Z= e = mJ =. ::::::. .

Z N e.CHAPTER 6.18 6. =Z "J gJ B BmJ 6. 2 coth y 2 2 2 Brillouin function 6.N @ @yZ @ = .21 1 1 BJ y = J J + 1  cothJ + 1 y . lnsinh y  2 2 1 J + 2  coshJ + 1 y 1 cosh y 2 .N @ ln Z @ ln @y = . 2 coth y  V 2 2 N g  JB y =V J B J 6.22 .NkT ln Z = . 2sinh y 2  M = N gJ B  1 V sinhJ + 2 y 2 1 1 = N gJ B J + 2  cothJ + 1 y .19 where We proceed to evaluate other thermodynamic quantities : Helmholtz free energy.NkT lnsinhJ + 1 y . F = . PARAMAGNETIC SYSTEMS Therefore.16 X Magnetization. U = .17 ln Z = lnsinhJ + 1 y . M = VN Z gJ B mJ e @Z = VN 1 @B Z N 1 @Z @y = V Z @y @B = VN gJ B @Z Z @y ln = N gJ B @ @yZ V gJ B BmJ 6.NgJ B BJBJ y 6. lnsinh y  2 2 Internal energy.20 6. 46 Then nJ = N e.

lnsinh y  T 2 2 At high T. NgJ B BJBJ y + Nk lnsinhJ + 1 y . x + x2 .x 6. 1 .CHAPTER 6. 1  1 + y  2 3 2 y 3 J + 1 y 2 2 1 2 1 1 J + 2  y .e 2x = e2x + 1 e . coth x = ex + e.27 . M = N gJ B J J + 1 y V 3 2 N gJ 2 J J + 1B = V B 3kT @ = 0 @B T 2 2 0J  = N gJ B 3kTJ + 1 V 1 Curie's law T 6. 1.26 6. y =J y+ 3 y 12 = 31 J 2 + J y J y J + 1 = 3 6.24 So. and for small x. 1 BJ y = J J + 1  2 Therefore.25 so. x + 2x + ::: + x + 2x :::::2 :::: x 3 3 1 1 + x .1 x2 = 21 2 + 2x + 2x2 + ::::1 + x + 23 + ::: x 2 2 = 1 1 + x + x2 + :::1 .x e .1 x2 x3 x2 = 1 + 2x + 42 + :::: + 11 + 2x + 42 + 83! + ::::: . x2 . x2 + 2:::: = x 3 2 = 1 1 + x + ::::: x 3 1+x = x 3 x 47 6. y 1. PARAMAGNETIC SYSTEMS Entropy. 1 1 + J + 2 y  .23 . S = U + NK ln Z T = .

y So.Jy + ln2J + 1  ln2J + 1 48 U = .33 where all spins are align in the same direction parallel to B. 1 .28 6.J + 2 2y . Since. Therefore 1.30 Then S = Nk ln2J + 1 for 2J + 1 levels.2y e 2 1 2 1 y + ln 1 + J + 1 2y + ::: .32 6. and for large x.Jy + ln J + 2 2 = . 1 = 1 2 2 6. 1 y. coth x = ex + e. PARAMAGNETIC SYSTEMS Since. NgJ B BJ J + 1y ! 0 3 ln Z  ln2J + 1 6. ln y 2 2 = ln2J + 1 6. ln y + :: = . ln ln Z = ln 2 2 = lnJ + 1 y .J + 2 y e . e.29 or 1 1 + y + ::: . hence ! 0. 1 .J + 2 2 2 2 1 y + :::: . ln 1 + y + :::: . 1 2 = . ln e . y + ::: 1 + J + 2 y + :::: . 1 = ln e.J + 1 y ln Z = ln 2 1 .31 .x = 1 e .CHAPTER 6. J + 1 + ::: 2 2 2 .e x 6. At low T. Proof : 2 2 eJ + 1 y .x 1 BJ y = J J + 1 . M = N gJ B J V . 1  + y .

As B. y . U = .eld increases.eld adiabatically. The paramagnetic system is in contact with the lattice and the heat bath. e.CHAPTER 6.2y  ln Z = ln 2 2 1 y + ln 1 . S = . ln e y . isolated from heat bath. Reduce the entropy by turning on the B. So adiabatic cooling is two-staged.NgJTB BJ + NkJy = 0 6.NgJ B BJ Entropy.J + 1 y  . dipoles align more and energy and entropy is taken out from the system. ln 1 = J + 2 2 2 2 = Jy 49 6.35 6.4 Adiabatic Cooling From the third law. But alignment can also be produced with a B.eld. 1. . e .e.36 6. PARAMAGNETIC SYSTEMS 2 2 2 eJ + 1 y . so we need the alignment to stay as we reduce the B.eld isothermally.34 Internal energy. so we need magnetic dipoles to align in one direction. i. Ts Spin System TL Lattice Heat Bath at constant T Heat flow Entropy passed to lattice and heat bath = dQ Ts 2. so cooling reduces the entropy of system. S ! 0 as T ! 0. Reduce the temperature by turning o the B.eld to zero.

dQ = TdS. S Entropy Curves obeying the third law P B=0 (1) (2) R Q B=B T Note : They obey the 3rd law Stage (1) : From P to Q. SLat is small. Hence both TS and TL will drop drastically. But this entropy is so small because of low TL . Sspin stays constant. Adiabatic Demagnetization . As B decreases. so the heat passing is very small. PARAMAGNETIC SYSTEMS Ts Spin System TL Lattice 50 Remove the B-field adiabatically to keep spins align. The lattice passes heat and entropy back to spin. so TS decreases.CHAPTER 6. Isothemal Magnetization Stage (2) : From Q to R.

= kT . Fermi-Dirac Distribution nj = e. egj" .1 7. we consider 2 fermion systems in thermal and di usive contact so to allow particle exchange. With the same constraints : X X ni + nj = N X ni "i + nj "j = E = i j Y Y i j = n !g g. egj" + 1 2.1 Fermi-Dirac Distribution From chapter 3. Bose-Einstein Distribution 7. 1 1 For either systems. The two s will reach equilibrium at same temperature.Chapter 7 Applications of Fermi-Dirac Statistics 7. Now to identify for Fermi-Dirac distribution. n ! n !g g.3 51 . This can be proven by having the quantum system in 1 contact with a classical perfect gas where = kT . We also assume that the same type of fermions for both systems. n ! i i i i j j j j 7.2 nj = e. we obtain two quantum distributions : 1.

CHAPTER 7. + "i = 0 ni gj . + "j dnj = 0 j 7. nj  lngj . = ln gi . nj  . APPLICATIONS OF FERMI-DIRAC STATISTICS ln = + 52 X X j i i gi ln gi . nj ln nj j ni = e. So. X X  dni + dnj  = 0 . gi . nj  . eg"ii + 1 nj = e. ln nj dnj .7 . ni . ni . X i Xj "idni + "j dnj  = 0 j i X i ln gi . nj dnj + dnj .6 Then Choose and . gi . gj . nj ln nj + nj X X = gi ln gi . ni  . ni ln ni + gj ln gj . The di usive contact gives rise to chemical equilibrium. eg"jj + 1 7. ni dni + ln gj n nj dnj ni j j i 7. ln nidni . ni dni + dni . which is related to . ni + gi . ln gj n nj . dni + X j 7.5 Using the method of Lagrange multipliers. nj ln nj j dln = X i lngi . nj  . gi . so that Then ln gi . + "idni + n i X j . nj  + gj . nj  lngj . gj . ni . ni  lngi . ni ln ni + ni gj ln gj . gj . nj  lngj . gj . so i = j =  chemical potential Suppose we take one of the systems : Sj = k ln j X = gj ln gj . ni lngi .4 lngj . nj . dnj =0 X X . + " = 0 ln n j j So the two systems in thermal contact have the same and the two systems in di usive contact will have the same .

we apply Fermi-Dirac Statistics . hence they have low ionisation potential. i. nj ln nj . dW = . k dW j j 7.e.g electrical work. " . there is free propagation and in nite conductivity of electrons.k dN + k dU . For perfect stationary lattice. nj ln nj dnj j X = k .kT dN + dU .2 Free Electron Model of Metals The valence electrons in the outermost shell are loosely bound. dW because 7. + "j dnj j X X = . lattice vibrations phonons and the scattering by the other electrons leads to resistance in the lattice. In metal. e jkT nj = gj 7. We neglect the lattice potential. we will obtain the solution to the Schrodinger equation in the form of Bloch waves. The energy will form a band.electrons of spin  1 and 2 =  1 . nj d"j = . In the free electron model. However lattice imperfections. dnj X gj . The electrons interact with the electrostatic potential of the positive ions in the lattice. the weakly attached conducting electrons are free" to move in the lattice. APPLICATIONS OF FERMI-DIRAC STATISTICS Then 53 dS = k =k X j lngj . takes little energy to detach them.11 +1 where  dN is the work done in moving the fermions from one place to another.8 TdS = . the electrons are con ned in a box body of 2 .10 7. If we consider the periodicity of the potential. nj dnj + dnj .k dnj + k dnj "j  . e.dN + dU .9 dU = TdS + dW + dN Therefore So  = kT same derivation for bosons 7.CHAPTER 7.

15 V m" Number of states between " and "+d" is g"d" = 2 2~2 dk d" d" V 2m" m d" = 2 ~2 ~2k r V 2m2 " ~2 d" = 2 4  ~ 2m" 3 m2 1 = 2V 2 2~3 " 2 d"  1 = V C" 2 d" 7. . i. APPLICATIONS OF FERMI-DIRAC STATISTICS metal and we neglect the mutual interactionselectron-electron scattering. the energy is given by : 54 "nx.13 nR ny nx 1 4 Number of states from k=0 to k=k = 8  3 n3  2 R 7. For single particle state nx.nz . ny and nz are all positive integers.ny . nx.e.CHAPTER 7.16 .12 where k is the wavevector 2  and is de ned by the following relation : 2 k2 = L2 n2 + n2 + n2  x y z nz 7. nz . = 2~  2 n2 + n2 + n2  mL x y z 2 = ~ k2 2m 2 2 7.14 Note : we multiply the relation by 2 because of the 2 spin states and 1 because we 8 only take the positive octant. ny . Number of states between k and k+dk = 1  4k2dk  2   L 3 8  V k2dk = 2  7.

At T = 0 Probability of occupation of state of energy is fF . APPLICATIONS OF FERMI-DIRAC STATISTICS where Therefore. 1 +1 7. + 1 0 gj 7. This is di cult to evaluate except at low T.D " = 1 " "F " "F . +1 Z 1 g"d" = e "j .18 +1 Z 1 "g"d" = e "j . V  and use  in 7. We shall try to evaluate this in 2 cases 1.18 to obtain ".17 E= = X X j j nj "j e "j .D " = f F-D (E) "j gj e "j . T.D " = 0 fF .CHAPTER 7.19 1 0 EF E For T = 0 = "F and Fermi energy 7. 2 1 2m 3 C = 22 ~3 55 N= = X X j j nj e "j . 7.20 fF . + 1 0 We solve equation 7.17 for N.

all electrons occupy the lowest possible state subject to the Exclusion Principle. E = 2.D"d" U= "g"d" ".D"d" 7. Total Energy. kT 1. " g"d" e F = + N"F ". ".21 and g"d" Z "F 1 = VC " 2 d" 0 3 2 = V C 2 "F 3 2 3 2 "F = 3N 2 ~ 3 3 2V 2m 2 2 ~2 3 =  3N  2 2m V 2 ~ 2 = 2m kF 1 kF =  3N  3 V 7.23 The meaning of Fermi energy is that all states below "F are occupied and all states above "F are unoccupied at T = 0. At T=0. g"fF . Z 1 0 g"fF .22 2 7. Z0 1 e" . we want to nd Cv and we know that the experimental value "F is proportional to T. + 1 e 0 Z 1 7.25 .24 N= Therefore. " +g1"d" " g"d"  F  = + Fj .CHAPTER 7. + 1 " +1 Z0 1 "e. so the states are lled until "F .D"d" Z "F 3 =VC " 2 d" 0 2"5 =VC 2 5 3 N" =5 F 0 Z 1 7. APPLICATIONS OF FERMI-DIRAC STATISTICS Hence 56 N= = Z Z 0 0 1 "F g"fF . At low T.

"F  + 12 @" The maximum occurs at " = "F . The physical picture : 7. So the function is sharp for small kT  "F . e ".29 7. The value drops to 1 of the maximum value when e " ."F  + 12 0 Now. @fF ."F  2 Z 01 x2e dx + 1 1 ex 2 where x = " . . "F  kT .D " 7.31 . "F e ". " g"e ".27 e ".28 e ".1 ex + 12 Therefore 2 Cv =  k2 Tg"F  3 where g"F  is the density of states of Fermi level."F V C" 2 d" Cv = kT 2 7. "  "F 1 V C" 1 Z 1 " . Z 1 x2 exdx 2 = 3 . so we assume @T = 0 and  = "F . Z 1 1 1 " . "F  = V C"F k2 T "F ex + 12 The lower limit can be extended to .26 1 1 @ F  " . 7.1 because kT "F .CHAPTER 7. e "j .30 7.e. + 12 0 @ Since  does not change much. kT @T  d" =."F  = . kT 2 . APPLICATIONS OF FERMI-DIRAC STATISTICS Then 57 Cv =  @U V @T Z 1 " . i. dfF-D (E) dE kT EF E The contribution to the Cv integral comes mainly from values of " near "F . "F 2e "."F d"d" 2 Cv = kT 2 F ".

.32 Contribution to Cv . The theory is in agreement but does not give the right constant of proportionality. APPLICATIONS OF FERMI-DIRAC STATISTICS g(E)f F-D (E) 58 T=0 T>0 EF E For T = 0 : All states are occupied within " = "F is a truncated parabola. Therefore Energy of excitation = g"F k2T 2 7. This results in a rounded-o cli at "F .CHAPTER 7. most electrons cannot gain kT because the states above them are already occupied. Only those electrons near "F can gain kT to move into unoccupied states. For T 0 : We will expect electrons to gain energy kT. However. and need to include e ective mass of electron m me because electrons are not completely free but the lattice potential e constrains them. heat capacity = The number of electrons participating  energy T = g"F kT  kT T = f "F k2 T 7.33 Experimental result : Cv T for a fermi gas. An alternative estimate : Number of electrons involved is g"F kT and they gain kT.

and all the walls are at temperature T. The photons have spin 1 bosons and they obey Bose-Einstein statistics. we assume a hole is cut in the chamber wall to emit some radiation. We note that the photons have the following characteristics : 1. 2. the distribution of photons will follow the temperature T. In this chapter. The black body will also absorb all radiation falling on it. in order to study the radiation. The radiation is enclosed in vessel. The hole is very small so that the equilibrium is not disturbed. 4. ! = ck. we will study black body radiation using statistical mechanics.Chapter 8 Applications of Bose-Einstein Statistics 8. At equilibrium. we discuss radiation in thermal equilibrium. the speed of light. The atoms in the wall will absorb and emit electromagnetic radiation. Second. The photons have zero rest mass and travel at c.1 Introduction to Black Body Radiation First. The radiation bounces inside the chamber until nally being absorbed. 3. The photons do not interact with one another. so. This will approximate to a blackbody. The photons satisfy the dispersion relation. " = ~! = ~ck 59 .

gj .3 X nj + gj . dnj = 0 8. 1! 8. nj ln nj 8. 1 lngj . The number of photons are not conserved because of absorption and re-emission.1 Maximise subject to E = constant only. 1! . 3. 1 . nj ln nj + nj . This implies that and  = 0. 1! j nj !gj . 1 + gj . 1 ln n dnj = 0 j . 1 . 1 lnnj + gj . nj ln nj . nj + gj . 1 lnnj + gj . E= For bosons. 1dnj + dnj . ln nj ! . The blackbody absorbs and emits radiation until thermal equilibrium is established. The blackbody is so small that heat capacity is negligible. 1 lngj . The energy content of photons are not changed.CHAPTER 8.2 Bose-Einstein Distribution Perfect Insulating Walls Small Blackbody We consider a system of a small blackbody placed inside a chamber with perfect insulating walls. 1 . 1 nj + gj . ln = = = X X j X j j lnnj + gj . APPLICATIONS OF BOSE-EINSTEIN STATISTICS 60 8. X j nj "j = constant for the photons = Y nj + gj .2 dln  = X j lnnj + gj . 1 . 1! nj + gj . gj . lngj . The features of the system are as follows : 1. 2.

APPLICATIONS OF BOSE-EINSTEIN STATISTICS X Therefore So. kz . k ! 2 = k2 = k2 + k2 + k2 x y z c2 For any ~ .5 X g ln nj +n j . "j dnj = 0 j nj = e "jgj.3 Planck's Radiation Formula Consider photons enclosed in a box L3 . j 61 dnj "j = 0 8. there are 2 polarizations . 1 8. standing electromagnetic waves result such that n = L 2 Therefore x kx = 2 = nL x 2 = ny  ky =  L y z kz = 2 = nL  z For any photon with ~ = kx. ky .6 1 Prove = kT by having the photon system in thermal contact with another system at temperature T and use walls that can exchange energy. for large gj and nj .CHAPTER 8. 1  .4 8. 1 Bose-Einstein function = e "j1. k nz 8.7 nR ny nx .2 linear or 2 circular. 8.

CHAPTER 8.13 T2 T1 T2>T1 w For T2 T1.12 8. T) 8. 12 ~! =0 .10 N !d! = Density of states  Bose-Einstein function !2 = 2c3V e ~d! 1  !. APPLICATIONS OF BOSE-EINSTEIN STATISTICS Therefore.8 since V Number of photon states between k and k+dk = 2 k2dk 2 Number of photon states between frequency range ! and !+d! = V2 !2 d!  c c V !2d! = 23 c The number of photons in frequency range ! and !+d! is 8. T is given by : e ~! 3!2 .11 8. the maximum of u!.9 8. Number of photon states for k=0 to k=k = 1  4 n3  2 8 3 R 3 =  L3 k3 3 2 n2 = L2 k2 R  62 8. Thus the energy of the photons in the frequency range ! and !+d! is V ~ !3d! ~!N ! d! = 2 3 ~!  c e . u(w. !2 ~e e ~! . T d! = 2c3 e !!d! 1 ~ .1 The energy density per unit volume in the frequency range is 3 ~ Planck's formula u!.

x = 2. 1 1 x3 dx ~ = c3 41~4 ex .822. as T rises. APPLICATIONS OF BOSE-EINSTEIN STATISTICS 63  3e ~! . T d! Z 1 !3d! ~ = 23  c 0 Ze ~! .19 8. by neglecting -1.16 8. Therefore. ~!max kT = 2:822 Wien's displacement law 8. 1 = ~e ~!  3ex .17 or !max = 2:822k T ~ So.CHAPTER 8. 1 0 4 4 4 = k2 T 3   c3~ 15 0 Z 1 8. uT = 2c = 2:822k T max ~ ~c 1 max = 2:822k T Therefore u!. 1 = xex where x = ~! Solving numerically. x  3.18 uT  = aT 4 where Stefan-Boltzmann law 8.4 Radiation emitted by blackbody d = r sin .15 8.14 8. the colour of the blackbody changes from red to blue : Total Energy Intensity. or more accurately.

d rd.

r2 = sin .

d.

with photons coming from direction . A.d 2 4 a = 15ck~3 3 Consider a tiny hole.

! .

+ d.

. where . ! + d . with a subtended solid angle d .

The volume of the parallelpied is dA  ct cos . 64 The photons that will pass through in time t are located in a parallelpiped of length ct.CHAPTER 8. APPLICATIONS OF BOSE-EINSTEIN STATISTICS The total solid angle = 4.

of photons passing per unit time from direction . θ θ c θ t dA Therefore.. No.

! .

+ d.

. ! + d  with a frequency range ! to ! + d! = Volume of Parallelpiped  Fractional solid angle  Number density in frequency interval t = dAc cos .

 d   N !d! 4 V Therefore. the total energy radiated per unit time in frequency interval ! to ! + d! Z 2 Z  2 = d sin .

d.

dAc cos .

T d! 4 . T dAd! =4 Therefore Power radiated per unit area in frequency interval from ! to ! + d! = 1 cu!.  ~! N !d! 4 V 0 0 = 1 c~!dA N !d! 4 V 1 cu!.

Therefore.8 W m.2 K. T d! Total power radiated = 4 0 1 caT 4 =4 = T4 where a = 15c3 ~3 65 2 k4 . APPLICATIONS OF BOSE-EINSTEIN STATISTICS 1 c Z 1 u!.CHAPTER 8.4 . 2 4 = 60ck~3 2 = 5:67  10.

 = e  e. including r = 0. we consider the continuous variable " rather than the discrete energy "r . Fermi-Dirac and Bose-Einstein distributions approximate to Maxwell-Boltzmann distributions in the classical regime. nr M-B= N e. The energy spacing is " kT. and nr unoccupied states.1 The Classical Regime In the classical regime. since "0 ! 0 for ground state. 1 nr F-D. which are averaged over time.e. e so that "r . "r . 66 .Chapter 9 The Classical Limit 9. there is a lack of discreteness. the classical regime is only satis ed if 1 1 e "r .1 1.B-E  e.  1 i. "r M-B distribution So all the 3 distributionsMaxwell-Boltzmann. According to the Maxwell-Boltzmann statistics. "r Z for all r. So we require N Z 1 9. 1 which means that there are many In the Fermi-Dirac or Bose Einstein statistics.

so.2 Monatomic Gas For monatomic gas. THE CLASSICAL LIMIT 67 9. .CHAPTER 9.

3 V 2mkT 2 Z = h3 .

1 3 2 Nh3 V 2mkT T 2 .

N 3 h2 V 2mk 1 The conditions are high temperature. p p = 2m" = h in QM terms dB Then . m. V Assume the energy is equipartitioned. " = 3 kT for each atom 2 p2 = 2m So. T and low density N . and high mass.

3 .

1 3 2 2 1 = 4 2mkT 3 m" .

3 3 1 2 = 2 p3 .

3 3 .

 3 2 dB = 2 h and .

3 N 3 2 3 1 V 2 dB i. 1 1 .e.

2 1 .

V 3 .

3 .2 9. 2 2 2 dB 3 N = 3 l0 where l0 is the average seperation between atoms. Examples : 9.

hence N  1023 per cm3 V l0  2  10. 68 N = 1020 per cm3 V m = 6 41023 g l0 . dB l0. Hence Maxwell-Boltzmann distribution is applicable.7cm At T = 273 K.9 cm For liquid He at T = 4 K. Since dB l0 . so Fermi-Dirac statistics apply. He gas : so l0 = 2  10.31 kg and T = 273 K. and so dB = 8 10.8cm For m = 9:1  10. For conduction electrons : Assume 1 electron per atom. 2. N = 2  1022 per cm3 V so l0 = 4  10. g(E)f F-D (E) T=0 Approximately M-B T>0 EF f F-D (E) E 1 T=0 T>0 0 EF E . so Bose Einstein statistics apply. THE CLASSICAL LIMIT 1.CHAPTER 9.8cm.

9. V N T S V N T S S = U + Nk ln Z T  . 69 " for M-B distributions. Now we mix the volumes of identical atoms. we assume the atoms to be distinguishable. THE CLASSICAL LIMIT Note that 2 n" " 1 e.3 Gibbs Paradox For classical ideal gas.CHAPTER 9.

4 3 S = 3 2N k + 2N k ln 2V + 2 ln T + 3 ln 2mk 2 2 h2 9. V ! 2V.5 = 2Sold + 2Nk ln 2 The problem lies with distinguishability and overcounting. Hence we use a corrected . However. 9. we expect S!2S. old Corrected = N ! Y gjnj = n!  .  3 Nk + Nk ln V + 3 ln T + 3 ln 2mk = 2 2 2 h2 Suppose now N ! 2N.

 9. N   . kN ln N . Corrected S = k ln Corrected .6 j j Therefore.

.

7 .  5 Nk + Nk ln V + 3 ln T + 3 ln 2mk = 2 N 2 2 h2 9.

CHAPTER 9. 70 2V S = 5 2N k + 2Nk ln 2N + 3 ln T + 3 ln 2mk 2 2 2 h2 = 2Sold  . THE CLASSICAL LIMIT Then for N ! 2N. V ! 2V.

.

8 .  9.

For the Hamiltonian : 1. The Boltzmann law applies to every coordinate in the Hamiltonian.2 where A Z 1 . 2.p2 10.mvx 2 e 2kT dvx = 1 . etc of system of gas molecules in thermal equilibrium.mv2 10.z can have any momentum px. pz . momentum. The probability that x-momentum which lies between px and px+dpx is : x P px dpx = Ae 2mkT dpx .1 71 .1 10.e.1 2. energy.Chapter 10 Kinetic Theory of Gases 10. py .1 Introduction Consider the distribution for e. For example.y. velocity. i. The kinetic energy KE terms are determined by px.4 A0 Z 1 . the momentum and spatial coordinates are independent of each other. At thermal equilibrium. The probability that x-velocity lies between vx and vx+dvx is : P vx dvx = A0e 2kTx dvx where . position.p2 x e 2mkT dpx = 1 . y and z.g.3 10. a molecule in any position x. 1. py and pz . The potential energy PE terms are determined by x.

dφ dc dθ P vx.CHAPTER 10.5 10. KINETIC THEORY OF GASES 3. v x 2 2 2 For speed distribution : P c dc where c2 = vx + vy + vz .1 We concentrate on the momentum and velocity distributions. hence we do not require the interaction potential except for establishing thermal equilibrium.V x kT dx 10.6 B Z 1 .V x e kT dx = 1 . The probability that the molecule is found between and x and x+dx is : 72 P x dx = Be where . P[px]. vz dvxdvy dvz = P vx dvxP vy dvy P vz dvz . P[v x ] px. vy . For graphs of P px or P vx : the gaussian curves centred at zero.

2mvy e .2mvz2 dv dv dv kT kT kT = 2kT x y z .2mvx e . 3 2 2 m 2 e .

mc2 2 e 2kT dccd. m 3 .

csin.

d  = 2kT Integrating over all angles : 3 .

8 . we can calculate : 10.7 10. m 2 .mc2 P c dc = 4 2kT e 2kT c2dc Hence.

cmax : For cmax. Most probable speed. KINETIC THEORY OF GASES 1.CHAPTER 10. put .

1 dP c = 0  c = 2kT 2 max dc m 2.9 c=  3. c2 : Z 0 1 1 . Mean square speed. Mean speed c :  73 10.

Root mean square speed.10 p 4. c2 : c2 = Z 0 1 kT c2P c dc = 3m 10. 8kT 2 cP c dc = m 10. Mean kinetic energy KE : Note : so kT c2 = 3m .11 p 5.

14 10.12 Mean KE = 1 mc2 = 3 kT 2 2 2 2 2 c2 = vx + vy + vz 2 = 3vx 2 vx = kT m 10.13 10. 1 2 10.2 Number of impacts on Area A of a wall θ A .15 10.

CHAPTER 10. KINETIC THEORY OF GASES The distribution of speeds : P c dc 74 The fraction of molecules travelling in direction .

! .

+ d.

. ! + d  is cd.

csin.

d = sin.

d.

16 4c2 4 The fraction that will reach A in time t for above direction = Ac cos .d 10.

Number of impacts on area A in time t = NP c dc sin.17 V where V is the volume of the gas.t 10. Therefore.

d.

d Ac cos .

t 4 V Number of impacts on unit area per unit time 2 N Z 1 cP c dc Z  sin .

cos .

d.

19 10.3 E usion of molecules The number of molecules with speeds c!c+dc from direction . Z 2 d = 4V 0 0 0 N c 1 2 = 4V 2 1  = 4 nc where the number density.18 10. n = N . V ZZZ 10.

! .

+ d.

. ! + d  imping a area in time t is N cP c dcsin.

d.

The mean speed of escape.d At 4V The distribution is proportional to c P c dc. ce : R 2 P dc ce = R ccP cc dc   .

m 1 2 = 9kT 8m = 3kT 1 8kT 2 m 10.20 .

75 .CHAPTER 10. KINETIC THEORY OF GASES Number of molecules escaping per unit time per unit area 1 mc = p 8kT 4  kT m 1 2 m1 So. the smaller molecules escapese uses faster.

 the probability of no collision in dx = e.dx  x e. The distribution of free path : Probability that free path in between x and x+dx We can prove this by a self consistent argument : Probablity that collision occurs between x and x+dx = Probability of no collision from 0 to x  Probability of collisions in dx Comparing with the above equation.   dx  . 1 2 10.22. for some are longer and some are shorter.  10.  The free path is de ned as the distance between collisions. the shorter is the free path. e dx + :::: =1.21 10. Probability of collision in dx = 1 .22 10. It is not all equal. dx Then. we write Probability of no collision in dx = e . The more probable the collision.24 Probability of collision in dx = dx  According to 10.23 10. 1.4 Mean Free Path.  dx .

dx  10. .23.25 which agrees with 10. .

  7  10.26 Z 0 1  . 1  = p n1 2 At stp.  dx  Z 0 1 x e. 10.27 10.e. Average volume occupied by each molecule = V = 1 N n 10. 11 00 11 00 11 00 11 00 d d The moving gas molecules sweeps out a cylinder of cross section : = d2 where d is the diameter of the each molecule.   = 1 0 which is as required for probability.  = V  1 2 N d 1 = nd2 Taking in account of the motion of gas molecules.xe. x 1 + 0 x xe.30 10. Mean free path = = 76 10.   5 m.28 So.  1 0 = 10. Mean free path.CHAPTER 10. Also. At 10.8m.  dx x = .31 . KINETIC THEORY OF GASES So the argument is self consistent.5 Collision cross-section. we see that Z 1 x dx e.6 mbar.29 10. Therefore.

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