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Statistical Mechanics DR Alfred Huan PDF
Statistical Mechanics DR Alfred Huan PDF
Dr Alfred Huan
Contents
1 What is Statistical Mechanics?
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Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Bose-Einstein Distribution for Bosons . . . . . . . . . . . . . . . . .
Fermi-Dirac Distribution for Fermions . . . . . . . . . . . . . . . .
Alternative Derivation for Bose-Einstein and Fermi-Dirac Statistics
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2 Distribution Law
3 Indistinguishable Particles
3.1
3.2
3.3
3.4
First Law . . . . . . . . . . . . . . . . . . . . .
Second Law . . . . . . . . . . . . . . . . . . . .
Third Law . . . . . . . . . . . . . . . . . . . . .
Calculation of Other Thermodynamic Variables
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3
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4
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5
6
7
11
11
11
14
15
16
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20
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21
23
24
26
26
27
29
30
33
6 Paramagnetic Systems
42
CONTENTS
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59
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59
60
61
63
66
71
Introduction . . . . . . . . . . . . . . . .
Number of impacts on Area A of a wall .
Eusion of molecules . . . . . . . . . . .
Mean Free Path, . . . . . . . . . . . .
Collision cross-section, . . . . . . . . .
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71
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74
75
76
Chapter 1
What is Statistical Mechanics?
1.1 Key Ideas in the module
We begin with the introduction of some important ideas which are fundamental in our
understanding of statistical mechanics. The list of important terms are as follows :
1.
2.
3.
4.
5.
Microstate
Macrostate
Partition Function
Derivation of Thermodynamic laws by Statistical Mechanics
The idea of interaction
(a) particle (system) - external environment
(b) particle (within a system of many particles)
6. Entropy : Disorder Number
7. Equipartition Theorem : the energies are distributed equally in dierent degrees of
freedom.
8. Temperature
9. Distributions : Maxwell-Boltzmann, Fermi-Dirac, Bose-Einstein
In the 3rd year course, we shall restrict to equilibrium distributions, and static macroscopic variables. We will deal with single particle states and no ensembles, weakly interacting particles and the behaviour for distinguishable (degeneracies) and indistinguishable
particles.
where
= linear combination of
For example, we consider particles conned in a cubic box of length L. From quantum
mechanics, the possible energies for each particle is :
2
2
E = 2~m L 2 (n2x + n2y + n2z )
For example in an ideal gas, We assume that the molecules are non-interacting, i.e.
they do not aect each other's energy levels. Each particle contains a certain energy. At T
> 0, the system possesses a total energy,E. So, how is E distributed among the particles?
Another question would be, how the particles are distributed over the energy levels. We
apply statistical mechanics to provide the answer and thermodynamics demands that the
entropy be maximum at equilibrium.
Thermodynamics is concerned about heat and the direction of heat
ow, 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, for e.g., heat
capacity.
1.3 Denitions
1.3.1 Microstate
A Microstate is dened as a state of the system where all the parameters of the constituents (particles) are specied
Many microstates exist for each state of the system specied in macroscopic variables
(E, V, N, ...) and there are many parameters for each state. We have 2 perspectives to
approach in looking at a microstate :
1. Classical Mechanics
The position (x,y,z) and momentum (Px, Py , Pz ) will give 6N degrees of freedom
and this is put in a phase space representation.
2. Quantum Mechanics
The energy levels and the state of particles in terms of quantum numbers are used
to specify the parameters of a microstate.
1.3.2 Macrostate
A Macrostate is dened as a state of the system where the distribution of particles over
the energy levels is specied..
The macrostate includes what are the dierent energy levels and the number of particles having particular energies. It contains many microstates.
In the equilibrium thermodynamic state, we only need to specify 3 macroscopic variables (P,V,T) or (P,V,N) or (E,V,N), where P : pressure, V : Volume, T : Temperature,
N : Number of particles and E : Energy. The equation of state for the system relates the
3 variables to a fourth, for e.g. for an ideal gas.
PV = NkT
We also have examples of other systems like magnetic systems (where we include M, the
magnetization). However, the equilibrium macrostate is unknown from thermodynamics.
In statistical mechanics, the equilibrium tends towards a macrostate which is the most
stable. The stability of the macrostate depends on the perspective of microstates. We
adopt the a priori assumption which states the macrostate that is the most stable contains the overwhelming majority of microstates. This also gives the probabilistic approach
in physics.
Chapter 2
Distribution Law
2.1 Distribution Law & Ensemble Approaches
The distribution law is dependent on how we dene the system. There are three approaches in dening the system and we adopt the three ensemble approaches.
1. Microcanonical Ensemble : Isolated system with xed energy, E and number of
particles, N.
2. Canonical Ensemble : The system is in a heat bath,at constant temperature with
xed N.
3. Grand Canonical Ensemble : Nothing is xed.
The disorder number,
is dened as the number of microstates available to a
macrostate, and is very large for the equilibrium macrostate. The disorder number is
related to entropy, which is maximum at equilibrium.
To enumerate
, we need to decide whether the particles are distinguishable or indistinguishable. If they are indistinguishable, every microstate is a macrostate.
Let us now consider independent particles, with energy levels xed and the particles
don't in
uence each other's occupation. The energy levels are xed by each particle's interaction with its surroundings but not particle-particle interactions. Mutual interaction
exist only for energy exchange (during collisions).
Each level j has energy "j , degeneracy gj , and occupation nj .
lisions, i.e. non-localised. However, localised particles are distinguishable because they
are xed in space, the sites being distinguishable e.g. in a paramagnetic solid.
For an isolated system, the volume V, energy E and total number of particles, N are
xed.
X
N = nj
Xj
Total E = nj "j
j
The A Priori assumption states that all microstates of a given E are equally probable
thus the equilibrium macrostate must have overwhelming
.
Equilibrium
state
Macrostates
N!
N , n1!
n1 !(N , n1 !) n2 !(N , n1 , n2)! ::::::
N!
=
n1 !n2!::::nj !:::::
= QN !
n!
Number of ways =
(2.3)
j j
Level j has degeneracy gj so any of the nj particles can enter into any of the gj levels.
Number of ways = gjnj
For all levels,
Number of ways =
gjnj
Y gjnj
Total
= N ! n !
j j
(2.4)
(2.5)
(2.6)
2. Maximise
by keeping xed E, N. These constraints are introduced through Lagrange multipliers.
For a xed V, it means that the energy levels,"j are unchanged.
Maximise
subject to
and
nj = N
nj "j = E
At maximum,
d
= 0
(2.7)
) d(ln
) =
1 d
(2.8)
=0
ln
= ln N ! +
X
j
nj ln gj ,
X
j
ln nj !
(2.9)
(2.10)
Proof :
N
X
ln N ! =
Z1 N
ln n
ln ndn
(2.11)
= [n ln n , n]N1
= N ln N , N + 1
Or
N
X
1
ln n 4 n =
n + N ln N )d( n )
(
N
ln
1
N
N
N
1
= N [x ln x , x]1N1 + N ln N (1 , N1 )
= ,N + ln N + 1 + N ln N , ln N
= N ln N , N + 1
(2.12)
where 4n = d( Nn ) = dx.
Now we come back to ln
ln
N ln N , N +
= N ln N +
= N ln N +
X
j
(nj ln gj , nj ln nj + nj )
(nj ln gj , nj lnnj )
X
j
nj ln( ngj )
(2.13)
(2.14)
X
j
X
j
X
j
(2.15)
,
so we get
We choose and such that
X
j
10
X
j
X
j
dnj = 0
"j dnj = 0
(2.16)
(2.17)
(2.18)
We will prove later that is equal to kT1 where k is the Boltzmann constant (k =
1:38 10,23JK ,1 mol,1 ) and T is the temperature.
For "j > "i, we get nj < ni for gj = gi and T > 0
For T = 0, nj = 0, except for n1, i.e. all the particles are at ground state. For T > 0,
the upper levels get piled by particles provided
4" kT
(2.19)
Otherwise, the population of upper levels remain small.
In lasers, population inversion leads to negative temperature,
"
for g1 = g2 ,
n2 = g2e, kT2
n1 g1e, kT"1
"2
, kT
e
= , "1 > 1
e kT
(2.20)
(2.21)
because k > 0.
Since "2 > "1, then T < 0
11
P
n
(n )
n~j = Pj
j (in )j
j i j
(2.22)
j
Ng
j e kT
nj = P ,"j
gj e kT
(2.23)
2.3.1
nj = nj + nj
Since
ln
(nj ) = N ln N , N ,
= N ln N ,
X
j
(2.24)
X
j
(nj ln nj , nj )
nj ln nj
(2.25)
12
X
j
where
(2.26)
kT
nj = N
Ze
,"j
X
j
and
Thus,
nj = 0
X
j
nj "j = 0
ln
(nj ) = ln
(nj ) ,
It follows that
1
(nj ) =
(nj )e 2
P (nj )2
nj
(2.27)
(2.28)
Since nj are large, the
uctuations allowed are very small, by comparison, e.g. if
nj 1020, nj . 1010 for
(nj ) to be large. Thus nj nj , so the
uctuation is minor..
Ultimately, in deriving properties of the system, minor
uctuations will not matter very
much.
13
(i)
(ii)
(ii)
Macrostates
X (nj )2 X 2
= nj
n
j
j
j
2
= N
(2.29)
(nj ) =
(nj )e,2 N
(2.30)
Hence
which is small unless 2 . N1 , i.e,
(2.31)
N
so nj needs to be small in order for
(nj ) to be signicantly large. In either case, 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 :
(nj ) e
=
(nj )
Y
j
,n21
dn1 e
n1
(nj ) 12
,n22
n2
dn2 :::::::
(2.32)
14
(nj )( N ) G2
G
ln
Now
ln
(nj ) + G2 ln N , G2 lnG
ln
(nj ) N ln N ln N ln G
so
ln
ln
(nj )
(2.34)
(2.35)
(2.36)
If nj 1 for most levels, then we have many energy levels G N . This means that all
macrostates look roughly the same.
P The total number of microstates are not mainly due to the maximum term
(nj ), i.e.
6=
(n~j ). Hence Stirling's approximation is invalid in this case.
We resort to the following trick : Energy levels are closely spaced in groups because
G is large. They are grouped into bunches of gi with mi occupation. gi and mi can be
made large in this case.
i=1
i=2
first
bundle
1 of g1
bundles
2nd bundle
of g2
bundles
i
Ng
i e kT
mi = P ,"j
i gi e kT
,"i
Ng
i e kT
= P ,"j
e kT
(2.37)
15
We take the time average value of nj over a large number of dierent macrostates.
mi = mgi
i
,"j
(2.38)
kT
Ne
= P ,"j
j e kT
(mi ) = N !
Y gimi
i mi !
X
(2.39)
ln
(nj ) = ln
(2.40)
By grouping closely spaced levels, the time-averaged variations are small and the
Maxwell-Boltzmann distribution describes nj very well. Otherwise with nj 1, the
variation at each j level appears large. The treatment tries to obtain the average ni over
many dierent but similar macrostates.
After a series of attack on our fundamental assumptions, we come to establish the basis of statistical mechanics : All macrostates of signicant probability (i.e. large
) have roughly the same properties and distribution close to the MaxwellBoltzmann distribution ignoring minor changes.
The change in microstates will mean that the spin energy of the electron is exchanged
between neighbouring atoms so the atoms interchange energy levels. The typical time for
spin
ip is 10,12s. So for 1023 electrons :
The Transition Speed = 1012 1023 = 1035s,1
Now, the number of microstates :
16
E
i
Both the transitions from j to l or i to k requires the same amount of energy.
Rij!kl = Ni Nj Tij!kl
where Tij!kl is the transition probability.
The total rate out from level i :
Ri out = Ni
The total rate in to level i :
Ri in =
X
j;k;l
(2.41)
Nj Tij!kl
(2.42)
Nk Nl Tkl!ij
(2.43)
j;k;l
At equilibrium,
Ri out = Ri in
Therefore it follows that :
Ni
X
j;k;l
Nj Tij!kl =
X
j;k;l
Nk Nl Tkl!ij
(2.44)
(2.45)
Now we invoke the time-reversal invariance, which is true for almost all transitions,
Tkl!ij = Tij!kl
(2.46)
17
(2.47)
(2.48)
(2.49)
(2.50)
Ni = e e,"i
which is the Maxwell-Boltzmann Distribution.
(2.51)
g1 = 2
6 particles
We also note importantly that there are no equilibrium macrostate in this problem because all the macrostates have dierent total energies.
There are 7 macrostates namely : (6,0), (5,1), (4,2), (3,3), (2,4), (1,5) and (0,6).
Now we come to calculate the microstates :
For (6,0) macrostate,
= 26 ways
18
Macrostate (5,0,1,0,0),
1 =6 C5 1 C0 1 C1 0 C0 0 C0
= 6 ways
Macrostate (4,2,0,0,0),
2 =6 C4 2 C2 0 C0 0 C0 0 C0
= 15 ways
At equilibrium, we apply the weighted average for microstates, because the number of
microstates in either macrostate is not overwhelming enough.
P
n~j = nPj
i (nj )
(2.52)
i
Therefore,
4 15
n~1 = 5 66 +
+ 15
90
= 21
19
2 15
n~2 = 0 66 +
+ 15
30
= 21
0 15
n~3 = 1 66 +
+ 15
6
= 21
n~4 = 0
n~5 = 0
Note :
X
which is the same as
n~j = 6
Chapter 3
Indistinguishable Particles
3.1 Introduction
Why are particles indistinguishable?
This is a quantum mechanical eect. The exchange of quantum particles cannot be
detected. The 's of the individual particles combine to form a total , and they are
non-localised.
We can write a many particle wavefunction as a linear combination of a (1) b(2)::::::
plus all the possible permutations. For example, for three particle permutations, we get
six possibilities :
a (2) b (1) c (3):::::
a (2) b (3) c (1):::::
a (1) b (3) c (2):::::
etc.
All particles are identical so all permutations are solutions to Schrodinger's equations,
and so are all linear combination of the permutations.
There are two physically meaningful solutions.
1. Symmetric :
s=
X
p
P [ (1; 2; ::::; N )]
(3.1)
2. Antisymmetric
a=
X
p
(3.2)
21
where P is the permutation operator; (,1)P means (,1) every time we exchange
two particle states.
E.g., for 3 particles, we get
s
i + gi , 1)!
The number of ways = (m
mi !(gi , 1)!
(3.3)
Therefore,
= (mi + gi , 1)!
mi !(gi , 1)!
To maximise subject to the constraints :
X
i
X
i
mi = N
mi"i = E
(3.4)
22
Therefore,
ln
=
i
X
i
X
i
for gi; mi 1
d(ln
) =
X
i
X mi + gi
(ln m )dmi = 0
i
i
Add in :
(3.6)
(3.7)
X
dmi = 0
Xi
, "idmi = 0
i
So
X
i
(ln( mi + gi ) + , "i)dmi = 0
mi
Then,
Therefore,
(3.8)
mi + gi = e, e"i
mi
(3.9)
gi
mi = e, e"
i ,1
(3.10)
nj = e, e"1 j , 1
(3.11)
We will nd later that = kT where is the chemical potential. Two systems at thermodynamic equilibrium have the same temperature T. The systems at chemical (particle
number) equilibrium have the same .
23
Therefore
Y
i
gi
mi!(gi , mi)!
(3.12)
(3.13)
X
i
X
i
Therefore,
ln
where gi >> mi >> 1
X
i
mi = N
mi"i = E
d ln
=
=0
mi
Now we add in :
So
(3.14)
(3.15)
X
dmi = 0
Xi
, "idmi = 0
i
X
i
mi ) + , " )dm = 0
(ln( gi ,
i
i
m
i
(3.16)
24
gi , mi = e, e"i
mi
(3.17)
gi
mi = e, e"
i +1
(3.18)
nj = e,e"1 j + 1
(3.19)
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).
2) If nj = N is not a constraint, is zero and this is true for open systems. For
isolated systems with xed N, has a value.
Nj Tij!kl(1 Nk )(1 Nl )
(3.20)
Nk Nl Tkl!ij (1 Ni )(1 Nj )
j;k;l
X
= (1 Ni ) Nk Nl Tkl!ij (1 Nj )
(3.21)
Riout = Ni
Riin =
j;k;l
j;k;l
At equilibrium,
Ni
X
j;k;l
Nj Tij!kl(1 Nk )(1 Nl ) = (1 Ni )
X
j;k;l
Nk Nl Tkl!ij (1 Nj )
(3.22)
Tij!kl = Tkl!ij
(3.23)
25
(3.24)
Ni Nj = Nk Nl
1 Ni 1 Nj 1 Nk 1 Nl
(3.25)
(3.26)
(3.27)
with
which is the conservation of energy. Therefore
ln 1 NiN = , "i
i
then,
Ni = e e,"i
1 Ni
(3.28)
(3.29)
(3.30)
Ni = e,e"1 i 1
(3.31)
Chapter 4
Statistical Mechanics and
Thermodynamic Laws
4.1 First Law
The First law of Thermodynamics :
dU = dQ + dW
In Statistical Mechanics :
Total Energy; E = U =
Therefore
dU =
X
j
"j dnj +
X
j
(4.1)
X
j
nj "j
nj d"j
(4.2)
(4.3)
Now, we have dW = ,PdV or 0Hdm etc. This occurs when there is a change in the
boundary conditions (V, M, etc). When the boundary conditions change, the energy levels change.
For example : particle in a box
Hence
2 2
"j = ~2m 12 (n2x + n2y + n2z )
V3
dW =
(4.4)
nj d"j
(4.5)
,P =
X @"j
nj @V
j
(4.6)
0H =
X @"j
nj @m
j
(4.7)
So, e.g.
or
26
dW
Then dQ=
Original
27
dQ
In kinetic theory, the particles may collide with the chamber walls and acquire more
energy where the walls are hotter (with more heat added).
g(E; V; N )
(4.10)
Note : In adiabatic changes, for example, volume increase with no heat added (dQ = 0).
dS = 0 i.e. S is constant.Also dnj = 0 so
is also constant.
During irreversible changes, the total S in the Universe increases. The total
of the
Universe also increases because the equilibrium macrostate must be the maximum
.
Now we consider 2 systems with entropy S1 and S2 and disorder number
1 and
2 ,
Total entropy,S = S1 + S2
(4.11)
Total
=
1
2
(4.12)
S f (
)
(4.13)
Now
so S1 = f (
1 ) and S2 = f (
2), Now
f (
1
2 ) = f (
1 ) + f (
2)
(4.14)
28
Then
So
@f (
1
2 ) = @f (
1
2 )
= @f (
1 )
@
1
@ (
1
2 ) 2
@
1
(4.15)
@f (
)
= @f (
1 )
@
2
@
1
(4.16)
@f (
1
2 ) = @f (
)
= @f (
2 )
@
2
@
1
@
2
(4.17)
1 @f (
1 ) = 1 @f (
2 )
2 @
1
1 @
2
(4.18)
Also
Then
1 @f (
1 ) =
2 @f (
2 ) = k
@
1
@
2
where k is a constant by separation of variables.
(4.19)
So
S1 = f (
1 ) = k ln
1 + C
(4.20)
S2 = f (
2 ) = k ln
2 + C
(4.21)
S = k ln
1 + k ln
2 + C
= S1 + S2
(4.22)
S = k ln
(4.23)
= 1 and S = k ln
= 0. When more microstates are availiable
> 1 so S > 0. The
lesser the knowledge about a system, the more disordered it gets.
From the formula which we obtained for the relation of entropy with
, we are unable
to deduce the value of k. The value of k comes out from the ideal gas equation.
29
S = k log
(E0 ) = 0
Practically, some small interactions (e.g. nuclear paramagnetism) may lift the ground
state degeneracy. If kT > "int, then S 6= 0 at a given T. 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).
Note that it is meaningless to talk about the exchange of particles in the same state
because they do not exchange their positions.
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 internal energy U(T) increases
when T increases. Now we come to the formulation of the third law :
The Third Law of Thermodynamics states that as the temperature T ! 0, the
entropy S ! 0, it is approaching ground state as U(T) also approaches 0, ) that the
disorder number
tends to 1.
From the third law, T=0 is a theoretically correct statement, but it is an impossibility.
Why is this so?
The answer :
There exists very small interactions in the nucleus, made up of magnetic moments,
quadrapole moments and octapole moments etc. In order to make T = 0, the magnetic
moments are required to point in the same direction. However, experimentally, this is not
achievable.
The third law of thermodynamics can also be understood in a quantum mechanical
30
, 2~m @@x 2 + V ( ) = H
2
The V( ) consists of many interaction terms. Hence we can approach the total entropy,
S as a combination of entropies of many sub-systems :
Z=
X
j
,"j
gj e kT
(4.24)
@Z j = X ," g e,"j
@ V;N j j j
where
(4.25)
1
= kT
U=
nj "j
X ,"j
=N
Z j gj e "j
@Z j
= ,N
Z @ V;N
j
Since,
d = , 1
dT
kT 2
(4.26)
31
1 @Z = @ (ln Z )
Z
therefore,
ln Z j
U = ,N @ @
V;N
ln Z j
= NkT 2 @ @T
V;N
We know that
(4.27)
,"
nj = N
g
je j
Z
) ngj = NZ e"j
j
Then we work out ln
,
ln
= N ln N ! +
X
j
(nj ln gj , ln nj !)
= N ln N , N +
(4.28)
S = k ln
= kU + Nk ln Z
= UT + Nk ln Z
(4.29)
F = U , TS
(4.30)
F = ,NkT ln Z
(4.31)
dF = dU , TdS , SdT
= TdS , PdV , TdS , SdT
= ,SdT , PdV
(4.32)
Xj
= N ln N + ( nj "j ) + N ln Z , N ln N
= U + N ln Z
Therefore
Entropy :
32
@F ) dV + ( @F ) dT
dF = ( @V
T
@T V
@F )
P = ,( @V
T
= NkT ( @ ln Z )T
@V
S = ,( @F
@T )V
(4.33)
@Z
(4.34)
= Nk ln Z + NkT
Z @T
= Nk ln Z + UT
Then we can use the results above to compute the heat capacity at constant volume :
Cv = ( @U
(4.35)
@T )V
Chapter 5
Applications of Maxwell-Boltzmann
Statistics
5.1 Classical Perfect Gas
To apply the Maxwell-Boltzmann Statistics to the classical perfect gas, we require a few
conditions :
1. The gas is monatomic, hence we consider only the translational kinetic energy (KE).
2. There is no internal structure for the particles, i.e. no excited electronic states and
the paricles are treated as single particles.
3. There is no interaction with external elds, e.g. gravity, magnetic elds.
4. The energy is quantized as in the case of particle in a box (in QM).
5. There is a weak mutual interaction - only for exchanging energy between particles
and establishing thermal equilibrium, but there is no interference on each other's
"j .
6. The discrete levels can be replaced by a continuous one if the spacing is small as
compared to T, i.e. " kT which is the classical limit.
7. The atoms are pointlike - occupying no volume.
From quantum mechanics,
2 2
(n2 + n2 + n2 )
"j = 2~mL
x
y
z
2
33
34
Now we compute the partition function, Z and in this case gj = 1, because all the
states are summed over.
X "j
Z = e, kT
j
XXX
~2 2
Z1 2
2
1 1
2
mL
kT
e 2mL2 kT dnx = ( ~22 ) 2 2
e,x dx
Z 1,1 2
1
2
mkT
= L( h2 ) 2
e,x dx
~2 2 n2x
e,x2 dx = (
e,x2 dx
Z,1
1Z
1
,1
e,y2 dy) 21
So,
(5.2)
,1
,1
Therefore
~2 2 21
Let x = ( 2,
mL2 kT ) nx
where
(5.1)
(5.3)
3
2
)
Z = L3 ( 2mkT
h2
3
2
= V ( 2mkT
)
2
h
(5.4)
ln Z = lnV + 3 ln T + 3 ln 2mk
2
2
h2
(5.5)
ln Z )
P = NkT ( @@V
T
= NkT
V
(5.6)
35
i.e. PV = NkT
since
PV = nRT
N
n
because
Nk = nR
k = Nn R
k = NR
A
(5.7)
ln Z )
U = NkT 2 ( @ @T
V
= NkT 2 32 T1
= 23 NkT
(5.8)
U = 32 kT
dn
d"
(5.9)
(5.10)
(5.11)
To calculate the density of states, we consider the quantum numbers nx, ny and nz
making up the grid points with each grid point representing one state.
36
By writing
Using
we obtain,
Therefore,
dn " = 1 (4R2)R
d"
8
= 1 (4R2) dR "
8
d"
(5.12)
2 2
R2
" = 2~mL
2
d" = ~22 R
dR mL2
dn " = R mL2 "
d"
2 ~232
) 2 L3 " 12 "
= 4 (2m
~3 3
(5.13)
3
2
Therefore,
(2m 1
= 2V h3 ) " 2 "
"
3
3 , kT
2 1
(2
m
)
V
Nh
e
n =
2v h3 " 2 "
(2mkT ) 32
1 , "
2
kT
N"
= p e 3 "
2
4 (kT )
2
" = 2pm
d" = p
dp m
(5.14)
ZZZ
all p space
dpxdpy dpz =
=
2
Z0 1
0
dp
sin pdp
p2dp
4p dp
2
In =
p0
I0 = 2
I1 = 12
I2 = 12 I0
I3 = I1
I4 = 32 I2
e,x2 xndx
37
(5.15)
(5.16)
(5.17)
(5.18)
38
Z1 2
3
3
Nm
4
2
kT
2
g(v)dv =
( )
e,x x2dx
(2mkT ) 32 m
0
=N
(5.19)
Z1
1
v = N
vg(v)dv
0
Z1 2
3
m
4
2
kT
2
=
)
e,x x3 dx
3(
m
2
(2mkT )
0
r
= 8kT
m
(5.20)
1
0
v2 = N1
v2g(v)dv
0
Z1 2
3
m
4
e,x x4 dx
=
5
2
(2mkT ) 0
3
= kT
m
(5.21)
(5.22)
3kT > v
m
(5.23)
(5.24)
39
Vp
V2
"j = (j + 12 )~!
! = km0
Assume the oscillators are independent and distinguishable,
,"j
kT
nj = N
e
Z
Z=
1
X
j =0
(j + 1
2 )~!
e,
= e, 2~kT!
kT
1
X
j =0
j ~!
e, kT
1
~!
1 , e, kT
~!
1
= e, 2
1 , e,~!
= e, 2~kT!
(5.25)
1
X
n=0
arn = 1 ,a r
ln Z = , 1 ~! , ln(1 , e,~! )
2
U = ,N @lnZ
@
= 21 N ~! + 1 , Ne,~! ~!e,~!
= N ~![ 1 + ~!1 ]
2 e ,1
1
= N ~![ 2 + ~! 1 ]
e kT , 1
At low T, U 12 N~!, it means that the oscillators are in ground state.
At high T,
40
1
U = N ~![ 21 +
]
~!
1 + kT + ::: , 1
]
= N ~![ 12 + kT
~!
= NkT
(5.26)
(5.27)
(5.28)
The Equipartition theorem states that all terms in the Hamiltonian with squared coordinates (x or px etc) will contribute 12 kT to the average energy, provided quantization
is not important. This is re
ected in the classical regime at high T (where kT >> "int.
Example 1 : Ideal Gas,
H = kinetic energy only
2
p2y p2z
p
x
= 2m + 2m + 2m
Therefore
U = 32 kT N atoms
= 32 NkT
41
Therefore
With quantization setting in at low T, the Hamiltonian is frozen out and the contribution
is not 12 kT.
Example 3 : Diatomic gas,
For translational motion,
2
p2y p2z
p
x
Htrans = 2m + 2m + 2m
2
L2
Hrot = 12 LI x + 21 I y
Therefore, the total internal energy, U should be 72 NkT. However, the experimental
results show that U = 52 NkT.
The reason is because the vibrational motion is frozen out, i.e. ~!vib >> kT. So in
terms of Hvib , the atoms are in ground state, i.e. atoms don't appear to vibrate much at
normal temperature.
Total H = Hvib + Htrans + Hrot
(5.29)
Chapter 6
Paramagnetic Systems
6.1 Introduction
For a paramagnetic spin system, the atoms have unpaired electrons or partially lled
orbitals. The net angular momentum J~ for each atom is equal to both the linear orbital
angular momentum, L~ and spin, S~ . It also acts like the magnetic moment.
J = ,gJ B J
When the system interacts with an external magnetic eld,
Hamiltonian, H = ,~ B~
= gJ B B~ J~
= gJ B Bz Jz (Quantization)
(6.1)
(6.2)
42
43
3
2
1
2
-1
2
-3
2
B
0
(6.3)
(6.4)
(6.5)
44
So
"" = , 12 gsB B
"# = + 12 gsB B
Using the Maxwell-Boltzmann distribution,
g B B
+ s2kT
e
n" = N
Z
, gs2kTB B
n# = N
e
Z
where
gs B
The entropy S :
(6.7)
(6.8)
(6.9)
gs B
Z = e+ 2kTB + e, 2kTB
BB
= 2 cosh( gs2kT
)
gs B
gs B
(, 1 gsB Be+ 2kTB + 1 gsB Be, 2kTB )
E=N
Z 2
2
Ng
B
g
B
= , s B (sinh( s B ))
Z
2kT
Ng
g
s B B
=,
(tanh( sB B ))
Z
2kT
S = UT + Nk ln Z
= , NgsB B (tanh( gsB B )) + Nk ln(2 cosh( gsB B ))
T
2kT
2kT
The magnetization M :
where " = B
(6.6)
X
M = V1 nj j
j
X
j B
= VNZ j e+ kT
gs B
gs B
= VNZ [ 12 gsB e 2kTB , 21 gsB e, 2kTB
BB
= VNZ gsB sinh( gs2kT
)
gsB B )
= 12 N
g
sB tanh(
V
2kT
E
= , BV
(6.10)
(6.11)
(6.12)
(6.13)
45
0
-(J-1)
-J
B=0
mJ =,J
J
X
mJ =,J
= e,yJ
eymJ
2J
X
eymJ
mJ =0
(2J +1)y
= (e,yJ ) e ey , 1, 1
(J +1)y
,Jy
e
,
e
=
ey , 1
(J + 12 )y
,(J + 12 )y
,
e
e
=
e 12 y , e, 12 y
(6.14)
sinh(J + 12 )y
sinh y2
n
(G.P sum = a(rr ,,11) )
(6.15)
46
Therefore,
Then
where
,"J
nJ = N
e
Z
N
= Z e,gJ B BmJ
(6.16)
X
Magnetization, M = VNZ gJ B mJ egJ B BmJ
@Z
= VNZ 1 @B
@y
= VNZ 1 @Z
@y @B
= VNZ gJ B @Z
@y
@ ln Z
=N
g
J B
V
@y
(6.17)
(6.18)
(J + 21 ) cosh(J + 12 )y 12 cosh y2
g
(
, sinh y )
M=N
V J B
sinh(J + 12 )y
2
1
1
1
y
=N
g
J B ((J + ) coth(J + )y , coth )
V
2
2
2
2
N
= V gJ B JBJ (y)
(6.19)
(6.21)
(6.22)
So,
(6.23)
,x
coth x = ex + e,x
e ,e
2x
= e2x + 1
e ,1
2
3
2
= (1 + 2x + 42x + :::: + 1)(1 + 2x + 42x + 83!x + ::::: , 1),1
2
= 21x (2 + 2x + 2x2 + ::::)(1 + x + 23x + :::)
2
2
= 1 (1 + x + x2 + :::)(1 , (x + 2x + :::) + (x + 2x :::::)2 ::::)
x
3
3
2
x
1
= (1 + x , x + x2 , x2 , + 2::::)
x
3
2
= 1 (1 + x + :::::)
x
3
1
x
= +
x 3
x
47
1 + (J + 21 )y ) , 1 ( 1 + y2 )]
3
2 y2 3
(J + 12 )y
(J + 12 )2y 1 y
, y , 12 ]
= J1 [ y1 +
3
= 31J [(J 2 + J )y]
= y (J + 1)
3
(6.24)
BJ (y) = J1 [(J + 12 )(
Therefore,
so,
(6.25)
y
M=N
g
J B J (J + 1)
V
3
2 2
N
g
J
(
J
+
1)
B
= V J B 3kT
(6.26)
@ )
= 0( @B
T
gJ2 2B 0J (J + 1)
=N
V
3kT
1
/T
(Curie's law)
(6.27)
48
Since,
Since,
(6.28)
Proof :
(J + 12 )y
,(J + 12 )y
e
,
e
ln Z = ln
2 1
,(J + 2 )2y , 1
,y ey , 1
1
2
= ln[e,(J + 2 )y e
,
ln[
e
2
2 ]
1 + (J + 12 )2y + ::: , 1 y
1
= ,(J + )y + ln(
) + , ln( 1 + y + :::: , 1
2
2
2
2
1
y
= ,Jy + ln[(J + 2 )y + ::::] , ln[ 2 + ::]
= ,Jy + ln(2J + 1)
ln(2J + 1)
or
(6.29)
(1 + y2 + :::) , (1 , y2 + :::)
(1 + (J + 21 )y + ::::) , (1 , (J + 12 + :::)
] , ln[
]
ln Z = ln[
2
2
= ln(J + 1 )y , ln y
2
2
= ln(2J + 1)
(6.30)
Then
S = Nk ln(2J + 1)
(6.31)
So,
Therefore
,x
coth x = ex + e,x = 1
e ,e
BJ (y) = J1 [J + 12 , 12 ] = 1
(6.32)
M=N
V gJ B J
(6.33)
where all spins are align in the same direction (parallel to B), hence ! 0.
49
y
,y
(J + 12 )y
,(J + 12 )y
2 ,e 2
e
e
,
e
ln Z = ln(
) , ln( 2 )
2
= (J + 12 )y + ln 12 , y2 , ln 12
= Jy
(6.34)
(6.35)
(6.36)
TL
Spin System
Heat
Bath
Lattice
at constant T
Heat flow
Entropy passed to lattice and heat bath =
dQ
Ts
2. Reduce the temperature by turning o the B-eld adiabatically, i.e. isolated from
heat bath.
50
TL
Ts
Spin System
Lattice
As B decreases, Sspin stays constant, so TS decreases. The lattice passes heat and
entropy back to spin. But this entropy is so small because of low TL , SLat is small,
so the heat passing is very small. (dQ = TdS). Hence both TS and TL will drop
drastically.
S
B=0
(1)
(2)
R
B=B
T
Note : They obey the 3rd law
Stage (1) : From P to Q, Isothemal Magnetization
Stage (2) : From Q to R, Adiabatic Demagnetization
Chapter 7
Applications of Fermi-Dirac
Statistics
7.1 Fermi-Dirac Distribution
From chapter 3, we obtain two quantum distributions :
1. Fermi-Dirac Distribution
nj = e, eg"j + 1
2. Bose-Einstein Distribution
(7.1)
nj = e, eg"j , 1
(7.2)
For either systems, = kT1 . This can be proven by having the quantum system in
contact with a classical perfect gas where = kT1 . The two s will reach equilibrium at
same temperature.
Now to identify for Fermi-Dirac distribution, we consider 2 fermion systems in thermal and diusive contact so to allow particle exchange. We also assume that the same
type of fermions for both systems.
With the same constraints :
X
X
ni + nj = N
X
ni "i + nj "j = E
=
i
j
Y
Y
j
= n !(g g,i n )! n !(g g,
n )!
i
51
(7.3)
X
i
52
dln
=
X
i
X
ni )dn + X(ln gj , nj )dn
= (ln gi ,
i
j
ni
nj
j
i
X
j
(7.4)
ln(gj , nj )dnj + dnj , ln nj dnj , dnj
=0
(7.5)
, (
So,
X
i
Xj
"idni + "j dnj ) = 0
ni , + " )dn +
(ln gi ,
i i
n
i
Then
X
j
(7.6)
ni , + " = 0
ln gi ,
i
ni
ln gj n, nj , + "j = 0
j
gi
ni = e, e"
i +1
g
nj = e,e"jj + 1
So the two systems in thermal contact have the same and the two systems in diusive
contact will have the same , which is related to .
The diusive contact gives rise to chemical equilibrium, so
i = j =
(chemical potential)
Suppose we take one of the systems :
Sj = k ln
j
X
= gj ln gj , (gj , nj ) ln(gj , nj ) , nj ln nj
j
(7.7)
dS = k
X
j
53
X gj , nj
ln
nj dnj
j
X
= k (, + "j )dnj
j
X
X
= ,k dnj + k [d(nj "j ) , nj d"j ]
=k
(7.8)
= ,kdN + kdU , kdW
TdS = ,kTdN + dU , dW
= ,dN + dU , dW
(7.9)
because
dU = TdS + dW + dN
Therefore
So
= kT
nj =
(7.10)
gj
(7.11)
+1
where dN is the work done in moving the fermions from one place to another, e.g electrical work.
" ,
e jkT
54
k
2m
and is dened by the following relation :
=
2
~2
2
k2 = L 2 (n2x + n2y + n2z )
(7.12)
(7.13)
nz
nR
ny
nx
(7.14)
(Note : we multiply the relation by 2 because of the 2 spin states and 18 because we
only take the positive octant, i.e. nx, ny and nz are all positive integers.)
Number of states between k and k+dk = 18 4k2dk 2 ( L )3
= V2 k2dk
dk d"
Number of states between " and "+d" is g(")d" = V2 2~m"
2 d"
m d"
= V2 2~m"
2 ~2 k
r 2
2
V
2
m
"
~
= 2 4
d"
~
2m"
3
2
V
(2
m
)
= 22 ~3 " 21 d"
= V C" 21 d"
(7.15)
(7.16)
55
where
3
2
(2
m
)
1
C = 22 ~3
Therefore,
N=
=
X
j
nj
gj
(7.17)
e("j , + 1
Z 1 g(")d"
=
e("j ,) + 1
0
E=
=
X
j
X
j
nj "j
"j gj
(
"
e j ,) + 1
(7.18)
"g(")d"
e("j ,) + 1
0
We solve equation (7.17) for (N; T; V ) and use in (7.18) to obtain ". This is dicult
to evaluate except at low T. We shall try to evaluate this in 2 cases
=
1. At T = 0
Probability of occupation of state of energy is fF ,D (") =
e("j ,) + 1
(7.19)
f F-D (E)
EF
For
(T = 0) = "F
Fermi energy
and
fF ,D (") = 0
fF ,D (") = 1
(7.20)
N=
"F
g(")fF ,D(")d"
g(")d"
Z "F 1
= VC
" 2 d"
0
3
= V C 23 "F2
=
and
56
22~3 ] 32
"F = [ 32N
V (2m) 32
2
2
2 ~
3
= ( 3N
)
V 2m
(7.21)
(7.22)
= 2~m kF2
2
) 31
kF = ( 3N
V
2
(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, all electrons occupy the lowest possible state subject to the Exclusion
Principle, so the states are lled until "F .
g(")fF ,D(")d"
Z "F 3
=VC
" 2 d"
0
2
= V C " 52
5
3
= 5 N"F
Total Energy, E =
(7.24)
2. At low T, kT
"F << 1, we want to nd Cv and we know that the experimental value
is proportional to T.
N=
Therefore,
U=
g(")fF ,D(")d"
"g(")d"
e(",) + 1
(7.25)
57
Then
Cv = ( @U
@TZ )V
(7.26)
1 (" , " )g (")e(",)
1 , 1 @ )]d"
F
[(
"
,
)(
,
=,
kT 2 kT @T
(e("j ,) + 1)2
0
@ = 0 and = " ,
Since does not change much, so we assume @T
F
Z
1 (" , " )2 e(","F ) V C" 21 d"
F
Cv = kT1 2
(7.27)
(
e(","F ) + 1)2
0
Now,
e(","F ) = , @fF ,D (")
(7.28)
(e(","F ) + 1)2
@"
The maximum occurs at " = "F . The value drops to 1e of the maximum value when
" , "F kT . So the function is sharp for small kT (<< "F ).
dfF-D (E)
dE
kT
EF
The contribution to the Cv integral comes mainly from values of " near "F , i.e.
" "F
(7.29)
(7.30)
(7.31)
58
T=0
T>0
EF
For T = 0 : All states are occupied within " = "F is a truncated parabola.
For T> 0 : We will expect electrons to gain energy kT. However, 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. This results in a
rounded-o cli at "F .
An alternative estimate :
Number of electrons involved is g("F )kT and they gain kT. Therefore
Energy of excitation = g("F )k2T 2
(7.32)
Chapter 8
Applications of Bose-Einstein
Statistics
8.1 Introduction to Black Body Radiation
First, we discuss radiation in thermal equilibrium. The radiation is enclosed in vessel, and
all the walls are at temperature T. The atoms in the wall will absorb and emit electromagnetic radiation. At equilibrium, the distribution of photons will follow the temperature T.
Second, in order to study the radiation, we assume a hole is cut in the chamber wall to
emit some radiation. The hole is very small so that the equilibrium is not disturbed. This
will approximate to a blackbody. The black body will also absorb all radiation falling on
it. The radiation bounces inside the chamber until nally being absorbed.
In this chapter, we will study black body radiation using statistical mechanics. We
note that the photons have the following characteristics :
1. The photons have spin 1 (bosons) and they obey Bose-Einstein statistics.
2. The photons do not interact with one another.
3. The photons have zero rest mass and travel at c, the speed of light.
4. The photons satisfy the dispersion relation, ! = ck, so,
" = ~! = ~ck
59
60
We consider a system of a small blackbody placed inside a chamber with perfect insulating
walls. The features of the system are as follows :
1. The blackbody absorbs and emits radiation until thermal equilibrium is established.
2. The number of photons are not conserved because of absorption and re-emission.
This implies that and = 0.
3. The blackbody is so small that heat capacity is negligible. The energy content of
photons are not changed.
E=
X
j
nj "j = constant
For bosons,
Y (nj + gj , 1)!
j nj !(gj , 1)!
(8.1)
Maximise
subject to E = constant only.
ln
=
=
=
j
X
j
d(ln
) =
X
j
X nj + gj , 1
ln( n
)dnj = 0
j
(8.3)
X
j
dnj "j = 0
So,
61
(8.4)
nj = e"jgj, 1
(8.5)
(8.6)
Prove = kT1 by having the photon system in thermal contact with another system at
temperature T and use walls that can exchange energy.
(8.7)
nz
nR
ny
nx
62
Therefore,
since
(8.8)
2
n2R = L2 k2
T2
T2>T1
T1
e~! 3!2 , !2 ~e~! = 0
(e~! , 1)2
(8.9)
(8.10)
(8.11)
(8.12)
(8.13)
63
) 3(e~! , 1) = ~e~!
) 3(ex , 1) = xex
where x = ~!
Solving numerically, x 3, by neglecting (-1), or more accurately, x = 2.822.
Therefore,
~!max
kT = 2:822
or
kT
!max = 2:822
~
(8.14)
(8.15)
(8.16)
(8.17)
So, as T rises, the colour of the blackbody changes from red to blue :
u(T ) = aT 4
where
u(!; T )d!
Z 1 !3d!
~
= 23
c 0 Ze~! , 1
1 x3 dx
= c~3 41~4
ex , 1
0
4 4
4
= k2 T3 3
c ~ 15
(8.18)
(Stefan-Boltzmann law)
(8.19)
Therefore
2 4
a = 15ck3~3
Consider a tiny hole, A, with photons coming from direction ( ! + d, ! + d),
with a subtended solid angle d
, where
d
= r sin drd
r2
= sin dd
64
dA
Therefore,
No. of photons passing per unit time from direction ( ! + d, ! + d) with a
frequency range ! to ! + d!
= Volume of Parallelpiped Fractional solid angle Number density in frequency interval
t
= dAc cos d4
N (!V)d!
Therefore, the total energy radiated per unit time in frequency interval ! to ! + d!
Z 2 Z 2
~! N (!)d!
=
d sin d dAc4cos
V
0
0
= 1 c~!dA N (!)d!
4
V
1
= 4 cu(!; T )dAd!
Therefore
Power radiated per unit area in frequency interval from ! to ! + d!
= 14 cu(!; T )d!
2 k4
15c3 ~3
Therefore,
2 4
= 60ck2~3
= 5:67 10,8 W m,2 K,4
65
Chapter 9
The Classical Limit
9.1 The Classical Regime
In the classical regime, there is a lack of discreteness, we consider the continuous variable
" rather than the discrete energy "r .
The energy spacing is " << kT, and < nr > <<1 which means that there are many
unoccupied states, which are averaged over time.
In the Fermi-Dirac or Bose Einstein statistics, the classical regime is only satised if
1
e("r ,) 1 << 1
i.e.
M-B distribution
So all the 3 distributions(Maxwell-Boltzmann, Fermi-Dirac and Bose-Einstein) distributions approximate to Maxwell-Boltzmann distributions in the classical regime.
According to the Maxwell-Boltzmann statistics,
,"r
< nr >M-B= N
Z e << 1
for all r, including r = 0.
So we require
N
Z
66
(9.1)
67
32
V
Z = h3 2mkT
so,
1 32
Nh3
V 2mkT << 1
N 32 h2
T >> V 2mk
The conditions are high temperature, T and low density NV , and high mass, m.
Assume the energy is equipartitioned,
" = 32 kT
(for each atom)
2
p
=
2m
So,
p
p = 2m" = h
(in QM terms)
dB
Then
32 1 32
1
2mkT = 43 m"
3 32 1
= 2 p3
3 32 3
dB
= 2
h
and
3
N 3 2 3 << 1
V 2 dB
i.e.
2 12 V 31 2 21
dB << 3
N = 3 l0
where l0 is the average seperation between atoms.
Examples :
(9.2)
(9.3)
68
1. He gas :
so l0 = 2 10,7cm
At T = 273 K, and
m = 6 41023 g
so l0 = 4 10,8cm.
Since dB > l0 , so Bose Einstein statistics apply.
2. For conduction electrons :
Assume 1 electron per atom,
hence
l0 2 10,8cm
For m = 9:1 10,31 kg and T = 273 K, dB > l0, so Fermi-Dirac statistics apply.
g(E)f F-D (E)
T=0
Approximately
M-B
T>0
EF
f F-D (E)
T=0
T>0
0
EF
69
Note that
V
N
T
S
V
N
T
S
S = UT + Nk ln Z
2mk
3
3
3
= Nk + Nk ln V + ln T + ln
2
2
2
h2
Suppose now N ! 2N, V ! 2V, we expect S!2S.
However,
(9.4)
(9.6)
(9.7)
70
V + 3 ln T + 3 ln 2mk
S = 52 (2N )k + 2Nk ln 22N
2
2
h2
= 2Sold
(9.8)
Chapter 10
Kinetic Theory of Gases
10.1 Introduction
Consider the distribution (for e.g. velocity, momentum, position, energy, etc) of system
of gas molecules in thermal equilibrium.
At thermal equilibrium, the momentum and spatial coordinates are independent of
each other, i.e. a molecule in any position (x,y,z) can have any momentum (px, py , pz ).
For the Hamiltonian :
1. The kinetic energy (KE) terms are determined by px, py and pz .
2. The potential energy (PE) terms are determined by x, y and z.
The Boltzmann law applies to every coordinate in the Hamiltonian.
For example,
1. The probability that x-momentum which lies between px and px+dpx is :
,p2
1 ,p2x
e 2mkT dpx = 1
,1
(10.1)
(10.2)
A0
1 ,mvx2
e 2kT dvx = 1
,1
71
(10.3)
(10.4)
72
3. The probability that the molecule is found between and x and x+dx is :
P [x]dx = Be
where
,V (x)
dx
(10.5)
1 ,V (x)
e kT dx = 1
,1
(10.6)
kT
px, v x
d
dc
d
(10.7)
(10.8)
73
c =
3. Mean square speed, c2 :
8kT 21
cP [c]dc = m
1
0
c2 =
p
4. Root mean square speed, c2 :
1
0
kT
c2P [c]dc = 3m
kT
c2 = 3m
12
(10.9)
(10.10)
(10.11)
(10.12)
Mean KE = 1 mc2 = 3 kT
2
2
(10.13)
(10.14)
vx2 = kT
m
(10.15)
74
ZZZ
Ac cos t
NP [c]dc sindd
4
V
(10.18)
(10.19)
The number of molecules with speeds c!c+dc from direction ( ! + d, ! + d)
imping a area in time t is
N cP [c]dcsinddAt
4V
The distribution is proportional to c P[c] dc.
The mean speed of escape, ce :
R 2
dc
ce = R ccPP[[cc]]dc
=
3kT
8kT 21
( )
m
12
9
kT
=
8m
(10.20)
75
1 mc = p 8kT
4
kT m
/ 112
m
So, the smaller molecules escapes(euses) faster.
12
(10.21)
,dx
(10.22)
Probability of collision in dx = dx
(10.23)
(10.24)
According to (10.22),
Then,
Probability of collision in dx = 1 , e
,dx
dx
= 1 , 1 , + ::::
dx
(10.25)
76
1
0
xe, x dx
x
= [,xe, ]1 +
0
= [,e, x ]1
0
=
(10.26)
1
0
e, x dx
(10.27)
d
d
= d2
(10.28)
So,
(10.29)
(10.30)
(10.31)