THE THERMOI)Y AMICS OF GASES

Chapter 7 then obtained in logarithmic form by applying Stirling's approxi-

mation. Taking equation 2.7 to give

log W = N log N - N + I (l1s log gs -II, log ns + n.)

The Thermodynamics of Gases
= N log N +(I
log ~)
n. s
I1s

then the most probable configuration is obtained, on substituting

from equation 2.20 for sl»; as

In this chapter a discussion will be given of the thermodynamic log Wmax = N log N + I ns log {e-(~+(J<s)}

functions of a perfect gas in which any interactions between the

molecules, even those which occur during collisions between the 7.1
molecules, are considered to have a negligible effect on the thermo-
dynamic properties of the gas. It will be seen that anomalous Writing N = I I1s and E = I ns£s equation 7.1 becomes
results are obtained for the entropy and free energy of the gas if
all the molecules are treated as being distinguishable, classical log Wmax = N log N -aN - f3E 7.2
systems. In order to avoid these anomalies it is necessary to treat
the gas in a 'semi-classical' manner in which it is assumed that all where E is the total energy of the assembly. If the substitution is
molecules of the same isotope are completely indistinguishable. made for ea = A so that a = log A then, with f3 = - l/kT, equa-
It will also be seen to be convenient to introduce the quantity 1/h3 tion 7.2 gives
as the number of states per unit volume of phase space to replace E
log Wmax = N log N - N log A + kT
the undefined constant of classical statistical mechanics.
Except for a brief digression in the final section the molecules
N E
will be considered, in this chapter, to be structureless particles. = N log A + kT 7.3

(Although in certain cases it is mathematically convenient to

work with f3 as the variable instead of T-see for example equations
7.1. The weight Wmax for a classical perfect gas
6.19 and 6.21-it is not always convenient to use two alternative
As shown in equation 2.7 the weight of a given configuration of expressions for functions which depend on the thermodynamic
the molecules in a perfect gas which contains N classical structure- temperature. The future results will therefore be presented, in
less molecules is general, in terms of the temperature T while any simpler form
involving f3 may be given in parentheses.)
W = N! [1
s
{g=~}
ns·
(2.7)
7.2. The Boltzmann Partition Function
In place of the ratio N/A of equation 7.3 it will be found convenient
where ns is the occupation number of the sheet sand g. is the de-
to define a quantity Z such that
generacy of that sheet. Taking the energy of the sheet s to be £s
the occupation numbers for the most probable configuration are
given by equation 2.20 as ns = s.r:": where a and f3 are already
defined. The weight of this most probable configuration , Wmax s is

86 87
STATISTICAL PHYSICS FOR STUDE TS THE THERMODYNAMICS OF GASES

Using the values of ns from equation 2.20 this becomes The entropy is then obtained with the aid of equation 6.8 as

I gsea - <./kT S = k log Wmax

Z = -'-s _
ea E
klog Z+ T 7.7
or

7.4 (or, with Nk replaced by the universal gas constant R for a gram me
molecule of the gas,
E
In this form Z is known as the Boltzmann partition function (or S = R 10gZ+-)
T
simply as the partition function) of a system in the assembly.
This terminology is used because, in this expression for Z, indi- Substituting from equation 7.7 for the entropy in the expression
vidual terms in the summation determine how the systems of the F = E - TS allows the Helmholtz free energy to be expressed in
assembly are distributed, or partitioned, among the various terms of the partition function as, simply,
energy sheets.
The form of equation 7.4 is perfectly general but it is sometimes
useful to express the partition function in terms of the individual I F = -NkTlogZ I 7.8
energy states which are available. If the energy of the ith state is
taken to be Ei then, since the weight of an individual state is unity,
It is possible to obtain an expression for the total energy E in
terms of the partition function by direct substitution from equation
7.5 .
7 . 8 mto t h e expressIOn
. E = - T 2{a(F/T)}
--- 0f .
equation 6.1 8.
. aT v
However, a more direct method is as follows:
(Because of the possibility of expressing the partition function in The mean energy of a system in a classical assembly may be
this form, Z is sometimes referred to as the sum over states or the written as
state sum for a system in the assembly. The symbol Z is taken
from the equivalent German expression Zustandssumme.) E InsEs Igse(a-<s/kT)Es
?=_ = _s__ =-'s _
The partition function which is defined by equations 7.4 and
7.5 is not one of the generally measurable or measured thermo- N Ins I gse(a-<s/kT)
s
dynamic quantities nor does it appear in the normal thermo-
dynamic equations. However, it does form an important bridge Then, cancelling the common term ea and writing I gs e" <s/kT = Z,
between the statistical expressions for the state of an assembly this gives s
and the corresponding thermodynamic functions since these I gsEse - <s/kT
latter will be found to be given fairly simply in terms of the parti- 7.9
?=~----
tion function. Z
Substituting for Z = N /A in equation 7.3 gives the expression
Now, by differentiation of equation 7.4,
for the weight of the most probable configuration as
E
log Wmax = N log Z + kT 7.6

88 89
STATISTICAL PHYSICS FOR STUDENTS TI-IE THERMODY AMICS OF GASES

so that equation 7.9 may be written Finally it is noted that it is possible to obtain other thermo-
dynamic functions in terms of the partition function by reference
kT2{aZ} to the normal thermodynamic relationships. For example:
aT v (i) the specific heat at constant volume is obtained with the aid
f = ----'--'--
Z of equation 7.11 as

{aE}
= kT2{a log Z} 7.10 {alogZ 2a210gz}
aT v C, = aT = Nk 2T aT +T aT2 v
The total energy of the assembly is then (ii) the pressure of the gas is obtained from equations 6.15 and
E = Ns 7.8 as
or
p---_ {aF} _-NT--k {a log Z} 7.14
av T av T
E = NkT2{a log Z} 7.11
aT v
7.3. The Evaluation of the Classical Partition Function
(A simpler expression in terms of {3 is obtained from equation
In the evaluation of the classical partition function it is possible
7.11 as
to replace the summation over sheets in equation 7.4 by an inte-
_ {alogZ} gration over all possible energies. If the number of energy states
E - N a{3 v
in the energy range E to E + de is written as in equation 2.47, i.e.
Substituting this value for E in the equation 7.7 for the entropy
gives

S = Nk[IOg Z _{aa log Z}

log {3 v
]
then the partition function becomes

while the free energy is simply

F = N
logZ
)
= f~ e-·1kTg(E)dE
{3
Referring again to the expression for the free energy in equation = 211: BV(2m)t J~ E-! e-'lkT de
7.8 it is seen that
From equations A5.9 and A5.10 of Appendix 5 the integral In
F this expression is
10gZ =
NkT
or
Z = e-FINkT 7.12

Writing FIN = [, the free energy per system, the partition func- so that
tion becomes
\
I Z = BV(211:mkT)t I 7.15
7.13
as would be expected from the definition of Z as N I A (see

90 91
 I
STATISTICAL PHYSICS FOR STUDE TS THE THERMODYNAMICS OF GASES

equation 2.55). Substituting for this value of Z in equation 7.8 structureless the partition function will contain other energy
gives the free energy as terms than those due to purely translational motion and some
aspects of these energy terms are discussed in section 7.6. (A more
F = -NkTlog[BV(2nmkT)t] 7.16
complete discussion of the case of the diatomic molecule is given
and the entropy of the gas is in Chapter 8.) In particular the classical energy of the molecules
will be increased above the value given in equation 7.18 depending
S= _{aF}
aT v
on the increased number of degrees of freedom of the molecules
when they are no longer structureless.
= Nklog[BV(2nmkT)t]+tNk 7.17 The effect of the assumed distinguishability of the molecules
on the thermodynamic properties of the classical gas will now be
Since equation 7.15 gives
a log Z} 3 1 ' considered.
{ ---er v = - -, then the total energy
2 T
of the gas of N molecules is given by equation 7.11 as 7.4. Gibbs' paradox
E = tNkT 7.18 If the entropy of a classical perfect gas is computed from equation
7.17 there is found to be a paradoxical result for the case when two
as is expected for a classical perfect gas.
equal volumes of the same gas are mixed together. Consider the
In classical statistics the constant B in the density of states is
two equal volumes of the same gas, being at the same temperature
not determined and there is therefore an uncertainty in the classical
and pressure and containing the same number of molecules,
partition function of an assembly. This uncertainty gives an in-
which are shown as volume 1 and volume 2 in Fig. 21. If these
determinate factor, which depends on the value of log B, in both
two volumes separately each have an entropy S, the value of this
the free energy and the entropy of the assembly. However, there
entropy will be given by equation 7.17 as
is no uncertainty in the energy or the specific heat of the assembly
S = Nk log[BV(2nmkT)t] +tNk
since these quantities depend only on the differential of log Z
and any constant terms in Z are therefore eliminated in these cases.
The equation of state of the classical perfect gas may be ob-
tained from the partition function of equation 7.15 by the use of
equation 7.14 so that, since {a log z/avh = l/V,
E,V,NTS,

Volume1
1+ 6-1
Volume 2
2E_,2_V_,2_N_.T_,S_T_,P _

Volume1+Volume 2
Fig. 21. The mixing of two equal volumes of the same gas.
p=NT-- k {a log Z}
av T The total entropy ST, obtained by mixing together the two vol-
NkT umes, is given by replacing N by 2N and V by 2V while the temper-
7.19 ature, being an intensive quantity (i.e. independent of the extension
V
of the assembly) remains unchanged. Then
Writing Nk = R this gives the normal equation of state of a ST = 2Nk log[B~V(2nmkT)t]+t. 2Nk
gramme molecule of a perfect gas, i.e.
= 2{Nk[log BV(2nmkT)tJ+tNk} +2Nk log 2
pV= RT 7.20 = 2S + 2Nk log 2 7.21
with no indeterminate factors. From this equation it would appear that the removal of a partition
The thermodynamic quantities given so far have been derived from between two equal volumes of the same gas causes an in-
on the assumption that the molecules of the gas are structureless crease in the total entropy and that this increase is given by the
and that they are all distinguishable. If the molecules are not 'mixing term' 2Nk log 2 (or 2R log 2 for two gramme molecules).
92 93
STATISTICAL PHYSICS FOR STUDE TS THE THERMODY AMICS OF GASES

Conversely, the replacing of the partition to recreate two separate, Thus, with the entropy taken as S = k log W for each of the
equal volumes of the same gas would presumably return the total volumes independently, the total entropy becomes
entropy to its original value of 2S. It would be expected, however, ST = klog WT
that the presence, or otherwise, of a partition between the two
volumes would have no effect whatever on the entropy if the ga
= 2klog W+2Nklog2
in each volume is the same. This apparently contradictory be- = 2S+2Nklog2
haviour of the entropy is known as Gibbs' paradox. in agreement with equation 7.2l.
It may be seen from closer study that there is, in fact, no real
As has been pointed out, if the molecules in the two volumes
paradox in this phenomenon. Since the systems in a classical
were indeed identical the entropy of the combination would be
assembly, and hence the molecules in a classical perfect gas, are
simply ST = 2S and the removal or otherwise of the partition
defined as being completely distinguishable from each other, then
between the two volumes of the gas would have no effect on the
any two volumes of a classical gas must be taken to be completely
total entropy. From this it is seen that there is necessarily an error
dissimilar even if they are considered to be composed of molecules in the expressions derived classically for the entropy, and also the
of the same isotope of the same element. In this case of complete
free energy, of a perfect homogeneous gas composed of identical
distinguishability there is no difference in the entropy of mixing molecules. In the following section it is shown how this error can
of the combined volumes whether they are considered to be, say,
be eliminated if the gas molecules are treated in a 'semi-classical'
two equal volumes of oxygen or one volume of ~xygen and one manner.
volume of nitrogen. (There will, however, be a difference m the (It is interesting to note that the same mixing term arises from
individual entropies due to the dependence of the term (2nmkT)t
the thermodynamic expressions for the entropy of a gramme
in equation 7.17 on the mass of the molecules.) Thus, under ~his
molecule of a perfect gas, namely
assumption, once the partition has been removed the original
state cannot be restored by its being replaced.
S = C, log T + R log V + constant 7.22
and
The mixing term which occurs in equation 7.21 may be seen to S = CplogT-Rlogp+constant 7.23
arise from the increase in volume which is available to the mole- where Cp is the specific heat at constant pressure. If two equal
cules when the partition is removed. If the molecules were actually volumes of gas at the same temperature and pressure are added
identical so that the interchange of two molecules could not be together so that Cp, Cv, R and V must be replaced by 2Cp, 2Cv,
detected: there would be no new configurations of the assemblies 2R and 2V respectively then it is apparent that equation 7.22 will
created by the removal of the partition. However, since the mole- introduce a mixing term of 2R log 2 while equation 7.23 will not.
cules have been considered to be classical, the removal of the The difference clearly arises from the fact that V is an extensive
partition will ,create, for each molecule, two p.ossible positions in quantity which depends on the amount of gas considered while T
space for every single position which was available before. ~here and p are intensive quantities which do not. While it is a useful rule
are N molecules in each volume and it follows that there will be in thermodynamics that equation 7.22 is used in computing the
2N times as many arrangements for the molecules of each volume entropy of a mixture of two different gases and equation 7.23 is
as there were before the partition was removed. Thus, if the used for the entropy of two volumes of the same gas, it is only by
equilibrium weight of one of the assemblies when it occupies a the application of the statistical analysis that the problem can be
volume V is W, then the equilibrium weight of the assembly when properly resolved.)
it is allowed to expand into the volume 2V will be W. 2N.
If the..total weight WT of the combined volume of gas is taken as
the product of the individual weight then, on mixing,
7.5. The semi-classical perfect gas
It is possible to obtain a correct, consistent expression for the
entropy of a real perfect gas by using the appropriate quantum

94 95
STATISTICAL PHYSICS FOR STUDENTS THE THERMODYNAMICS OF GASES

statistics. The actual statistics chosen will depend, strictly speaking, where the approximations (ns + gs -1) ::= (ns + gs), gs + ns ::= ~ and
on whether the gas molecules are in fact bosons or fermions. n, ns
However, in dealing with a gas at ordinary temperatures and ns + gs}
Iog {-- = log {ns}
1 +- ::= -n, have been used.
pressures, it is mathematically convenient to go to the classical gs gs gs
limit of these quantum statistics where the occupation number of
each sheet, ns, is small compared with the number of available (iii) log WFD = L [gs log gs - ns log ns - (gs - ns) logtg, - ns)]
s
levels, gs. In-this limiting case it will be seen that the three types of
statistics give rise to the same result for the entropy and for the = ~[ n, 10g{ gs~ns}_ gs 10g{gs~ns}J
distribution of energies provided that the term N! is removed
from the weight of the classical assembly. It is necessary to remove
this term N! from the classical weight since this is the factor which ::= L (ns log~ns + ns)
s
7.25c
gives the number of arrangements of the molecules among them-
selves and which, therefore, arises explicitly from the assumed where approximations similar to those in (ii) have been intro-
distinguishability of the molecules. duced.
The weight of the configuration of an assembly of 'semi- It is clear that under the conditions postulated here the weight
classical' systems is obtained by modifying equation 2.7 of the of a given assembly is very nearly independent of the type of
Maxwell-Boltzmann statistics to give system of which the assembly is composed. The equilibrium energy
~s
distribution of the systems will therefore be very close to the
WMB = Il-, 7.24 Maxwell-Boltzmann form ns = gs e«-··/kT for each case and the
s ns· equilibrium entropy will be given by these values of ns.
The corresponding weights for the Bose-Einstein and Fermi-
Dirac distributions are T a kimg Iog-gs = {fS --IX } t h e equations
. .
7.25 give
ns kT
W. - n(ns+gs-I)! (c.f 43) 7.24'
BE - ( .
s ns! gs-I)! log Wmax= ~[ns{kf~-IX}+nsJ
and
w.FD -- Il gs! (cf. 5.4) 7.24" E
s ns·, ( gs-ns )'
. = --NIX+N
kT
respectively. In the classical limit when gs ~ ns ~ I Stirling's
approximation gives: since L ns = Nand L nsfs = E. The entropy of the assembly,

(i) log WMB = L (a, log gs - ns log ns + ns) s= k log Wmax, is thus
E
7.25a S = --kNIX+kN 7.26
= ~ ( ns log ~ + ns) T

The constant e« = A may be taken from equation 7.4 to be given

(ii) log WBE ::= L [(ns + gs) log(ns + gs) - ns log ns - gs log gs]
by N /Z so that IX= 10g(N /Z). The equation 7.26 can thus be
written in terms of the partition function as
S S
= ~[ns 10gt :' gs} + s, 10gt :' gs}]
Z E
S = Nklog-+-+Nk 7.27
N T
::= L (ns log~ns + ns)
s
7.25b
97
96
 STATISTICAL PHYSICS FOR STUDENTS THE THERMODYNAMICS OF GASES

For a gas composed of structureless, semi-classical molecules from equation 7.27 in the expression F = E - TS gives
the energy E is simply the energy of translation ~NkT. The parti-
Z
tion function for the quantum assembly is given by equation 7.15 F = -NkTlogN-NkT
with the indeterminate factor B replaced by h - 3, the quantum
mechanical expression for the number of allowed states per unit = -kT{N log Z-(N log N -N)}
volume of phase space. * That is
Using Stirling's approximation this gives

F = -kT(logZN-logN!)
7.28 or

ZN
On substituting for the values of E and Z in equation 7.27, the F = -kTlog- 7.30
entropy is obtained as N!

The quantity ZN/N! is sometimes referred to as the total parti-

S=N"1.og
'sl [V(2nmkT)t]
Nh3 +2
5} 7.29
tion function of the assembly while the partition function Z is taken
as referring to an individual system. Giving the total partition
function the symbol Z so that
ZN
This expression is the Sackur- Tetrode equation for the entropy
Z = -N! 731
.
of a gas which has a volume Vand is composed of N indistinguish-
able, structureless molecules at temperature T. In this expression
then equation 7.30 for the free energy becomes
the classical dependence of the entropy on the extensive variable
V is replaced by a dependence on the intensive variable V/N, F= -kTlogZ 7.32
which may be considered as the volume per molecule. Therefore,
The total partition function can thus be written as
if two equal volumes V of the same gas under the same conditions
- are added together to form a volume 2 V then, since the volume per
molecule remains unaltered, the mixing of the two volumes will I Z = e-FjkT I 7.33
produce no change in the total entropy as given by equation 7.29.
If, however, the two volumes of gas consist of two different types (A further discussion of the properties of the total partition
of molecules then the mixing of the two volumes will increase the function will be given in Chapter 9 when the canonical ensemble is
volume available to the two types of molecule from V to 2V. considered.)
The volume per molecule will thus be doubled and there will be a It is left as an exercise for the student to show that the equation.
corresponding increase in the total entropy due to the 'mixing' of state and the total energy of the gas, as derived from the free
term, 2N k log 2. energy given in equation 7.30, are the same as those derived for
the completely classical gas.
It is now possible to obtain an expression for the free energy F
for a perfect semi-classical gas. Using the form of the entropy
7.6. Components of the Partition Function
* In some texts the number of states per unit volume of phase spaee is
If the systems which make up an assembly are not structureless,
assumed to be given by 11- 3 for both quantum mechanical and classical
systems. While this may be convenient, and it is certainly valid in thd semi- the energies of the systems will not be due to their translational
classical case given here, in the strict classical limit this density of states, motion alone. Thus, in a gas consisting of polyatomic molecules,
here given the symbol B, will tend to infinity. it is possible for the gas molecules to take energy in a number of
98 99
I

/
 THE THERMODY AMICS OF GASES
STATISTICAL PHYSICS FOR STUDENTS

independent modes (e.g. vibrational, rotational and electronic Now the mean energy of a system, for which the partition
function is Z and the temperature of the assembly is T, is given by
energy modes) besides the normal translational mode.
Consider a system which has its energy state defined by three (I = kT2{ a I;; Z} v' Substitution from equation 7.38 thus gives
independent energies E I, E2 and E3 which. are, for example, the
energies of translation, vibration and rotauon. If the first form. of
motion is in its ith state with energy Eij and the second and third
- = kTZ{alogZl alogZz alogz 3}
E
I aT + aT + aT v 7.39
in the jth and lth states with energies E2j and E31 respectively, then
the total energy EI will be 7.40
7.34
EI(i,j,l) = Eli+EZj+E31 where (1' (2 and (3 may be taken as the mean energies correspond-
The partition function of the system in the assembly will then be ing to the three independent forms of the motion of a system.
(This equation for the mean energy is, of course, of the form
Z = L e-,,(i,j,/)/kT 7.35
expected for a system having its energy made up of three indepen-
i,j,l
dent components.)
where the sum must be taken over all possible values of i, j and I It may be concluded that, for a system having more than one
and all degenerate states are counted individually.* Substituting degree of freedom, it is possible for the partition function to be
from equation 7.34 into equation 7.35 gives divided into its component parts. The complete treatment of the
separation of such a partition function is given in section 8.3 for
Z = L e-('U+'2j+'31)/kT
the case of a diatomic molecule. However, it is convenient to give
i,j,1
a tentative discussion of the total partition function of a semi-
= L L L e-E1;1kT. e'2j/kT . e-'JdkT 7.36
classical perfect gas at this point. If a semi-classical perfect gas
i j I
consisting of N non-interacting molecules at temperature T is
ow because the product (XI +xz +X3 + .. ')(YI + Yz + Y3 + ...) considered as comprising a single, macroscopic system composed
(z I +'zz + Z3 + ...) includes all combinations of the product of molecular sub-systems, then the partition function of this
XiYjZ" it is possible to write macroscopic system may be written as a total partition function

LXiLYjLZ, = LLLXiYjZI Z = L e-('U+'2j+'31+'4m+ ... )/kT 7.41

j 1 i j 1
all states

It follows that, since Eli' EZj and E31 are independent, equation where Eli' EZj' etc., are the energies of the individual molecules,
7.36 may be written as or sub-systems, 1, 2, etc., in the states i, j, etc., and the summation
Z = Le-,u/kT L e-'2j/kT L e-'JdkT 7.37 is taken over all allowed states or arrangements of the gas mole-
j 1 cules. The partition function in equation 7.41 may be split into its
If, therefore, three independent partition functions are defined as component parts as was done in equation 7.37 to give

Z I = L e-,u/kT, z, = L e-'2j/kT, Z3 = L e-'31/

kT
Z = 1
-Le-E1;1~TLe-'2j/kTLe-'31/kT, .. 7.42
j 1
N! i j 1

then equation 7.37 can be written as the product The division by N! in equation 7.42 is necessary because, in the
Z = ZIZZZ3 7.38 product of the summations, each term will in fact occur N! times,
(Consider three molecules labelled 1, 2 and 3 and let them be in
* That is to say that, if two different states i and i' of one form of motion
the ith, jth and lth state respectively. If the molecules are indis-
have the same value of energy so that 'Ii' = 'Ii' the terms e-<t;fkT and
e-<t,lk1 must be counted independently in the partition function. tinguishable, the rearrangement of the molecules among the three
101
100
STATISTICAL PHYSICS FOR STUDENTS THE THERMODYNAMICS OF GASES

states does not produce new, distinguishable states or arrange- 1 in its six-dimensional phase space. The total partition function
ments. Thus the 3! arrangements of the energies Eli' E2j, E3/ be- in equation 7.42 is then
tween the three molecules in the form:
Z =~
N!h
f r, e-· I1kT
dpXldpYldpzldxldYldzl

3! equivalent indistinguishable
x f r2
e-'2/kT dPx2dpy2··· f fN
e-'N/kT dPxN··· dZN

arrangements

X dPxldpyldpZldxldYldzl ...
. . . dpXNdPYNdPzNdxNdYNdzN 7.43
are equivalent to a single arrangement. Extending this argument
to the case of N sub-systems it is seen that, because of the indis- where r6N represents the available volume of the 6N-dimensional
tinguishability of the sub-systems, there are N! times as many phase space for all the N sub-systems. Since the total energy of the
terms in the product of the summations in equation 7.42 as there N sub-systems is
are in the expression in 7.41.) E = EI +E2+E3+··· +EN
Because the molecules are indistinguishable the individual
summation terms in equation 7.42 will be the same so that it is equation 7.43 may be re-written as
possible to write
I e-·u/ kT
= I e-' 2i/kT = I···= ... = Z Z =~ 1
N!h
f r6N
e -E/kT dPxl··. d ZN 7.44
i j /

being the partition function for each molecule. Equation 7.42

In the case of a perfect gas of non-interacting molecules as con-
then gives the expression for the total partition function as
sidered here the energy is independent of the positions of the
. ZN molecules. Therefore the integrals over the 3N spatial coordi-
z=-N! nates will simply give U dxdydz]N = VN where V is the volume
occupied by the gas. Thl total partition function will then be
in agreement with equation 7.31.
The total partition function for the translational motion alone
may be obtained using an integral form similar to that used in
Z -- ~
N!h
VN
f <X)

-<X)
e -E/kT d Pxl d Pyl d Pzl···

obtaining equation 7.15 except that the density of states will be

replaced by dPxdpydPzdxdydz/h3. The single partition function for ... dpXNdpyNdPzN 7.45
the molecule 1 is simply where the range of the momentum from - 00 to 00 applies to
each momentum coordinate individually.
It must be remembered here that the derivation of equation 7.44

== f r,e- Et/kT dpXldpyldpZldxldYldzl

h3
is based on the assumption that there are no interactions between
the molecules. The extension of this equation to include interac-
tion energies will be given in Chapter 9.
where rl represents the available volume of phase space and the Finally it is noted that, for a molecule which is not structureless,
coordinates Pxl and XI' etc., define the position of the sub-system there will be contributions to the total partition function due to
102 103
STATISTICAL PHYSICS FOR STUDENTS THE THERMODY AMICS OF GASES

the different modes of motion. If, for example, these modes of 5. Show that the total partition function derived from equation
motion give a partition function for each sub-system of the form 7.45, on the assumption that the energy of the N sub-systems is
Z = ZIZ2Z3, as in equation 7.38, the total partition function will 2 2 2 2 2 2
then be given by equation 7.31 for N such sub-systems as E = PXI +P)'I +Pz1 + ... +PXN +P)'N +PZN
2m 2m 2m 2m 2m 2m
(ZIZ2Z3t
Z= N! 7.46 agrees with that obtained by substituting equation 7.28 in equa-
tion 7.31, i.e.
PROBLEMS
VN
1. Show that, when two different gases A and B of volume VA Z = --(2nmkT)3N/2 7.47
N!h3N
and VB and with N A and NB molecules respectively are mixed
together at constant temperature to form a volume VA + VB'
there is an increase in the total entropy given by the mixing term 6. Using equation 7.3 obtain a value for log Wmaxin terms of the
energy E and the number of systems N only. (Use must be made
k[(N A + NB) 10g(VA+ VB)- N A log VA - NB log VB] of the values of T and ex given in Chapter 2.)
Hence deduce that, when VA = VB and N A = N B = N, the mixing
term is 2N k log 2.

2. Show that the Sackur- Tetrode equation (7.29) may also be

written as

s= Nk(-~log T-logp+~logk+~log2nm-310gh+~)
where P is the pressure of the perfect gas.

3. Derive the equation of state and the total energy of a semi-

classical perfect gas from the expression for the free energy as
given in equation 7.30. Explain why the results obtained are the
same as for a classical perfect gas while the entropy obtained from
this .free energy is not.

4. By evaluating the integral

f:=of:=-oo e-Pld2mkTdx:px = z,
obtain a partial partition function for the translation of a system
in one dimension with the motion limited to the region 0 ::::;x ::::;L.
Hence show that the partition function for translational motion
in three dimensions as given in equation 7.28 is given by

Z = ZxZ)'Zz
and that the energy per degree of freedom calculated as
kT2{O log Zx/oTh· is tkT.
104
105
 APPLICA TIONS OF STATISTICAL THERMODYNAMICS

Chapter 8 there is no interaction between the molecules. When a magnetic

field is applied to the gas any molecule which has its magnetic
moment pointing at an angle f) to the direction of the field will
Applications of Statistical ha ve a magnetic energy of
£( f) = - J1H cos f) 8.2
Thermodynamics
compared with its magnetic energy when f) = n/2. (The particu-
lar angular position of the magnetic moment which is taken as
representing zero magnetic energy is unimportant since £(f) is
In this chapter consideration will be given to a few examples of an energy of rotation, not of translation, and hence any constant
the physical application of statistical thermodynamics. The terms in £(f) will disappear from the subsequent analysis.)
methods given will not, in general, be the only ones by which the The partition function for the magnetic energy of the molecules
chosen problems could be treated and alternative methods are is given by
therefore indicated where this appears to be appropriate. Also, Z mag = "
L... e - «8)/kT
because the statistical method has been developed so far only for \ 8
those assemblies having a fixed energy and a fixed number of 8.3
systems, the applications considered do not, strictly, include any
which involve interactions between the systems. However, because
where the summations are over all possible values of the angles f).
the properties of the assemblies have been considered in terms of
Let it now be assumed that the number of states available for
the temperature rather than the energy, it will be seen later that
molecules with their magnetic moments pointing at an angle f)
the results are more general than would be the case for fixed
energy assemblies. :lj
.
within an element of solid angle dw is proportional to the magni-

8.1. The paramagnetic gas ~(

~~~cltr1'r" tude of dw. Equation 8.3 may then be replaced by an integral so that

8.4
Consider a gas in which each molecule has an intrinsic magnetic
moment. When a magnetic field is applied to thega; there will be where C is some constant of proportionality which it is not neces-
an induced paramagnetic moment per unit volume of the gas sary to define here.
given by The solid angle which is included in the conical element between
m = XH 8.1
the direction f) and f) + df) is
where X is the paramagnetic susceptibility of the gas per unit
volume and H is the applied field. The form which is found for the doi = 2n sin f) df)
paramagnetic susceptibility will depend on whether the magnetic so that equation 8.4 can be written
moments are treated classically or quantum mechanically (al-
though, as will be seen, the difference between the results in the Zm.g = 2nCf" el'Hcos8/kT sin f) df)
8=0
two cases is slight). In order to illustrate this point both cases will
be treated here even though the problem is only strictly amenable
to a quantum mechanical treatment.

THE CLASSICAL PARAMAGNETIC SUSCEPTIBILITY kT J1H

Suppose that the gas contains n molecules per unit volume, each = 4nC'-sinh- 8.5
J1H kT
molecule possessing an intrinsic magnetic moment J1, and that
107
106
STATISTICAL PHYSICS FOR STUDE TS APPLICATIO S OF STATISTICAL THERMODYNAMICS

The magnetic energy of the n molecules in unit volume of the gas The corresponding behaviour of the Langevin function is illus-
is obtained using equation 7.11 in the form trated in Fig. 22.

E = nkT2 aZmag
mag Zmag et 1 -----------------------

which, on substitution from equation 8.5, becomes

Emag = ---nkT {. pH pH
smh---cosh-
I1H}
I1H kT kT kT
sinh kT
8 10 x_

= nul] {kT
--coth- I1H} 8.6 Fig. 22. The Langevin function L(x) = coth x-~.
I1H kT x
If there is an induced magnetic moment m per unit volume in From equation 8.9 the paramagnetic susceptibility, defined in
the direction of the applied field then this magnetic energy may equation 8.1 by the relationship X = mfH, is given as
be expressed in a form similar to that of equation 8.2 so that
nl12
Emag = -mH 8.7 X = 3kT 8.10
Substitution from equation 8.6 now gives for the low field case.
E (It is left as an exercise for the student to show that the same
m= --- mag results for m and X are obtained if the value of the total magnetic
H
moment along the direction of the magnetic field is taken to be
the sum of all the components 11 cos () of the individual moments
= nl1{coth ~~ - ~~} of the molecules. This is equivalent to evaluating the average
moment in a manner similar to that indicated in equation 3.4, i.e.
= nI1L{~~} 8.8 _ f~11 cos () el'H cos 8/kT C dw
11 = g el'H cos 8/kT C dw
where the Langevin function L(x) is defined so that L(x) = coth x
-l/x. When the condition -x ~ 1 is satisfied then L(x) will approx- where C and dw have already been given and el'Hcos8/kT is the
imate to unity; thus at values of applied magnetic field such Boltzmann factor e" '/kT. The induced magnetic moment per unit
that I1H ~ kT equation 8.8 predicts that the induced magnetic volume is then m = nji.)
moment will approach its maximum, or saturation, value nil.
When, on the other hand, x ~ 1 then expansion of L(x) to terms THE QUANTUM MECHANICAL PARAMAGNETIC

involving x3 gives the approximation SUSCEPTIBILITY

In quantum mechanics the angular momentum of an atom or
x
L(x) ~- molecule is defined by the total angular momentum quantum
3 number J which is, of course, an integer. The magnetic quantum
In this case equation 8.8 gives the magnetic moment as number M J, the component of J along the direction of an applied
magnetic field, can take only the allowed integral values
2
nl1
m = 3kTH 8.9 MJ = J,J-1,J-2, ... ,0, ... -(1-1),-J
109
108
STATISTICAL PHYSICS FOR STUDENTS APPLICA TIONS OF STATISTICAL THERMODYNAMICS

For a molecule with a given value of M J the component of its In the low field limit where gflBH ~ kT the denominator of equa-
magnetic moment along the direction of the applied magnetic tion 8.14 is very nearly 2J + 1 and therefore
field is given by
ng2fl~J(J + 1)H2
flH = gflBMJ 8.11 8.15
3kT
where flB is the Bohr magneton and g is the spectroscopic (or
This energy again corresponds to a magnetic moment per unit
Lande) splitting factor of the molecule. Taking the magnetic
volume of -EmaJH so that
potential energy of the molecule as - flHH in agreement with
equation 8.2 the partition function for the molecule becomes _ ng2flV(J + l)H 816
m - 3kT .
MJ= +J
Zmag = L eI'HH/kT
The corresponding susceptibility per unit volume, m/H, is
MJ=-J
MJ= +J ng2fl~J(J + 1)
L egI'BMJH/kT 8.12
X = 3kT
8.17
MJ=-J
Again it is convenient to evaluate this partition function in the A comparison of equation 8.17 with the paramagnetic suscepti-
two limiting cases where H is either very large or very small. bility given by equation 8.10 shows that the quantum mechanical
When H is very large the term in which MJ = J will be very much molecule behaves, in this approximation, as a classical molecule
larger than any of the others. This will correspond to the case with an effective magnetic moment
where all the magnetic moments are aligned along the direction
of the applied field to give the maximum possible magnetic fl = gflBv'{J(J + I)}
moment ngflBJ. (Again it is left as an exercise for the student to show that the same
In the low field region the approximation e" ~ 1 + x + tx2 may results are obtained by finding the average moment of the mole-
be used in equation 8.12 to give cules in the direction of the field from the relationship

MJ= +J [{gflBH}
Zmag ~ MJ~-J 1+ ~ MJ+2
1{gflBH}2
~
2J
MJ
MJ= +J
L gflBMJ egI'BMJH/kT
- MJ= -J
2 flH = MJ- +J
gflBH} J(J + 1)(2J + 1) L egI'BMJH/kT
= (2J+1)+ { -- kT 8.13
6 MJ= -J
Substituting once again in equation 7.11, the total magnetic and taking m = njiH.)
energy for a gas with n such molecules per unit volume becomes
8.2. The harmonic oscillator
Emag = nkT2 a~ IOg[(2J + 1) According to classical mechanics there is no restncnon on the

gflBH}2 J(J + 1)(2J + l)J energy of a simple harmonic oscillator. It follows therefore that,
as shown in section 3.6, the mean energy of a classical one-dimen-
+{ kT 6 sional harmonic oscillator in an assembly at temperature Tis kT.
(gflB
H)2 J(J + 1)(2J + 1) On the other hand if the one-dimensional harmonic oscillator
n 3 obeys quantum mechanics it may only have an energy given by
- kT (2 1) {gflBH}2 J(J + 1)(2J + 1) 8.14 one of the discrete values
J + + kT 6
E = (n +t)hv 8.18
110 111
STA TISTICAL PHYSICS FOR STUDENTS APPLICATIONS OF STATISTICAL THERMODYNAMICS

where v is the oscillator frequency and n is a positive integer. The By treating the atoms in a solid as simple harmonic oscillators
lowest energy available to such a quantum mechanical oscillator with their mean energies given by equation 8.21 it is possible to
is thy and is known as the zero point energy. calculate the specific heat of the solid. Such a calculation would
The mean energy of a quantum mechanical harmonic oscillator involve the assumption of a distribution of the oscillator fre-
at a temperature T can be found by setting up the partition func- quencies in a manner such as that of Debye which is described in
tion as section 4.4. While the result obtained on the basis of this assump-
L
0:)

Z = e-(n+t)lIv/kT tion may be seen by inspection to be the same as the Debye specific
n=O heat of section 4.4, it is left as an exercise for the student to calcu-
late the specific heat obtained from Einstein's assumption of a
= e-thv/kT L e-nhv/kT
8.19 single oscillator frequency (see problem 8).
n=O

The summation term in equation 8.19 is equivalent to the sum-

co
mation L x" = (1- X)-l so that the partition function is 8.3. The diatomic molecule
n= 0
In a diatomic molecule the energy may be considered as being
made up of five independent contributions. These contributions
Z = e-thv/kT
8.20 are due to:
(1- e-hv/kT)
the translational and rotational motion of the molecule as a

The mean energy of the oscillator, as given by . . E

{a
= kT2 ---log Z} ,
whole,
the vibrational motion of the two atoms along the axis of the
is thus aT v molecule,
the motion of the electrons around the nuclei,

E = hv{t+ ehV/k~ _ J I 8.21

the nuclear spin.
The energy levels which are available for these five forms of
motion are necessarily quantized and only in the case of the
(At high temperatures where hv/kT ~ 1 it is possible to sub- translational motion is it possible to treat these levels as an ap-
stitute in equation 8.21 for proximate classical continuum. In the other cases the energy levels
must be treated as completely discrete except, perhaps, at very
e',v/kT ~ 1+ _
{hV}
kT
+1. _
2
{hv}2
kT high temperatures.
In order to study the thermodynamic properties of the perfect
with the higher order terms neglected. The mean energy of the diatomic gas it is necessary to establish the partition function of a
oscillator is then molecule in the gas in terms of the separate partition functions
for the different forms of motion. Following the method outlined
E ~ hV{t+ ~ :(~)'} in section 7.6 it is possible to factorize the partition function so
kT+2 kT that

Z = Z,ZrZvZeZn 8.22
kT( 1- 1 hV)}
~ hv{ t+hv 2kT where Z, is the translational partition function,
Zr" " rotational "
= kT
Zv" " vibrational
as is expected for the high temperature limit where the distinction Ze" " electronic
between classical and quantum systems is not important.) and Zn" " nuclear spin
112 113
STATISTICAL PHYSICS FOR STUDE TS APPLICATIONS OF STATISTICAL THERMODY AMICS

Since the nuclear spin partition function generally involves harmonic oscillator; i.e.
only multiplication by a constant factor, discussion of this term e-thv/kT
will be given later in the section after values have been determined Z,. = -e
I -hv/kT (8.20)
for the other components.
The translational motion of the diatomic molecule is quite where v, the characteristic frequency of the molecular vibrations,
analogous to that already considered for a structureless molecule is determined by the mass of the atoms making up the molecule
and the partition function Z, will therefore be equal to that given and the nature of the coupling between them.
in equation 7.28, i.e. The electronic partition function can usually be represented
with sufficient accuracy by the first two energy terms in the normal
V t
Z, = h3 (2nmkT) (7.28) summation. If the energies required to excite an electron from the
ground state to the first, second, etc., excited states of the mole-
In the determination of the rotational partition function of the cule are fe I> fe2' etc., then the partition function will be effectively,
diatomic molecule it is necessary to write the allowed rotational
Z; = gO+gl e-'el/kT+g2 e-'e2IkT + ... 8.25
energy levels fj in the quantum mechanical form*
h2 where go is the degeneracy of the ground state and gl' g2' etc.,
fj = j(j+ 1)8n~ 8.23 are the degeneracies of the respective excited states. The energies
fe 1 and fe2 are, in general, very much larger than the thermal
energy kT except in the case of very high temperatures as will be
where j, the total angular momentum quantum number of the
discussed below. It is generally possible, therefore, to replace
rotational motion, is a positive integer and .f is the moment of
inertia of the molecule about an axis through its centre of gravity equation 8.25 by
and normal to the line joining the two atoms. For each value of z. ~ gO+gl e-'el/kT 8.26
the quantum number j the magnetic quantum number mj may The complete partition function of a diatomic molecule is thus
take any of the integral values between j and - j, i.e. anyone of obtained from its component parts, as indicated in equation 8.22,
(2j+ 1) values. Each energy level fj thus represents (2j+ 1) states
hV kT
and, allowing for this degeneracy, the rotational partition func- as V { 00 j }" { -t / }
Z = h3(2nmkTf j~O (2j+1)e- (j+l)K/kT 1~e-hV/kT
tion becomes
00

z, = L (2j+ 1) e-'i/kT x {gO+gl e-'etlkT}Zn 8.27

j=O
00 The total partition function of a gas of N identical molecules will
= L (2j+1)e-j(j+l)K/kT 8.24 then follow from equation 7.31 as ZN/N!.
j=O Following the method used in the derivation of equation 7.38
where K 2
= h /8n2 •.f. the energy of the gas of N diatomic molecules may be written as

The vibrational motion of the molecule may be assumed, to _ 2[0 log z, 0 log Zr 0 log Zv a log Ze]
good approximation, to be simple harmonic in form and to be E - NkT aT + oT + oT + aT
sensibly free from any anharmonic distortions. It is. possible,
therefore, to take the vibrational partition function of the mole- = N{tkT+kT2aIOg[
aT
I:
j=O
(2j+1)e-j(j+l)K/kT]
cule as that given in equation 8.20 for the one-dimensional simple
1)g f e-,el/kT}
*A proof of this equation 8.23 is given, for example,
Theoretical Chemistry, D. Van Nostrand Co. Inc. 1947.
in Glasstone, S.:
+hv (t+ ehv/kT -1 +gO~~l e-'el/kT 8.28

114 115
STATISTICAL PHYSICS FOR STUDENTS APPLICATIONS OF STATISTICAL THERMODYNAMICS

and there is no contribution from the term Z, which is taken to the case where the temperature is further increased to values
be temperature independent. T ~ Oro, it is possible to obtain an approximate value for the rota-
So that the magnitudes of the various contributions to the tional partition function Z, by replacing the summation in equa-
energy E in equation 8.28 may be more readily appreciated it is tion 8.24 by an integration over the variable). Then, since 0roJT ~
convenient to define characteristic temperatures for the rotation, 1, in this case
vibration and electronic energies. As will be appreciated from the 00

subsequent discussion these temperatures are most conveniently z, = L (2)+\}e-j(j+l)Brot/T

taken as Orot = Kfk = h2/8n2.fk; 0vib = hv/k and Oe = Eel/k. The i= 0
magnitudes of these characteristic temperatures may be found becomes
from the properties of the molecules and in general they are found Z, = ((2)+I)e-j(j+l)Brot/T d)
to satisfy the inequalities Oro, ~ Ovib ~ Oe. For example, in the
case of the hydrogen molecule their values are: = eBrot/4T ( e-(j+t)2Brot/T2(j+t) d(j+t)

For other diatomic molecules the characteristic temperatures

have a similar relationship to those for the hydrogen molecule
but are, in general, rather lower. Thus, for the chlorine molecule, or, with eBro,/4T ~ 1 in this approximation,
Oro, = 0'35°K,Ovib = 810 K and Oe = 25,500oK.
0
T
At low temperatures where T ~ Oro, it is clear from the forms of Z ~- 8.30
r - Oro,
the partition functions that only an insignificant fraction of the
molecules will be in rotation, vibration or electronic energy levels The rotational energy at these temperatures is obtained as
above the ground state. In this case the total energy of the mole-
cules will be due to their translational motion together with the
E = NkT20 log Zr
zero point energy of the vibrational motion, i.e. tNhv, and the
r oT
ground state energy of the electrons. Of these three terms only the = NkT 8.31
translational energy, given by equation 8.28 as tNkT, will be
dependent on the temperature so that, for T ~ Oro,' the specific which corresponds to a classical energy of tkT for each of the two
heat of the gas at constant volume will be classical degrees of freedom for the rotation of the molecules. The
contribution to the specific heat of the gas at constant volume,

C" = {~~t obtained by differentiation of equation 8.31, is

8.32
= tNk 8.29
The vibrational energy levels of the molecules will not contri-
(At these low temperatures the components of the partition func-
bute to the temperature dependent part of the energy or to the
tion given in equation 8.27 may be taken as Z, = V/h3(2nmkT)t,
specific heat of the gas until the temperature approaches the
Z, ~ 1, Z; ~ e-thv/kT, Z, ~ go while Z, is again a constant.)
If the temperature °
is increased until it is of the order of rot
some of the molecules will be excited to take up rotational energy
characteristic temperature Ovib' However, for high temperatures
T ~ Ovib, the average vibrational energy will of course approach
the classical value of kT per molecule as shown in section 8.2.
states above the ground state. The rotational motion will then
Thus the vibrational energy of the gas will approach the value
contribute to both the total energy and the specific heat of the gas
while the vibrational motion will still be in its ground state. In E; = NkT 8.33
116 117
 --.-- ------

STATISTICAL PHYSICS FOR STUDE rs A PPLICA TlONS OF STATISTICAL THERMODYNAM ICS

and the vibrational contribution to the specific heat in the temper- simple multiplicative factor go, the weight of the ground state. On
ature region T ~ Ovib is then the other hand the molecules of nitric oxide (NO) have a value of
C"v = Nk 8.34
e which is much smaller than for the oxygen molecule and the
electronic energy levels give a contribution to the specific heat
The total temperature dependent energy of the gas at high for temperatures in the neighbourhood of 80oK. This case is, how-
temperatures e e
(for which rO' ~ vib ~ T ~ Dc) is given by com- ever, an' unusual one.
bining the translational, rotational and vibrational energy contri- The variation of the specific heat which would be expected for
butions of equations 8.29, 3.32 and 8.34 as a two energy level system, such as that discussed for the electronic
energy states in the partition function of equation 8.26, will be
E = "tNkT 8.35
considered in some detail in the next section.
and the corresponding total specific heat is The contribution of the nuclear spin to the partition function
Cv = "tNk will arise, in general, from the degeneracy of the nuclear spin state.
8.36
If the total spin contributed by the two nuclei of the molecule has
This high temperature specific heat will be approached in a the quantum number I then this spin state will be (2I + I)-fold
series of 'steps' as the temperature rises and will have a form degenerate. These (2I + 1) states of very nearly the same energy
similar to that shown in Fig. 23 where N k has been replaced by the correspond to the allowed values which may be taken by the mag-
gas constant R. netic quantum number m., i.e. I, (1-1), ... ,0, ... , -(1-1), -I.
The partition function Z; may thus be replaced by the ground
state term (2I + 1).
When the complete partition function is written, with the
electronic and nuclear degeneracy terms included, it then becomes
8.37

The temperature independent term go(2I + 1) results in a contri-

bution Nk log[go(2I + 1)] to the entropy of the gas but does not
contribute to either the temperature dependent energy or the
specific heat of the gas.

Fig. 23. The specific heat of a diatomic gas as a function of temperature. HOMONUCLEAR MOLECULES
The discussion of the effect of the nuclear spin which has been
The derivation of the specific heat given so far has neglected any given so far will only apply to the case of molecules in which the
possible contribution from the electronic energy levels. This im- two nuclei are of different species (i.e. heteronuclear molecules). In
plies that for all the diatomic molecules the condition T ~ ee is the case of a diatomic molecule in which the two nuclei are iden-
satisfied except at the very highest temperatures. For example, in tical (i.e. a homonuclear molecule) the state of the nuclear spin
oxygen the value of ee is about 11,000oK and this is one of the will determine the allowed rotational wave functions of the mole-
lowest values of ee
for diatomic molecules. It follows that, in a gas cule because of the natural symmetry of the molecule. For example,
composed of oxygen molecules, there will be no significant specific for a hydrogen molecule (in which both nuclei are single protons)
heat contribution from the electronic energy levels until the the total nuclear spin quantum number may be either I = 0 or
temperature of the gas is increased substantially above 2000oK. I = 1. The allowed rotational wave functions are then such that),
In this case the contribution of the electronic states to the partition the total angular momentum quantum number of the rotation
function will thus be given, to sullicicnt approximation, by the of the molecule, must be even for I = 0 (para-hydrogen) and odd
118 119
STATISTICAL PHYSICS FOR STUDENTS A PPLICA TIONS OF STATISTICAL THERMODYNAMICS

for 1 = 1 (ortho-hydrogen). The total rotational partition function 8.4. The two energy level system
of the hydrogen molecule will thus be a combination of the rota- Following the discussion which was given in the previous section
tional partition functions, Zro and Zrp, for ortho- and para- on the effect of the electronic energy levels in a diatomic molecule,
hydrogen respectively. ow, because the nuclear partition function more detailed consideration will be given here to the case of a
is different for the two cases, the contribution to the total parti- system for which there are two available energy levels.
tion function due to the term ZrZn must be replaced by Consider an assembly of N systems, localized in space, each of
which may be in one of two non-degenerate energy levels f2 and
fl where f2' 'the excited state', is greate: tha? fl' As an alter?ative
to the partition function method which has been used In the
where, using equation 8.24 with K/k = Brot, previous sections of this chapter, the equilibrium distribution of
this assembly will be calculated by determining the condition for
Zro = L (2j+ 1) e: j(j+ l)8rodT
the free energy F to be a minimum.
jodd
As the first step it is required to determine the entropy of the
and
z., = L (2j+1)e-j(j+l)8rodT assembly when it is in a given configuration by applying the rela-
j even tion S = k log W. Let there be n systems in the upper energy state,
f2' and (N -n) systems in the lower energy state, fl' as shown in
Also, since Z, = (21 + 1), then Zno = 3 for 1 = 1 (the triplet state)
and Znp = 1 for 1 = 0 (the singlet state).
The actual numbers of molecules in the ortho- and para-states
will depend on the magnitudes of the various terms in the partition
€2-r------------
Fig. 24. The number of ways in which the configuration of Fig. 24

n systems

function summations. At T = OaK, the only state which will be €

occupied is that for which j = 0 since this has the lowest energy.
Therefore, in the equilibrium state at this temperature, all the €t_! (N-nlSystems

molecules will be in the form of para-hydrogen with 1 = O. How- Fig. 24. Distribution of the systems among the two energy levels.
ever, as the temperature is lowered towards absolute zero from
some higher value, a considerable period may be required for the may be formed is*
final equilibrium state to be established in view of the substantial
relaxation time required for the nuclei to change from the 1 = 1 N! 8.38
W=---:-:-
state to the 1 = 0 state. n! (N -n)!
Alternatively, at high temperatures where the summations over
if the localized systems are considered to be completely distinguish-
odd and even j-values are the same, there will be a 3 to 1 mixture
able. The entropy of the assembly in the configuration of Fig. 24 is
of the ortho- and para-hydrogen respectively.
then given by
(If it is desired to treat more complex molecules than the simple S = klog W
diatomic molecule which has been considered here then, not only N!
must allowance be made for a greater number of degrees of free- = k log n.'(N _ n )' .
dom for the rotational and vibrational motions, but also more
complicated motions of the molecules, such as 'wagging' and N!
'rocking', need to be taken into account. Also it becomes necessary * For the upper state the n systems may be chosen in NCn = n.'(N _ n )'.
to allow for the fact that the rotational and vibrational motions and then the remaining (N - n) systems of the lower state may only be
can no longer be treated as being entirely independent.) chosen in one way.
121
120
 STATISTICAL PHYSICS FOR STUDE TS APPLICATIONS OF STATISTICAL THERMODY AMICS

which becomes, on using Stirling's approximation, The specific heat obtained from equation 8.43 with the volume,
and hence the energy levels, maintained constant is
S = k[N log N -n log n-(N -n) 10g(N -n)l 8.39
The free energy of the assembly is therefore cv = {aE}
aT v
F=E-TS

= n£2 +(N -n)£1 -kT[N log N -n log n- N£2 e</kT

8.44
- (N - n) 10g(N - n)] 8.40 kT2 (1 + e</kT)2

r
or
For the assembly to be in the equilibrium configuration at temper-
ature T the number of excited systems, n, will be such that this 8.45
free energy is a minimum. That is
c, = Nk{ ~ (1 :::T)2

where 8 = £Ik = (£2 - £ dlk is the characteristic temperature of the

assembly. In Fig. 25 this specific heat is plotted as a function of
81T. It will be seen that there is a maximum value of C, ~ 0-45Nk
Applying this condition to equation 8.40 gives for 81T ~ 2·5 while C, is clearly zero for both T = 0 and T = 00.

h- £1)-kT[log(N -n)-log n] = 0
or
N-n
__ = e«2 - <,j/kT 8.41
n
as would be expected if the ratio of the numbers of systems in the
two states were obtained simply from the application of the
Boltzmann factor. (It is left as an exercise for the student to show
that equation 8.41 indeed represents the condition for a minimum
of the free energy rather than a maximum.)
The number of systems in the upper energy level is obtained Fig. 25. Variation of the specific heat of an assembly of systems having
from equation 8.41 as two energy levels.

The variation of the entropy ofthe assembly may be considered in

terms of the Boltzmann or Planck expressions which are here
N equivalent. It is clear that, when the assembly is ordered with all
8.42 the systems in the ground state, the entropy will be zero. This
1+e</kT
follows from the fact that there is only one way of arranging such
where £ = £2 - £1 is the energy gap between the two levels. an ordered configuration, so that W = 1 and log W = O. This
The total energy of the assembly is then simply ordered condition will correspond to the case where the temper-
E = n£2 +(N -nh ature T in equation 8.42 is zero. As the temperature rises above
the absolute zero the disorder and the entropy will increase as
N£ the number of excited systems, n, increases. If the temperature
= N£I + 1+e< /kT 8.43
could tend to infinity then, according to equation 8.42, the
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STATISTICAL PHYSICS FOR STUDE TS APPLICATIONS OF STATISTICAL THERMODY AMICS

number of excited systems, n, would tend to a value 1N and the o 0 0 0

entropy, as given by equation 8.39, would have its maximum value
x X X
Smax = Nk log 2 8.46
o o o o
If it were possible to excite all the systems to the upper energy
state so that n = N the assembly would again be completely X X X
ordered and in a state of zero entropy. According to equation 8.42
this ordered situation could only be achieved if the temperature
o o o o
T approached a value of zero from the negative temperature
Fig. 26. ormal (0) and interstitial (x) positions in a lattice.
side. (That is, 1/{l + e</k(- Tl} ~ 0 as T ~ 0.) While a negative
temperature of this magnitude is not obtainable in practice, it is
possible to obtain finite negative temperatures as defined by atoms among the N localized, interstitial positions is NCn =
equation 8.42. The mechanisms for producing such negative tem- N!I{ n! (N - n)!} while the number of ways of arranging the (N - n)
peratures would be similar to those used in lasers for exciting the remaining atoms among the N normal positions is also NCn.
systems so that there are more in the upper energy state than in The weight of the configuration in which there are n interstitial
the lower. When this occurs the populations in the two states are atoms is thus the product of these numbers so that
said to be 'inverted' and, under this condition, it is necessary to
ascribe a negative temperature to the particular aspect of the N! }2
assembly under consideration. However, such a condition of the w= { n! (N-n)!
assembly is not an equilibrium condition and is therefore outside
the general scope of this book. and the entropy arising from the displacement of the atoms is
(It is left as an exercise for the student to show that the results
S = klog W
obtained here for the entropy and energy are also obtainable by
the partition function method.) N!
= k log { n! (N - n) !
}2
8.5. The disordered lattice
or, using Stirling's approximation,
As a final application of statistical thermodynamics in this chapter
consideration will be given to the thermal disorder which may S ~ 2k[ N log N - n log n - (N - n) 10g(N - n)]
occur in a crystal lattice. One way in which this disorder may arise
is through the displacement of atoms from their normal positions The corresponding free energy of the lattice, measured from the
to interstitial positions by the thermal vibrations in the lattice. ground state, is
Suppose that in Fig. 26 the circles represent the normal positions F = nE-2kT[NlogN-nlogn-(N-n)log(N-n)]
of the atoms in a monatomic cubic lattice and that the crosses
represent the possible interstitial positions which the atoms may The condition for equilibrium, 8F/8n = 0, becomes
occupy. If there are N normal lattice points in the volume con-
sidered there will also be N interstitial positions. E-2kT[log(N -n)-log nJ = 0
Let the energy required to remove an atom from a normal so that
position to an interstitial position be E. Then, if there are n such
interstitial atoms, the energy of the lattice will be nE above its N 8.47
n = ----,;:-;-;;;
ordered ground state. The number of ways of arranging these n 1 + e</2kT

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STATISTICAL PHYSICS FOR STUDENTS APPLICATIONS OF STATISTICAL THERMODYNAMICS

PROBLEMS 8. As a basis for the calculation of the specific heat of a solid,

Einstein assumed that the N atoms in the solid could be con-
1. Show that at normal temperatures the entropy of a diatomic sidered as forming 3N harmonic oscillators each with the same
gas is, approximately, frequency v. Show that the specific heat of the solid in this case
would be
S = Nk(log V+ilog(2nmkT)-3Iogh
BE}2
+ log {.f
J= 0
(2J+ 1) «: j(j+ ll6'OdT} c, = 3R { T
e6E/T
[e6E/T _1]2

e-6vib/T }
where BE = hvlk is known as the Einstein temperature and the
+ log { 1_ e 6vib/T
mean oscillator energy is taken from section 8.2.

+ log go + log(21 + 1)+i-Iog N)

2. Two different groups of n fermions are distributed among m

states of the same energy where m > n. Show that the entropy is

2k[m log m-n log n-(m-n) log(m-n)].

3. Show that, at high temperatures, the free energy of an assembly

of quantum mechanical, one-dimensional oscillators approxi-
mates to kT 10g(hv/kT) per oscillator, corresponding to a mean
energy of kT.

4. Evaluate the partition function at temperature T for a classical

one-dimensional oscillator having an energy

and hence find the mean energy of such an oscillator at this

temperature.

S. Show that the equation of state of a diatomic gas as derived

from the partition function of equation 8.27 is the same as for a
monatomic gas.

6. Calculate the maximum specific heat for an assembly of systems

having two energy levels separated by an energy v if the upper level
is doubly degenerate.

7. Write out the partition function for a three-dimensional har-

monic oscillator assuming that it obeys (a) classical, (b) quantum
mechanics. Show that both give a mean energy of 3kT at high
temperatures.

126 127