Instructor’s Manual

Containing Solutions to
Over 250 Problems
Selected From

STATISTICAL MECHANICS
(THIRD EDITION)

By
R. K. Pathria and PAUL. D. BEALE

1
2
Preface

This instructor’s manual for the third edition of Statistical Mechanics is based
on RKP’s instructor’s manual for the second edition. Most of the solutions
here were retypeset into TeX from that manual. PDB is responsible for the
solutions of the new problems added in the third edition. The result is a manual
containing solutions to some 280 problems selected from the third edition.
The original idea of producing an instructor’s manual first came from RKP’s
friend and colleague Wing-Ki Liu in the 1990’s when RKP had just embarked
on the task of preparing the second edition of Statistical Mechanics.
This should provide several benefits to the statistical mechanics instructor.
First of all, there is the obvious advantage of saving time that one would oth-
erwise spend on solving these problems oneself. Secondly, before one selects
problems either for homework or for an exam, one can consult the manual to
determine the level of difficulty of the various problems and make one’s selection
accordingly. Thirdly, one may even use some of these solved problems, especially
the ones appearing in later chapters, as lecture material, thereby supplementing
the text. We hope that this manual will enhance the usefulness of the text –
both for the instructors and (indirectly) for the students.
We implore that instructors not share copies of any of the material in this
manual with students or post any part of this manual on the web. Students
learn best when they work together and struggle over difficult problems. Readily
available solutions interfere with this crucial aspect of graduate physics training.

R.K.P. San Diego, CA

P.D.B. Boulder, CO Waterloo, Ontario, Canada

3
4
Chapter 1

1.1. (a) We expand the quantity `nΩ(0) (E1 ) as a Taylor series in the variable
(E1 − Ē1 ) and get

`nΩ(0) (E1 ) ≡ `nΩ1 (E1 ) + `nΩ2 (E2 ) (E2 = E (0) − E1 )

= {`nΩ1 (Ē1 ) + `nΩ2 (Ē2 )}+
 
∂`nΩ1 (E1 ) ∂`nΩ2 (E2 ) ∂E2
+ (E1 − Ē1 )+
∂E1 ∂E2 ∂E1 E1 =Ē1
( 2 )
1 ∂ 2 `nΩ1 (E1 ) ∂ 2 `nΩ2 (E2 ) ∂E2

+ (E1 − Ē1 )2 + · · · .
2 ∂E12 ∂E22 ∂E1
E1 =Ē1

The first term of this expansion is a constant, the second term van-
ishes as a result of equilibrium (β1 = β2 ), while the third term may
be written as
   
1 ∂β1 ∂B2
2 1 1 1
+ E1 − Ē1 = − + (E1 −Ē1 )2 ,
2 ∂E1 ∂E2 eq. 2 kT12 (Cv )1 kT22 (Cv )2

with T1 = T2 . Ignoring the subsequent terms (which is justified

if the systems involved are large) and taking the exponentials, we
readily see that the function Ω0 (E1 ) is a Gaussian in the variable
(E1 − Ē1 ), with variance kT 2 (Cv )1 (Cv )2 /{(Cv )1 + (Cv )2 }. Note that
if (Cv )2 >> (Cv )1 — corresponding to system 1 being in thermal con-
tact with a very large reservoir — then the variance becomes simply
kT 2 (Cv )1 , regardless of the nature of the reservoir; cf. eqn. (3.6.3).
(b) If the systems involved are ideal classical gases, then (Cv )1 = 23 N1 k
and (Cv )2 = 32 N2 k; the variance then becomes 32 k 2 T 2 · N1 N2 /(N1 +
N2 ). Again, if N2 >> N1 , we obtain the simplified expression
3 2 2
2 N1 k T ; cf. Problem 3.18.

1.2. Since S is additive and Ω multiplicative, the function f (Ω) must satisfy
the condition
f (Ω1 Ω2 ) = f (Ω1 ) + f (Ω2 ). (1)

5
6 CHAPTER 1.

Differentiating (??) with respect to Ω1 (and with respect to Ω2 ), we get

Ω2 f 0 (Ω1 Ω2 ) = f 0 (Ω1 ) and Ω1 f 0 (Ω1 Ω2 ) = f 0 (Ω2 ),

so that
Ω1 f 0 (Ω1 ) = Ω2 f 0 (Ω2 ). (2)
Since the left-hand side of (2) is independent of Ω2 and the right-hand side
is independent of Ω1 , each side must be equal to a constant, k, independent
of both Ω1 and Ω2 . It follows that f 0 (Ω) = k/Ω and hence

f (Ω) = k `n Ω + const. (3)

Substituting (3) into (1), we find that the constant of integration is zero.
1.4. Instead of eqn. (1.4.1), we now have

Ω ∝ V (V − v0 )(V − 2v0 ) . . . (V − N − 1v0 ),

so that

`n Ω = C + `n V + `n (V − v0 ) + `n (V − 2v0 ) + . . . + `n (V − N − 1v0 ),

where C is independent of V . The expression on the right may be written

as
N −1 N −1 
N 2 v0
  
X jv0 X jv0
C+N `n V + `n 1 − ' C+N `n V + − ' C+N `n V − .
j=1
V j=1
V 2V

Equation (1.4.2) is then replaced by

N 2 v0
 
P N N N v0
= + = 1 + , i.e.
kT V 2V 2 V 2V
 −1
N v0
PV 1 + = NkT .
2V

Since N v0 << V, (1 + N v0 /2V )−1 ' 1 − N v0 /2V . Our last result then
takes the form: P (V − b) = NkT , where b = 12 N v0 .
A little reflection shows that v0 = (4π/3)σ 3 , with the result that
 3
1 4π 3 4π 1
b= N· σ = 4N · σ .
2 3 3 2

1.5. This problem is essentially solved in Appendix A; all that remains to be

done is to substitute from eqn. (B.12) into (B.11), to get
X (πε∗1/2 /L)3 (πε∗1/2 /L)2
(ε∗ ) = V ∓ S.
1 6π 2 16π
 7

Substituting V = L3 and S = 6L2 , we obtain eqns. (1.4.15 and 16).

The expression for T now follows straightforwardly; we get
       
1 ∂ `n Ω k ∂ `n Ω k R+N k Nhν
=k = = `n = `n 1 + ,
T ∂E N hν ∂R N hν R hν E
so that   
hν Nhν
T = `n 1 + .
k E
For E >> Nhν, we recover the classical result: T = E/Nk .
1.9. Since the function S(N,V,E) of a given thermodynamic system is an ex-
tensive quantity, we may write
   
V E V E
S(N, V, E) = Nf , = Nf (v, ε) v = ,ε = .
N N N N
It follows that
       
∂S ∂f −V ∂f −E
N =N f +N · 2 +N · 2 ,
∂N V,E ∂v ε N ∂ε v N
       
∂S ∂f ∂S. ∂f 1
V = VN · = EN · .
∂V N,E ∂v ε ∂E N,V ∂ε v N
Adding these expressions, we obtain the desired result.
1.11. Clearly, the initial temperatures and the initial particle densities of the two
gases (and hence of the mixture) are the same. The entropy of mixing may,
therefore, be obtained from eqn. (1.5.4), with N1 = 4NA and N2 = NA .
We get
(∆S)∗ = k[4NA `n(5/4) + NA `n 5]
= R[4 `n(5/4) + `n 5] = 2.502 R,
which is equivalent to about 0.5 R per mole of the mixture.
1.12. (a) The expression in question is given by eqn. (1.5.3a). Without loss of
generality, we may keep N1 , N2 and V1 fixed and vary only V2 . The
first and second derivatives of this expression are then given by
   
N1 + N2 N2 N1 + N2 N2
k − and k − + 2 (1a,b)
V1 + V2 V2 (V1 + V2 )2 V2
respectively. Equating (1a) to zero gives the desired condition, viz.
N1 V2 = N2 V1 , i.e. N1 /V1 = N2 /V2 = n, say. Expression (1b) then
reduces to
 
n n knV1
k − + = > 0.
V1 + V2 V2 V2 (V1 + V2 )
Clearly, (∆S)1≡2 is at its minimum when N1 /V1 = N2 /V2 , and it is
straightforward to check that the value at the minimum is zero.
8 CHAPTER 1.

(b) The expression now in question is given by eqn. (1.5.4). With N1 =

αN and N2 = (1 − α)N , where N = N1 + N2 (which is fixed), the
expression for (∆S)∗ /k takes the form

−αN `n α − (1 − α)N `n (1 − α).

The first and second derivatives of this expression with respect to α are
 
N N
[−N `n α + N `n(1 − α)] and − − (2a,b)
α 1−α

respectively. Equating (2a) to zero gives the condition α = 1/2, which

reduces (2b) to −4N . Clearly, (∆S)∗ /k is at its maximum when N1 =
N2 = (1/2)N , and it is straightforward to check that the value at the
maximum is N `n2.
1.13. Proceeding with eqn. (1.5.1), with T replaced by Ti , it is straightforward
to see that the extra contribution to ∆S, owing to the fact that T1 6= T2 ,
is given by the expression
3 3
N1 k `n (Tf /T1 ) + N2 k `n(Tf /T2 ),
2 2
where Tf = (N1 T1 + N2 T2 )/(N1 + N2 ). It is worth checking that this
expression is always greater than or equal to zero, the equality holding if
and only if T1 = T2 . Furthermore, the result quoted here does not depend
on whether the two gases were different or identical.
1.14. By eqn. (1.5.1a), given on page 24 of the text, we get
3
(∆S)v = Nk `n(Tf /Ti ).
2
Now, since PV = NkT , the same equation may also be written as
    
kT 3 5 2πmkT
S = Nk `n + Nk + `n . (1b)
P 2 3 h2

It follows that
5 5
(∆S)P = Nk `n(Tf / Ti ) = (∆S)V .
2 3
A numerical verification of this result is straightforward.
It should be noted that, quite generally,

(∆S)P T (∂S / ∂T )P CP
= = =γ
(∆S)V T (∂S / ∂T )V CV

which, in the present case, happens to be 5/3.

 9

1.15. For an ideal gas, CP − CV = nR, where n is the number of moles of the
gas. With CP /CV = γ, one gets

CP = γnR / (γ − 1) and CV = nR / (γ − 1).

For a mixture of two ideal gases,
 
n1 R n2 R f1 f2
CV = + = + (n1 + n2 )R.
γ1 − 1 γ2 − 1 γ1 − 1 γ2 − 1

Equating this to the conventional expression (n1 + n2 )R/(γ − 1), we get

the desired result.
1.16. In view of eqn. (1.3.15), E − TS + PV = µN . It follows that

dE − TdS − SdT + PdV + VdP = µdN + Nd µ.

Combining this with eqn. (1.3.4), we get

−SdT + VdP = Nd µ, i.e. dP = (N / V )dµ + (S / V )dT .

Clearly, then,

(∂P / ∂µ)T = N / V and (∂P / ∂T )µ = S / V.

Now, for the ideal gas

( 3/2 )
h2

NkT N
P = and µ = kT `n ;
V V 2πmkT

see eqn. (1.5.7). Eliminating (N/V ), we get

 3/2
2πmkT
P = kT eµ/kT ,
h2

which is the desired expression. It follows quite readily now that for this
system  
∂P 1
= P.
∂µ T kT
which is indeed equal to N/V , whereas
" (  3/2 )#
h2
 
∂P 5 µ 5 N Nk
= P− 2 P = 2 − `n
∂T µ 2T kT V 2πmkT V

which, by eqn. (1.5.1a), is precisely equal to S/V .