Chemistry 5302 Homework Problem Set 2 Solutions

McQuarrie, Chapters 1, 2, and 3

1. (a) Show that

∂ 2A
2
∝ h(E − hEi)2 i (1)
∂T
Solution:
Using X X
A = −kT ln Q = −kT ln e−βEi = −kT ln eEi /kT (2)
i i

we have that

∂A 1 X Ei −Ei /kT
= −k ln Q − kT e
∂T Q i kT 2
X Ei e−Ei /kT
= −k ln Q −
| {z } T Q
(1) |i {z }
(2)

(1) (2)
z }| { z }| ( ){
∂ A2 X Ei e−Ei /kT X Ei e −Ei /kT
1 ∂ X Ei e−Ei /kT
= −k · + · −
∂T 2 i
kT 2 Q i
T2 Q T ∂T i
Q
( )
1 ∂ X Ei e−Ei /kT
=−
T ∂T i
Q
( ! !)
1 X Ei2 e−Ei /kT 1 X X Ei
=− 2
· − 2 Ei e−Ei /kT 2
e−Ei /kT
T kT Q Q kT
( i ) i i

∂ A2
1 h(E − hEi)2 i
=− Average Fluctuation in Energy
∂T 2 T kT 2
 
∂S 1 ∂ Ē
− =−
∂T T ∂T
2
where ∂∂TA2 = − ∂T
∂S
comes from the thermodynamic square. The last expression is
(dE)V = T dS.

1
(b) Show
∂ 2A
 
∝ h(p − hpi) (E − hEi)i (3)
∂β∂V
Solution:

A = −kT ln Q (N, V, β)
X
= −β −1 ln Q = −β −1 ln e−βEi
i
(P )
∂Ei −βEi
∂A (−β) e
= −β −1 i
= −p ∂V
∂V Q
(P )
  ∂Ei −βEi
∂ ∂A ∂ i ∂V e
=
∂β ∂V ∂β Q
P ∂Ei ( )( )
−βEi


−E i e 1 X ∂Ei X
= i ∂V e−βEi −Ei e−βEi


− 2
Q Q i
∂V i

We define pi ≡ − ∂E
∂V
i
,

( )( )
−βEi X pi e−βEi X Ei e−βEi
 
∂ ∂A X e
= (pi Ei ) −−
∂β ∂V i
Q i
Q i
Q
= hpEi − hpihEi
= h(p − hpi) (E − hEi)i

2
2. Show that µp = µV = µ.
Solution:
We want to show that    
∂G ∂A
=
∂N p,T ∂N V,T

From the thermodynamic square,

we have:

G(T, P ) = A(T, V ) + pV
   
∂G ∂A
= + d(pV )N |T,p
∂N T,p ∂N T,p
     
∂A ∂V ∂A
= +p where p = −
∂N T,p ∂N T,p ∂V T,N
     
∂A ∂A ∂V
= − where all particles have constant T
∂N p ∂V N ∂N p
 
∂A
=
∂N V

In order to get from the last line from the penultimate line, we used the chain rule:
       
∂f ∂f ∂f ∂y
= +
∂x z ∂x y ∂y x ∂x z

where f = A, x = N , y = V , and z = p.

3
3. Show that:    
∂µ ∂µ α
= + V◦T (4)
∂T V ∂T p κ

Solution:
By the rules of calculus:
       
∂f ∂f ∂f ∂y
= +
∂x z ∂x y ∂y x ∂x z

with z(x, y) = constant. Let f = µ, x = T , y = p, and z = V . Then:

       
∂µ ∂µ ∂µ ∂p
= +
∂T V ∂T P ∂p T ∂T V
∂p


We can simplify ∂T V
using
 
  ∂z
∂x ∂y
=− ∂z

x
∂y z ∂x y

with x = p, y = T , and z = V . Then,

∂V
 
 
∂p ∂T p −V α α(vol. coeff. expansion)
= −  = =
∂T V
∂V −V κ κ(isotherm. compressibility)
∂p
T
 
∂µ
What is ∂p
?
T

G = µN = E − T S + pV
(dG)N = N dµ = −SdT + pdV
dµ = −(S/N )p dT + (V /N )T dp
   
∂µ V
= ≡ VoT partial molar volume
∂p T N T

Therefore,

VoT α
   
∂µ ∂µ
= +
∂T V ∂T p κ
or the partial molar entropy at constant volume:

VoT α
− [So ]V = − [So ]p +
κ
We have shown in problem (2) that:

4
    
∂G ∂A
=
∂N p,T ∂N V,T
and in the current problem we have shown that

∂ 2G ∂ 2A
   
6=
∂T ∂N p ∂T ∂N V

Note that
∂ 2G ∂ 2A
       
∂µ ∂µ
= and =
∂T ∂N p ∂T p ∂T ∂N V ∂T V

This is a specific example of the general rule that:

(a) The 1st derivatives of thermodynamic potentials with respect to a common vari-
able are equal, because the 1st derivatives depend on mean values.
(b) The 2nd derivatives of thermodynamic potentials with respect to two common
variables are not equal, because the 2nd derivative depends on fluctuations about
mean values, which are different in different ensembles.
4. Extra Credit: McQuarrie, Problem 2-13: Show that for a particle confined to a cube
of length a that:
2 Ej
pj = (5)
3V
By taking the ensembles average of both sides, we have
2E
p= (6)
3V
If we use the fact that E = 23 N kT (to be provided in Chapter 5), we get the ideal gas
equation of the state.

Solution: First required to find an expression for the pressure of a given quantum
state pj  
∂Ej
pj = − (7)
∂V
For particle in a box quantum mechanics tells us that:
n2 h2 n2 h2
Ej = = (8)
8ma2 8mV (2/3)
Then,
n2 h2 2 (−2/3)−1
   
∂Ej
pj = − =− (− )V
∂V 8m 3
 2 2 (9)
n2 h2
  
nh 2 (−2/3) −1 2 2 Ej
=− (− )V V =( ) (1/V ) =
8m 3 3 8mV (2/3) 3V

5
5. Extra Credit: McQuarrie, Problem 3-12: Calculate the probability of observing an
energy that differs 10−4 precent from the average energy of 1 mole of an ideal gas.

Solution: Gaussian distribution for the energy:

 
(EN −E0 )2
1 − 2
pE = √ e 2σ
(10)
2πσ 2
−E0 ) 2
Let’s treat the exponential factor and exponential pre-factor terms x = (EN2σ 2 and
1 −4
y = √2πσ . Required to find P E for a energy differs 10 % from E 0 , i.e. E = E0 +
−6
2
2 2
√
10 E0 . For the ideal gas σ = KT cV , σ = kT 2 cN kNA , E0 = cN RT = cN kNA T
so Cv = cN R. Using all theses equations and numeric values c = 23 , N = 1, NA =
6.023x1023 , R = 8.314, T = 300, k = 1.381x10−23 ;
The exponential factor and exponential pre-factor terms x = 4.51725x1011 and y =
1.01308x108 . Thus,
11
P(E=E0 +10−6 E0 ) = 1.01308x108 e−4.51725x10 which is too slow to evaluate.

6. Extra Credit: McQuarrie, Problem 3-18: Derive an expression for the fluctuation in
the pressure in a canonical ensemble.

Solution: By definition
X
σP2 =< p2 > − < p >2 = p2 PN,j − < p >2 (11)
j

e−Ej β e−Ej β
PN,j = P −Ej β = (12)
je Q
Considering term:

e−Ej β
 
X X 1 X ∂Ej 1 ∂Q
p =< p >= pj PN,j = pj = − e−Ej β = (13)
j j
Q Q j ∂V βQ ∂V

From Eqn. 13 we have that

 
X ∂Ej
pQ = − e−Ej β (14)
j
∂V
and

1 ∂Q
= pβ (15)
Q ∂V

∂pQ ∂p ∂Q
=Q +p (16)
∂V ∂V ∂V
6
and from Eqn. Eqn. 14
P   
∂Ej
∂pQ ∂ j− ∂V
e−Ej β
=
∂V ∂V
X ∂ 2 Ej X  ∂Ej 2
−Ej β
= e +β e−Ej β (17)
j
∂V j
∂V
X ∂pj X
= e−Ej β + β p2j e−Ej β
j
∂V j

Equating Eqn. 16 and Eqn. 17 we have:

∂p ∂Q X ∂pj −Ej β X
Q +p = e +β p2j e−Ej β (18)
∂V ∂V j
∂V j

Dividing throughout by Q:
∂p 1 ∂Q 1 X ∂pj −Ej β β X 2 −Ej β
+p = e + pe (19)
∂V Q ∂V Q j ∂V Q j j

Using Eqn. 15 and definition for of an ensemble average:

 
∂<p> ∂p
+ β < p >2 = + β < p2 > (20)
∂V ∂V
Thus,   
1 ∂<p> ∂p
σp2 2
=< p > − < p > = 2
− (21)
β ∂V ∂V