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# Solutions to Statistical Mechanics Problems

## April 30, 2001

1. 1 cal. = 4.186 ×107 ergs = 4.186 J. Hence, 639 kcal = 639 × 4.186 kJ = 2675 kJ.

!
∂E 3
CV = = N kB
∂T V
2
! ! !
∂Q ∂E ∂V
Cp = = +p
∂T p
∂T p
∂T p
3
= N kB + N kB
2
Cp − CV = N kB

## f rom E = CV T and dE + pdV = 0

CV dT + (Cp − CV )T dV /V = 0
dT /T + (γ − 1)dV /V = 0
V γ−1 T = constant
or pV γ = constant

## 3. For adiabatic expansion into vacuum, E is a constant. Hence

2an
T2 = T1 + {1/V2 − 1/V1 }
3R

## 4. From the definition of latent heat:

∆E = L − p∆V
= 4.06 × 10 − 1.013 × 3.02 × 105−2
4

= 3.75 × 104 J

## 5. (a) Work done is 1 atm cm3 = 1.013 × 105 × 10−6 J = 0.1013 J.

(b) Work done is 73 × 10−7 J.
Thus in considering macroscopic volume changes of gases, the change in surface energy can be
neglected.

## 6. The correct statements are:

(a) The entropy change in a reversible cyclic process is zero.
R
(b) The entropy change in a reversible QSP process is dQ/T .

## 7. Rate of production of heat is I 2 R. Thus in time dt, dQ = I 2 Rdt and dS = I 2 Rdt/T .

8. (a) In p−V diagram, the adiabats obeying pV γ = K = constant are steeper than the isothermals
where pV = N kB T and are thus curves 2 → 3 and 4 → 1. Use the equations of state connecting
pi , Vi with each other.

p2 V2γ = p3 V3γ
p1 V1γ = p4 V4γ
p 1 V1 = p 2 V2

1
p 3 V3 = p 4 V4
!γ !γ
V4 p 1 p 3 V1
Hence =
V3 p 2 p 4 V2
p1 V2 p3 V4
but = and =
p2 V1 p4 V3
!γ−1 !γ−1
V4 V1
thus =
V3 V2
or V4 /V3 = V1 /V2

## (b) As the gas is ideal,

p i Vi
Ti =
N kB
(c) The work done on the gas is
Z i+1
− pdV = −N kB T ln Vi+1 /Vi isothermal stage
i
−K
= (V 1−γ − Vi1−γ ) adiabatic stage
1 − γ i+1
!γ−1
p i Vi Vi
=− { − 1}
γ − 1 Vi+1

(d) The energy change along the isothermal stages is zero and along the adiabatic ones is
3N kB (Ti+1 − Ti )/2.
(e) The heat absorbed is found from the differences between the change in the internal energy
and work done. This must be zero for adiabatic stages.
(i) For isothermal stage 1 → 2, ∆E = ∆Q−N kB T1 ln V2 /V1 = 0. Hence, ∆Q = N kB T1 ln V2 /V1 .
(ii) For adiabatic stage 2 → 3, ∆Q = 0.
(iii) For isothermal stage
3 → 4, ∆E = ∆Q − N kB T3 ln V4 /V3 = 0.
Hence, ∆Q = N kB T3 ln V4 /V3 .
(iv) For adiabatic stage, 4 → 1, ∆Q = 0.
(f) The total work done during cycle is, as ∆E = 0, equal to ∆Q = N kB T1 ln V2 /V1 +
N kB T3 ln V4 /V3 .
The heat absorbed at the hot stage is the first of these terms namely N kB T1 ln V2 /V1 .
The efficiency is then
∆W T3 ln V4 /V3
η= =1+
∆Q(1 → 2) T1 ln V2 /V1
= 1 − T3 /T1 as V4 /V3 = V1 /V2

## 9. To show that H is stationary for a system in equilibrium with constant N, T, p, differentiate H

and use the second law:

H = E + pV
dH = dE + pdV + V dp = V dp + T dS + µdN from the second law.

Thus at constant N, p, S, then dH = 0 or H stationary. The other relations are proved in the
same way.

2
10. To determine E and S from equation of state for one component gas, we use a Maxwell’s relation
derived from S.

T dS = dE + pdV

! ! ! !
∂S 1 ∂E ∂S 1 ∂E p
= , = +
∂T T ∂T ∂V T ∂V T
!V V
! T
! T
!
∂2S 1 ∂2E 1 ∂2E 1 ∂p
= = +
∂V ∂T T ∂V ∂T T ∂V ∂T T ∂T V
!
1 ∂E p
− −
T 2 ∂V T
T2
! ! !
∂E ∂p ∂S
or p + =T =T
∂V T
∂T V
∂V T

This gives a differential equation relating the change in E changes with V at fixed T . Apply
this to Van der Waals gas:

an2
(p + )(V − nb) = nRT
V2 !
∂E nRT
p+ =
∂V T V − nb
!
∂E an2
=
∂V T
V2

an2 3
E=− + c(T ) → nRT as V → ∞
V 2
3 an2
Hence E = nRT − .
2 V
Here we have used the fact that integration constant is independent of V and can only depend
on T . The dependence on this is known for large V where ideal behaviour is valid.
Similarly, S can be found:
! !
∂S ∂p nR
= =
∂V T
∂T V
V − nb
Integrating S = nR ln(V − nb) − nR ln n + nc(T )

The last two terms are constants of integration and written like this to ensure that S is extensive.
Now use
! !
∂S 1 ∂E 3
= = nR
∂T V
T ∂T V
2T
3
S = nR ln T + nd(V )
2
Where d(V ) is a constant of integration wrt T . Comparing these expressions gives
3
S = nR ln(V /n − b) + nR ln T + nc0
2
Where c0 is independent of both V and T .

3
11.

dE = T dS − f dl F = E − T S....(1)
dF = −f dl − SdT
! ! !
∂2F ∂f ∂S
Hence − = =
∂l∂T ∂T l
∂l
! ! !T
∂E ∂S ∂f
Now = −f + T = −f + T
∂l T
∂l T
∂T l
! ! ! ! ! !
∂2E ∂T ∂f ∂f ∂T ∂f T
From (1) = = = =
∂l∂S ∂l S
∂S l
∂T l
∂S l
∂T c
l l
Z Z !
dT ∆T 1 ∂f
Hence for isentropic small change ≈ = dl
T T cl ∂T l

12.

G = E − T S + pV
dG = dE − T dS − SdT + pdV + V dp
= −SdT + V dp + µdN
!
∂G
S=−
∂T p,N
!
∂G
V = Hence
∂p T,N
! !
∂S ∂V
=−
∂p T,N
∂T p,N

13. To show that the Joule-Thomson coefficient vanishes for an ideal gas. Recall,
V
αJT = − (1 − αT )
Cp
whereas expansion coefficient for ideal gas is
!
1 ∂V N kB
α= = = 1/T
V ∂T p,N
pV

## 14. Number of distinct arrangements of n atoms occupying N interstitial sites is

N!
Ω1 =
n!(N − n)!
which is also number of ways, Ω2 , of arranging N − n atoms on lattice sites. Hence entropy is
!2
N!
S = kB ln
n!(N − n)!
∼ 2kB (N ln N − n ln n − (N − n) ln(N − n))
F = E − T S = n +
2kB T (n ln n + (N − n) ln(N − n)) + const

4
Minimising F wrt n gives

n = N e−/2kB T

when   kB T .

## 15. The probabilities of occupying the three energy levels are:

z = e−/kB T
1
p1 =
1 + 2z + z 2
2z
p2 =
1 + 2z + z 2
z2
p3 =
1 + 2z + z 2
E = N (p1  + p2 2 + p3 3)
= N ( + p2  + p3 2)
2z
= N ( + )
!
1 +z
∂E 2N 2 z
=
∂T kB T (1 + z)2
2

16. The gases have same numbers of particles and and final temperature is same as initial one as
no energy is added to the system. Hence, as each gas occupies a volume 2V in the final state,
then from the Sackur-Tetrode formula:
3
S(initial) = 2N kB ln T +
2
V
2N kB ln + 2N c0
N
3
S(f inal) = 2N kB ln T
2
2V
+2N kB ln + 2N c0
N
∆S = 2N kB ln 2

This is greater than zero and hence the gases irreversibly expand into the larger volume. If
gases are identical, then we have 2N particles occupying volume 2V which has final entropy:
3
S(f inal) = 2N kB ln T +
2
2V
2N kB ln + 2N c0
2N
= S(initial)

## In this case, no extra entropy arises from ‘mixture’.

4!
17. Number of arrangements of n Ge atoms around C is (4−n)!n! . Probabilities of realising these
arrangements are:
(1 − x)4
p0 =
Z
3
4x(1 − x) e −/k BT
p1 =
Z
6x (1 − x)2 e−2/kB T
2
p2 =
Z

5
4x3 (1 − x)e−3/kB T
p3 =
Z
x4 e−4/kB T
p4 =
Z
Here,

Z = (1 − x)4 + 4x(1 − x)3 e−/kB T + 6x2 (1 − x)2 e−2/kB T + 4x3 (1 − x)e−3/kB T + x4 e−4/kB T
= (x + (1 − x)e−/kB T )4

At 700◦ C, kB T = 8 × 973 × 10−5 = .07784 eV. Hence e−/kB T = .2767. Thus Z = 2.6571 and pi
are: .3763, .4166, .1729, .0319, .0022.
This assumes equilibrium is achieved. In practice this may not be the case as the diffusion
energies of the atoms are so large that initial distributions are frozen in.

## 18. Ratio is approximately e−h̄ω/kB T = 0.03.

19.
N!
Ω=
n!(N − n)!
ln Ω = N ln N − n ln n − (N − n) ln(N − n)
ln Ω(2N, 2n) = 2N ln 2N − 2n ln 2n
−2(N − n) ln 2(N − n)
= 2 ln Ω + 2N ln 2 − 2n ln 2 − 2(N − n) ln 2
= 2 ln Ω

## This shows S = kB ln Ω is extensive function.

20. Let n1 , n2 be number of right and left pointing links and l = L/a, z = l/n.

L = (n1 − n2 )a
1 1
n = n1 + n2 n1 = (l + n) n2 = (n − l)
2 2
n!
W =
n1 !n2 !
S = kB ln W = kB (n ln n − n1 ln n1 − n2 ln n2 )
n
= kB (n ln n − ((1 + z) ln((1 + z)n/2) + (1 − z) ln((1 − z)n/2))
2
n
∼ kB (n ln 2 − {(1 + z)z − (1 − z)z + ..})
2
= nkB (ln 2 − z 2 /2),

## where we have Taylor expanded about z = 0. Hence

F = nkB T (z 2 /2 − ln 2)
!
∂F L
τ =− = kB T
∂L na2

21. Energy levels are Ek = kµB with k = −1, 0, 1. The statistical weight is
N!
Ω= ,
n1 !n2 !n3 !

6
X
F = nk Ek − kB T ln Ω
k
X X
= nk Ek − kB T {N ln N − nk ln nk }.
k k
X
M inimise f = F − α( nk − N )
k
with respect to α and nk
!
∂f X
= nk − N = 0,
∂α k
!
∂f
= Ek + kB T ln nk + kB T − α = 0,
∂nk
nk = N e−Ek /kB T /Z,
X
where Z = e−Ek /kB T .

Ek = kµB, k = 0, + 1, −1
x = µB/kB T
Z = 1 + 2 cosh x
2N µ sinh x
M=
1 + 2 cosh x
→ 2N µ2 B/3kB T as T → ∞
→ Nµ as T → 0