Callen
Callen
Callen
Homework #1
Prakash Gautam
April 17, 2018
3As2 As3
T = (thermal equation of state), P = (mechanical equation of state).
v v2
Where A is a constant.
(a) Find µ as a function of s and v, and then find the fundamental equation.
Solution:
Given P and T the differential of each of them can be calculated as
6As 3As2 6As2 3As3
dT = ds − dv ⇒ sdT = ds − 2 dv
v v2 v v
3As2 2As3 3As2 2As3
dP = ds − dv ⇒ vdP = ds − 2 dv
v2 v3 v v
The Gibbs-Duhem relation in energy representation allows to calculate the value of µ.
dµ = vdP − sdT
3As2 2As3 6As2 3As3
= ds − 2 dv − ds + 2 dv
v[ v ] v ( 3v)
3As2 As3 As
=− ds − 2 dv = −d
v v v
As3
This can be identified as the total derivative of v so the rel
( 3)
As As3
dµ = −d ⇒ µ=− +k
v v
Where k is arbitrary constant. We can plug this back to Euler relation to find the fundamental
equation as.
u = Ts − Pv + µ
3As3 As3 As3 As3
= − − +k = +k
v v v v
As3
So the fundamental equation of the system is v + k. □
(b) Find the fundamental equation of this system by direct integration of the molar form of the equation.
Solution:
The differential form of internal energy is
du = T ds − P dv
3As2 As3
= ds − 2 dv
v v
1
3
As before this is just the total differential of As
v so the relation leads to
( 3)
As As3
du = d 2
⇒ u= +k
v v
This k should be the same arbitrary constant that we got in the previous problem. □
0.16
0.14
0.12
0.1
(b) If the internal wall is now made diathermal and the system is allowed to come to equilibrium, what
are the internal energies of each of the individual systems?
Solution:
If the wall is made diathermal and the energy can flow the total energy of the remains constant
E = EA + EB . Taking differential on both sides we get dE = dEA + dEB = 0. Since there is no
change in volume or the number of molecules dV = 0 and dN = 0. Thus the differential relation of
entropy reduces to dS = T1 dE. The additive property allows us to write
1 1 dEA dEB 1 1
dS = dSA + dSB = dEA + dEB ⇒ =− ⇒ =
TA TB TA TB TA TB
The quantities TA and TB for each systems can be from the fundamental equation thus
( ) ( )1/3 ( ) ( )1/3
1 ∂SA C NA VA 1 ∂SB C NB VB
= = 2 = = 2
TA ∂EA 3 EA TB ∂EB 3 EB
2
These expressions can be simplified down to get and noting EA + EB = 80J we have two linear
expressions
√
NB VB
EB = EA EA + EB = 80 ⇒ EA = 51.93J EB = 28.07J
NA VA
So the after equilibrium the internal energy of system A is EA = 51.93J and for system B it is
EB = 28.07J. □
3. An impermeable, diathermal, and rigid partition divides a container into two subvolumes, of volume nV0
and mV0 . The subvolumes contain respectively, n moles of H2 and m moles of N e, each to be considered
as a simple ideal gas. The system is maintained at a constant temperature T . The partition is suddenly
ruptured and equilibrium is allowed to re-establish. Find the change in entropy of the system. How is the
result related to the “entropy of mixing”?
Solution:
The fundamental equation of ideal gas can be written as U = cN RT and equivalently as P V = N RT thus
the quantities
1 N cR
U = cN RT ⇒ = cR =
T U u
P N R
P V = N RT ⇒ =R =
T V v
Sine it is true for each of these systems we can write
( ) ( )
1 P cR R uf vf
ds = du + dv ⇒ ds = du + dv ⇒ s = s0 + cR ln + R ln
T T u v ui vi
The initial and final molar volume for each of the gases is
nV0 mV0
vih = = V0 vin = = V0
n m
(m + n)V0 ( m) (m + n)V0 ( n)
vf h = = 1+ V0 vf n = = 1+ V0
n n m m
Also since the temperature of system is constant and that no heat flows in or out of the composite system
the change in internal energy is zero thus ui = uf for both thus the total final entropy become
( ) ( ) (
uf h vf h m)
sh = s0h + cR ln + R ln = s0h + R ln 1 +
uih vih n
Similarly for N e the final entropy of system is
( n)
sn = s0n + R ln 1 +
m
The total change in entropy is
∆S = msn + nsh − (ms0n + ns0h )
( n) ( m)
= mR ln 1 + + msn0 + nR ln 1 + + nsh0 − (ms0n + ns0h )
( m
) ( ) n
m n
= n ln 1 + + m ln 1 +
n m
This is exactly equal to the Entropy of mixing. □
3
4. The entropy of blackbody radiation is given by the formula
4
S= σV 1/4 E 3/4 ,
3
where σ is a constant.
(a) Show that S is an extensive parameter.
(b) Determine the temperature and the pressure of the radiation.
Solution:
The Entropy relation can be inverted to get
( )1/3
81S 4
E=
256σ 4 V
Differentiating this with repsect to V to get the pressure gives
( ) √
3 4
∂E 6S 3
P =− = 4 4
∂V 8V 3 σ 3
The temperature similarly is
( ) √ √
∂E 3
63S
T = √
= 3 4
∂S 2 V σ3
Thus the temperature and pressure are determined. □
5. For a particular system, it is found that e = (3/2)P v and P = AvT 4 . Find the molar Gibbs potential and
molar Helmholtz potential for the system.
Solution:
Since there are two equations of state we can modify them to express the intensive parameters as
( )1/4 ( )1/4
2e P 2u
P = T = =
3v Av 3Av 2
These can be used in Entropy differential equation to get
1 P
ds = de + dv
T T
( )
2 1/4
( )1/4
3A v 8A e3
= de + dv
2 e 27 v 2
( )1/4
128Av 2 e3
The above expression can be recocnized as the total differential of 27
( )1/4 ( )1/4
128Av 2 e3 128Av 2 e3
ds = d ⇒ s= + s0
27 27
4
Multiplying thourgh by N to get the non molar quantities we get
( )1/4
128A V 2 E 3
S= + S0
27 N
This above relation can be inverted to get the fundamental energy representation. So we get
[ ]1/3
27 N
E= (S − S0 )4
128A V 2
This serves as the fundamental Energy relation which can be used to find the Gibbs and Helmholtz potential.
We can now find the intensive parameters T and P in terms of the extensive parameters as
( ) [ ]1/3 ( )1/3
∂E ∂ 27 N 1 N
T = = 2
(S − S0 ) 4
= √ (S − S0 )1/3
∂S ∂S 128A V 3
2A V 2
We can invert to find S as a function of T so
2AV 2 3
S = S0 + T
N
Similarly we can find the intensive parameter P as
( ) ( )1/3
∂E 1 S − S0
P =− = √ N 1/3
∂V 3
2 2A V5
Equipped with these functions we can now find the Gibbs potential as
G = E − TS + PV
[ ]1/3 ( ) [ ]1/5
27 N 2AV 2 3 1 N (S − S0 )4
= (S − S0 )4
− T · S0 + T +P ·
128A V 2 N 16A P3
( 3 2 )1/5
A P 12 8 AT 4 V 2
= T V −
N3 2N
This gives the Gibbs Potential now the Helmholtz potential can be similarly found as
F = E − TS
[ ]1/3 ( )
27 N 2AV 2 3
= (S − S 0 ) 4
− T · S 0 + T
128A V 2 N
4 2
AT V
=−
2N
4 2
Thus the Helmholtz potential is − AT2NV . □