Homework 2

David Sirajuddin
Physics 715 - Statistical Mechanics
Professor Michael Ramsey-Musolf
February 22, 2010
1. (Huang 1.5)
A substance has the following properties:
At a constant temperature T
0
the work done by it on expansion from V
0
to V is
W = RT
0
ln
V
V
0
The entropy is given by
S = R
V
V
0
_
T
T
0
_
a
where V
0
, T
0
, and a are xed constants.
(a) Calculate the Helmholtz free energy, F
The Helmholtz free energy F is dened as
F = E TS
where E, T, and S are the internal energy, temperature, and entropy of the system
respectively. Dierentiating this equation:
dF = dE (TdS +SdT)
And, recalling that the internal energy dE = TdS PdV , for pressure P and
volume V , admits
dF =

TdS PdV

TdS SdT
dF = PdV SdT (1)
Such that Huangs Eqn. (1.19) is retrieved [1]. It is noted that the variables V
and T have incidentally been chosen to be independent. The remaining parameter
(pressure P) may be obtained from the equation of state (see part (b)). The above
equation furnishes the following denitions:
1
Sirajuddin, David Homework 2 Physics 715, Spring 2010
_
F
V
_
T
= P and
_
F
T
_
V
= S (2)
Which may formally be obtained by independently letting V be constant (dV
0), and T be constant (dT 0) in Eqn. (1) followed by solving for the re-
maining parameter. Thus, the subscripts corresponding to the partial dieren-
tiation explicitly indicate which quantity is held constant during the operation
(e.g. (F/V )
T
instructs to dierentiate F with respect to V while holding the
temperature T constant). The partial dierential equations (2) are solved in order
to nd the state function F. Preliminarily, a partial integration is performed on
the left-hand equation over the interval V
0
V

V ,
_
F
V
_
T
= P
_
F(V,T)
F(V
0
,T)
F

=
_
V
V
0
PV

. .
=W
F(V, T) F(V
0
, T) = W
F(V, T) = W +F(V
0
, T)
F(V, T) = RT
0
ln
_
V
V
0
_
+F(V
0
, T) (3)
(Primed dummy variables are used for clarity). In the last step, the expression
for work given in the problem statement has been inserted. Due to the partial
integration, an arbitrary function F(V
0
, T) must be appended given that the only
constraint on the above expression for F(V, T) follows from Eqn. (2), i.e. that
the F(V
0
, T) term vanishes under partial dierentiation with respect to V so that
Eqn. (2) is recovered. This restriction allows for the integration constant to
be, in general, a function of the temperature T.
In order to solve for the function F(V
0
, T), a partial derivative with respect to V
may be performed on Eqn. (3) so as to establish an equivalence with the right
hand equation of Eqn. (2). Beginning with Eqn. (3):
_
F
T
_
V
=

_

T
_
V
RT
0
ln
_
V
V
0
_
. .
=0, not a function of T
+
_

T
F(V
0
, T)
_
V
_
F
T
_
V
=
_

T
F(V
0
, T)
_
V
(4)
Noting that the problem statement informs S = R
V
V
0
_
T
T
0
_
a
, the right-hand equa-
tion in Eqn. (3) may be written as
2
Sirajuddin, David Homework 2 Physics 715, Spring 2010
_
F
T
_
V
= S = R
V
V
0
_
T
T
0
_
a
(5)
Equating the right-hand sides of Eqns. (4) and (5) and integrating over the
interval [T
0
, T],
_

T
F(V
0
, T)
_
V
= R
V
V
0
_
T

T
0
_
a
_
F(V
0
,T)
F(V
0
,T
0
)
F

= R
V
V
0
_
T
T
0
_
T

T
0
_
a
T

F(V
0
, T
0
) F(V
0
, T) = . . .
F(V
0
, T) = R
V
V
0
_
T
T
0
_
T

T
0
_
a
T

+F(V
0
, T
0
) (6)
The integral over T is solved by the substitution,
=
T

T
0
T
0
d = dT

so that
_
T
T
0
(. . .)dT

T
0
_
T/T
0
1
(. . .)d
where the partial integration has been replaced by ordinary integration for con-
venience, with the constant volume condition taken to be understood.
The integral is then,
_
T
T
0
_
T

T
0
_
a
dT

= T
0
_
T/T
0
1

a
d
=
T
0
a + 1
_

a+1

T/T
0
1
_
T
T
0
_
T

T
0
_
a
dT

=
T
0
a + 1
_
_
T
T
0
_
a+1
1
_
Inserting this result into Eqn. (6) gives
F(V
0
, T) = R
V
V
0
T
0
a + 1
_
_
T
T
0
_
a+1
1
_
+F(V
0
, T
0
)
Finally, substituting this result into Eqn. (3) yields the nal result,
3
Sirajuddin, David Homework 2 Physics 715, Spring 2010
F(V, T) = RT
0
ln
_
V
V
0
_
+F(V
0
, T)
F(V, T) = RT
0
ln
_
V
V
0
_

V
V
0
RT
0
a + 1
_
_
T
T
0
_
a+1
1
_
+F(V
0
, T
0
)
F(V, T) F(V
0
, T
0
) = RT
0
ln
_
V
V
0
_

V
V
0
RT
0
a + 1
_
_
T
T
0
_
a+1
1
_
Letting F(V, T) F(V, T) F(V
0
, T
0
), the Helmholtz free energy is determined
to be
F(V, T) = RT
0
_
ln
_
V
V
0
_
+
V
V
0
1
a + 1
_
_
T
T
0
_
a+1
1
__
(7)
For some constant F(V
0
, T
0
) that may be specifed by boundary conditions.
(b) Find the equation of state
Using result (7) with the left-hand Eqn. (2), the equation of state is computed:
P =
_
(F)
V
_
T
=
_
F(V, T)
V
_
T

_
F(V
0
, T
0
)
V
_
T
. .
=0, constant
=
_
F(V, T)
V
_
T
=
_

V
_
T
_
ln
_
V
V
0
_
+
V
V
0
1
a + 1
_
_
T
T
0
_
a+1
1
__
= +RT
0
_
1/

V
0
V/

V
0
+
1
V
0
1
a + 1
__
T
T
0
a+1
1
___
P = RT
0
_
1
V
+
1
V
0
1
a + 1
__
T
T
0
a+1
1
___
(8)
Despite the universal gas constant R appearing in these equations, the equation
of state (8) reveals that the substance in question is not an ideal gas, where
P = NRT/V .
4
Sirajuddin, David Homework 2 Physics 715, Spring 2010
(c) Find the work done at an arbitrary constant temperature T.
The equation of state P = P(V, T), above, may be used to nd the work W done
at arbitrary temperature T in the expansion from volume V
0
to V .
W =
_
V
V
0
PdV
=
_
V
V
0
RT
0
_
1
V
+
1
V
0
1
a + 1
__
T
T
0
a+1
1
___
dV
= RT
0
_
ln V +
V
V
0
1
a + 1
__
T
T
0
a+1
1
___
V
V
0
= RT
0
_
ln V ln V
0
+
V V
0
V
0
1
a + 1
__
T
T
0
a+1
1
___
it then follows that
W = RT
0
_
ln
V
V
0
+
V V
0
V
0
1
a + 1
__
T
T
0
a+1
1
___
(9)
2. Prove the following two relations:
TdS = C
P
dT T(V/T)
P
dP (10)
(C
P
/P)
T
= T(
2
V/T
2
)
P
(11)
Eqn. (10) proof
Beginning with the dQ Eqn. (1.6) from Huang [1]:
dQ =
__
U
T
_
P
+P
_
V
T
_
P
_
dT +
__
U
P
_
T
+P
_
V
P
_
T
_
dP
where the notation of Huang is adopted, U is the internal energy, Qrepresents heat, and
all other quantities are as previously dened. Noting that the enthalpy H = U +PV ,
the specic heat at constant pressure C
P
can be computed as follows,
5
Sirajuddin, David Homework 2 Physics 715, Spring 2010
C
P
=
_
H
T
_
P
=
_

T
_
P
(U +PV )
=
_
U
T
_
P
+

T
(PdV )
=
_
U
T
_
P
+

_
P
T
dV
_
P
. .
=0,P=constant
+P
_
V
T
_
P
C
p
=
_
U
T
_
P
+P
_
V
T
_
P
(12)
Inputting this result into the dQ equation, and letting dQ = TdS implies
dQ =
__
U
T
_
P
+P
_
V
T
_
P
_
. .
=C
P
dT +
__
U
P
_
T
+P
_
V
P
_
T
_
dP
TdS = C
p
dT +
__
U
P
_
T
+P
_
V
P
_
T
_
. .
'
dP (13)
The solution strategy proceeds by proving term ' is identical to T(V/T)
P
in
Eqn. (10). Motivated by this end, the desired form of term ' may be obtained by
manipulating the above equation. Specically, it is noted that dS itself is an exact
dierential,
dS =
C
p
T
dT +
1
T
__
U
P
_
T
+P
_
V
P
_
T
_
dP
which necessarily constrains the terms on the right-hand side of the equation to satisfy:

P
_
C
P
T
_
T

=

T
_
1
T
_
U
P
_
T
+
P
T
_
V
P
_
T
_
P

(14)
Evaluating both sides of the above equation, beginning with the left-hand side (term
), the specic heat C
P
is replaced with expression (12):
6
Sirajuddin, David Homework 2 Physics 715, Spring 2010
=

P
_
C
P
T
_
T
=
1
T
_
C
P
P
_
T
, T is held constant
=
1
T

P
__
U
T
_
P
+P
_
V
T
_
P
_
T
=
1
T
_

2
U
PT
_
P,T
+
1
T
P
_

2
V
PT
_
P,T
+
1
T

_
P
P
_
T
=1
_
V
T
_
P
=
1
T
_

2
U
PT
_
P,T
+
1
T
P
_

2
V
PT
_
P,T
+
1
T
_
V
T
_
P
And, the right-hand side term of Eqn. (14) admits
=

T
_
1
T
_
U
P
_
T
+
P
T
_
V
P
_
T
_
P
=
_

T
_
P
_
1
T
_
U
P
_
T
_
+
_

T
_
P
_
P
T
_
V
P
_
T
_
=

T
_
1
T
_
P
. .
=1/T
2
_
U
P
_
T
+
1
T
_

2
U
TP
_
T,P
+

T
_
P
T
_
P
. .
=P/T
2
_
V
P
_
T
+
P
T
_

2
V
TP
_
T,P
=
1
T
2
_
U
P
_
T
+
1
T
_

2
U
TP
_
T,P

P
T
2
_
V
P
_
T
+
P
T
_

2
V
TP
_
T,P
Equating terms and above, Eqn. (14) yields,

P
_
C
P
T
_
T

=

T
_
1
T
_
U
P
_
T
+
P
T
_
V
P
_
T
_
P

1
T
_

2
U
PT
_
P,T
J
+

P
T
_

2
V
PT
_
P,T

+
1
T
_
V
T
_
P
=
1
T
2
_
U
P
_
T
+

1
T
_

2
U
TP
_
T,P
J

P
T
2
_
V
P
_
T
+

P
T
_

2
V
TP
_
T,P

where correspsonding terms are cancelled in pairs as per the labels J and . The
cancellation is substantiated on the enforcement that the functions U and V are uni-
formly convergent such that the order of partial dierentiation may be interchanged
(i.e.
P

T
U =
T

P
U and
P

T
V =
T

P
V ). Thus,
7
Sirajuddin, David Homework 2 Physics 715, Spring 2010
1
T
_
V
T
_
P
=
1
T
2
_
U
P
_
T

P
T
2
_
V
P
_
T
T
_
V
T
_
P
=
_
U
P
_
T
+P
_
V
P
_
T
= '
So that desired form of term ' of the TdS equation (14) is retrieved. Inputting this
result into Eqn. (14) provides the nal result,
TdS = C
p
dT +
__
U
P
_
T
+P
_
V
P
_
T
_
. .
'
dP
TdS = C
P
dT T(V/T)
P
dP 7
Eqn. (11) proof
The second relation (Eqn. (11)),
_
C
P
P
_
T
= T
_

2
V
T
2
_
P
can be proved by using result (10) above:
TdS = C
P
dT T(V/T)
P
dP
Equations are developed by setting P and T constant independently, and solving for
the remaining parameter. Letting P be constant implies dP 0 in the above equation,
such that it can be written
(TdS)
P
= (C
P
dT)
P

_
S
T
_
P
=
C
P
T

_

2
S
PT
_
P,T
=
1
T
_
C
P
P
_
T
(15)
where a subsequent dierentiation with respect to P has been performed to obtain
an equation for (C
P
/P)
T
as per Eqn. (11). The additional relation is obtained by
allowing T to be constant so that dT 0, implying
8
Sirajuddin, David Homework 2 Physics 715, Spring 2010
(
TdS)
T
=
_
T
_
V
T
_
P
dP
_
T

_
S
P
_
T
=
_
V
T
_
P

_

2
S
TP
_
T,P
=
_

2
V
T
2
_
P
(16)
The left-hand sides of Eqns. (15) and (16) are recognized to be identical provided that
the dierential operators commute. Thus, upon equating the right-hand terms of both
equations,
1
T
_
C
P
P
_
T
=
_

2
V
T
2
_
P
which gives,
_
C
P
P
_
T
= T
_

2
V
T
2
_
P
7
And, the proposition is proved.
3. (a) Derive equations 14(a-e) from Lecture V [2]
The equations to be proven are as follows,
_
E
P
_
T
= T
_
V
T
_
P
P
_
V
P
_
T
(17)
_
H
V
_
T
= T
_
P
T
_
V
+V
_
P
V
_
T
(18)
_
H
P
_
= V T
_
V
T
_
P
(19)
_
E
T
_
P
= C
P
P
_
V
T
_
P
(20)
_
H
T
_
V
= C
V
+V
_
P
T
_
V
(21)
where the notation of Ramsey-Musolf is used [2] (E is the internal energy, and
all other quantities are as previously dened), and the equation numbers have
been shifted in order to avoid confusion with previous equation labels used in this
assignment. Obtaining these results is done with aid of the following diagram [2]:
9
Sirajuddin, David Homework 2 Physics 715, Spring 2010
Figure 1: Diagram summarizing thermodynamic parameter relationships [2]
Which visually summarizes the relationships of thermodynamic quantities and
potentials. Partial dierentiation with respect to one of the anking parameters
of a given o-diagonal element (while the other anked quantity is held constant)
admits the corresponding thermodynamic quantity traced out by the diagonal
arrow followed. Following the arrow implies that one performs this derivative
with respect to the parameter it connects with, while the other quantity that
anks the potential of interest is held constant. Going against an arrow suers a
change by a minus sign.
Eqn. (17) proof
The result is found by dierentiating the rst law with respect to the pressure P
at constant temperature T:
dE = TdS PdV (22)
_
E
P
_
T
=
_

P
_
T
(TdS)
_

P
_
T
(PdV )
=

_
T
P
_
T
=0 , T =constant
dS +T
_
S
P
_
T

_
_

_
P
P
dV
_
T
=0
+P
_
V
T
_
T
_
_
T
_
E
P
_
T
= T
_
S
P
_
T

P
_
V
P
_
T
(23)
From Figure 1, the relation S = (G/T)
P
, is used to evaluate term above:
10
Sirajuddin, David Homework 2 Physics 715, Spring 2010
= T
_
S
P
_
T
=
_

P
_
T
_
G
T
_
P
=
_

T
_
P
_
G
P
_
T
. .
=V
=
_

T
_
P
V =
_
V
T
_
P
Substituting this result into term into Eqn. (23) completes the derivation
_
E
P
_
T
=

T
_
S
P
_
T
P
_
V
P
_
T
_
E
P
_
T
=
_
V
T
_
P
P
_
V
P
_
T
7
Eqn. (18) proof
Denition (18):
_
H
V
_
T
= T
_
P
T
_
V
+V
_
P
V
_
T
is furnished by the denition of enthalphy dH = TdS +V dP. Dierentiating this
equation,
_
H
V
_
T
=
_

V
_
T
(TdS) +
_

V
_
T
(V dP)
=

_
T
V
_
T
=0 , T =constant
dS +T
_
S
V
_
T
+

_
V
V
dP
_
T
=0
+V
_
P
V
_
T
_
H
V
_
T
= T
_
S
V
_
T
1
+V
_
P
V
_
T
From Figure 1, the relation S = (F/T)
V
, is used to evaluate term 1 above:
11
Sirajuddin, David Homework 2 Physics 715, Spring 2010
1 = T
_
S
V
_
T
=
_

V
_
T
_
F
T
_
V
=
_

T
_
V
_
F
V
_
T
. .
=P
1 =
_

T
_
V
(P) = +
_
P
V
_
T
Inputting this result into term 1 into Eqn. (24) completes the proof
_
H
V
_
T
=
1
T
_
S
V
_
T
+V
_
P
V
_
T
_
H
V
_
T
= T
_
P
V
_
V
+V
_
P
V
_
T
7
Eqn. (19) proof
The same procedure as in the derivation of Eqn. (18) above is used to demonstrate
the validity of Eqn. (19), which reads
_
H
P
_
T
= V T
_
V
T
_
P
This time, the enthalphy dH = TdS +V dP is dierentiated with respect to P at
constant T,
_
H
P
_
T
=
_

P
_
T
(TdS) +
_

P
_
T
(V dP)
=

_
T
P
_
T
=0 , T =constant
dS +T
_
S
P
_
T
+

_
V
P
dP
_
T
=0
+V

_
P
P
_
T
=1
_
H
P
_
T
= T
_
S
P
_
T
*
+V
From Figure 1, it is seen that S = (G/T)
P
, is used to evaluate term * above:
12
Sirajuddin, David Homework 2 Physics 715, Spring 2010
* = T
_
S
P
_
T
=
_

P
_
T
_
G
T
_
P
=
_

T
_
P
_
G
P
_
T
. .
=V
* =
_

T
_
P
(V ) =
_
V
P
_
T
Combining this result with Eqn. (25) shows that,
_
H
P
_
T
=
*
T
_
S
P
_
T
+V
_
H
P
_
T
= T
_
V
T
_
P
+V 7
Eqn. (20) proof
Verifying Eqn. (20),
_
E
T
_
P
= C
P
P
_
V
T
_
P
is accomplished by dierentiating the First Law, dE = TdS PdV , with respect
to T at constant P.
dE = TdS PdV (24)
_
E
T
_
P
=
_

T
_
P
(TdS)
_

T
_
P
(PdV )
=

_
T
T
_
P
dS
=0
+T
_
S
P
_
T

_
_

_
P
P
dV
_
T
=0
+P
_
V
T
_
T
_
_
T
_
E
P
_
T
= T
_
S
P
_
T
"
P
_
V
P
_
T
(25)
Term " can be shown to be identical to the specic heat at constant pressure P
by invoking the denition of enthalphy: dH = TdS + V dP. Holding P constant
implies dP 0, such that
13
Sirajuddin, David Homework 2 Physics 715, Spring 2010
(dH)
P
= (TdS)
P

_

T
_
P
(H) =
_

T
_
P
(TdS)
_
H
T
_
P
=

_
T
T
_
P
dS
. .
=0, T=constant
+T
_
S
T
_
P
_
H
T
_
P
= T
_
S
T
_
P
C
P
= "
Where term " has been identied as the specic heat C
P
. Inserting this result
into Eqn. (25) admits,
_
E
T
_
P
= C
P
P
_
V
T
_
P
7
Thus, proving statement (20).
Eqn. (21) proof
Equation (21),
_
H
T
_
V
= C
V
+V
_
P
T
_
V
is proven in a similar manner to Eqn. (20). The denition of enthalphy, dH =
TdS +V dP, is rst dierentiated with respect to T at constant V .
_
H
T
_
V
=
_

T
_
V
(TdS) +
_

T
_
V
(V dP)
=

T
(TdS)
V
+

_
V
T
_
. .
=0, V =constant
dP +V
_
P
T
_
V
_
H
T
_
V
=

_
T
T
_
V
dS
=0
+T
_
S
P
_
T
+V
_
P
T
_
V
_
H
T
_
V
= T
_
S
P
_
T

+V
_
P
T
_
V
(26)
Term is shown to be identical to the specic heat C
V
at constant volume by
employing the First Law (dE = TdS PdV ). Allowing V to be constant implies
dV 0, so that
14
Sirajuddin, David Homework 2 Physics 715, Spring 2010
(dE)
V
= (TdS)
V

_

T
_
V
(E) =
_

T
_
V
(TdS)
_
E
T
_
V
=

_
T
T
_
V
dS
. .
=0
+T
_
S
T
_
V
_
E
T
_
V
= T
_
S
T
_
V
C
V
=
Where term has been identied as the specic heat C
V
. Substituting this result
into Eqn. (26) validates that,
_
H
T
_
V
= C
V
+V
_
P
T
_
V
7
(b) Use the results from part (a) to determine the change in internal energy E when
an ideal gas goes from pressure P
1
to pressure P
2
and the change in enthalpy H
when the systems temperature changes from T
1
to T
2
.
E calculation
Equation (17) of part (a) may be used to directly nd the change in internal
energy E = E(P
2
, T) E(P
1
, T). Equation (17) reads,
_
E
P
_
T
= T
_
V
T
_
P
P
_
V
P
_
T
For an ideal gas law, the equation of state V = NkT/P, may be used in the terms
above. Computing the necessary derivatives,
_
V
T
_
P
=
Nk
P
and
_
V
P
_
T
=
NkT
P
2
Inputting these expressions into the above equation,
_
E
P
_
T
= T
_
Nk
P
_

P
_
NkT
P

2
_
=
NkT
P
. .
V
+
NkT
P
. .
V
= V +V
_
E
P
_
T
= 0
Integrating over the pressure for P
1
P

P
2
implies
15
Sirajuddin, David Homework 2 Physics 715, Spring 2010
E E(P
2
, T) E(P
1
, T) = 0 7
H calculation
Equation (21),
_
H
T
_
V
= C
V
+V
_
P
T
_
V
can be used in tandem with the ideal gas law (P = NkT/V ) to nd the change in
enthalpy, H = H(P, T
2
) H(P, T
1
), when an ideal gas changes from a temper-
ature T
1
to T
2
. Computing the second term on the right-hand side of the above
equation,
V
_
P
T
_
V
=

V
_
Nk

V
_
= Nk
So that the above equation gives,
_
H
T
_
V
= C
V
+Nk
=

C
V
+ (C
P

C
V
)
_
H
T
_
V
= C
P
Where the identication Nk = C
P
C
V
follows from the discussion of Huang (pg.
9). This substitution has tacitly assumed that the specic heat C
V
is independent
of temperature. Should the specic heat C
P
also be independent of temperature
for the range [T
1
, T
2
], the change in enthalpy may be directly obtained,
H H(P, T
2
) H(P, T
1
) = C
p
(T
2
T
1
) 7
4. Show that
C
P
C
V
= T
[(P/T)
V
]
2
(P/V )
T
Equating the two TdS equations (1.13) and (1.14) of Huang, and choosing P and V to
be independent variables (where the temperature T may be obtained by the equation
of state), the following equation is arrived at [1]:
_
(C
P
C
V
)
_
T
V
_
P
T
_
P
T
_
V
_
dV =
_
(C
P
C
V
)
_
T
P
_
V
T
_
V
T
_
P
_
dP
16
Sirajuddin, David Homework 2 Physics 715, Spring 2010
Since the parameters V and P have been chosen as independent, the coecients (square
bracketed terms) of their dierential elements must vanish. Equating the right-hand
coecients to zero admits the result quoted in the problem statement.
(C
P
C
V
)
_
T
P
_
V
T
_
V
T
_
P
= 0
C
P
C
V
= T
(V/T)
P
(T/P)
V
The lemmas provided by Huang are used to recast this equation into the desired form
given in the problem statement [1, pg. 20]. Lemma (b) implies,
C
P
C
V
= = T
(V/T)
P
(T/P)
V
(27)
= T
_
V
T
_
P
1
(T/P)
V
. .
=(P/T)
V
C
P
C
V
= T
_
V
T
_
P
_
P
T
_
V
(28)
The term (V/T)
P
is replaced by use of the cyclic permutation lemma (c),
_
V
T
_
P
_
T
P
_
V
_
P
V
_
T
= 1 (29)
An expression for (V/T)
P
is obtained from this equation by aid of lemma (b), which
allows the following identies,
_
T
P
_
V
=
1
(P/T)
V

_
T
P
_
V
_
P
T
_
V
= 1
_
P
V
_
T
=
1
(V/P)
T

_
P
V
_
T
_
V
P
_
T
= 1
Thus, multiplying Eqn. (29) by the indicated derivatives above such that these prod-
ucts are equal to unity isolates an equation for (V/T)
P
(which may be substituted
back into the original equation [Eqn. (28)] to recover the result). Performing this
multiplication on Eqn. (29) admits
_
V
T
_
P

__
T
P
_
V
_
P
T
_
V
_
=1

__
P
V
_
T
_
V
P
_
T
_
=1
=
_
P
T
_
V
_
V
P
_
T
17
Sirajuddin, David Homework 2 Physics 715, Spring 2010
giving
_
V
T
_
P
=
_
P
T
_
V
_
V
P
_
T
Using this result in Eqn. (28),
C
P
C
V
= T
_

_
P
T
_
V
_
V
P
_
T
_ _
P
T
_
V
= T
_
P
T
_
2
V
_
V
P
_
T
Finally, using lemma (b) once more implies (V/P)
T
= 1/(V/P)
T
so that the
above equation can be written in its nal form
C
P
C
V
= T
[(P/T)
V
]
2
(P/V )
T
7
which veries the equation.
5. Show that
_
T
P
_
S
=
_
T
C
P
__
V
T
_
P
(30)
From the TdS Eqn. (1.14) in Huang [1]:
TdS = C
P
dT T
_
V
T
_
P
dP
Letting the entropy S be constant implies dS 0,
0 = C
P
dT T
_
V
T
_
P
dP
C
P
dT = T
_
V
T
_
P
dP
Solving for (T/P)
S
yields the proposed equation,
_
T
P
_
S
=
T
C
P
_
V
T
_
P
7
18
Sirajuddin, David Homework 2 Physics 715, Spring 2010
6. Show that
lim
T0
_
P
T
_
V
0
The proof follows from a direct application of the Third Law. That is to say, that
the entropy at absolute zero approaches a constant, which may be taken to be zero.
Equivalently, the result follows from pure mathematical considerations after an initial
physical denition is introduced. This denition is given as Eqn. (1.40) in Huang
as the entropy S(T) at a state corresponding to a temperature T calculated from an
initial state at absolute zero [1, pg. 26]:
S(A) =
_
T
0
C
V
(T)
dT
T
where, in the notation of Huang, the term C
R
is taken to be C
V
. The claim is made
that
_
P
T
_
V
=
_
S
V
_
T
and will be proven a posteriori. Proceeding with the denition of the entropy S(T), it
can be written
_
S
V
_
T
=
_

V
_
T
_
T
0
C
V
dT
T
=
_
T
0
_
C
V
V
_
T

dT
T
(31)
Term may be recasted by aid of the TdS equation (1.13) [1].
TdS = C
P
dT +T
_
P
T
_
V
dV
dS =
C
P
T
dT +
_
P
T
_
V
dV
where the parameters T and V are independent. Letting each of these quantities be
constant independently, and solving for the remaining parameter allows the following
two relations to be written,
19
Sirajuddin, David Homework 2 Physics 715, Spring 2010
_
S
T
_
V
=
C
V
T

_

2
S
V T
_
V,T
=
1
T
_
C
V
V
_
T
(32)
and
_
S
V
_
T
=
_
P
T
_
V

_

2
S
TV
_
T,V
=
_

2
P
T
2
_
V
(33)
where a subsequent dierentiation has been performed on each equation. Enforcing
that the partial dierential operators commute, the left-hand sides are identical and
the right-hand terms may be equated:
_
C
V
V
_
T
= T
_

2
P
T
_
V
(34)
It is noted that the the left-hand term is exactly that of term of Eqn. (31). Inserting
this result implies
_
P
T
_
V
=
_
T
0
_

2
P
T
2
_
V
=
__
P
T
_
V
_
T
0
_
P
T
_
V
=
__
P
T
_
V
_
T

__
P
T
_
V
_
T=0
Where, for want of a clearer notation, the subscripts labeling the square brackets refer
to the temperature at which the quantity is evaluated at (rather than indicate which
parameter to hold constant under partial dierentiation). It is seen that the original
claim has been proven (i.e. (P/T)
V
= (S/V )
T
Evaluating this expression in the
limit T 0, directly proves the posit of the problem statement,
lim
T0
_
P
T
_
V
0 7
20
Sirajuddin, David Homework 2 Physics 715, Spring 2010
References
[1] Huang, Kerson Statistical Mechanics 1987. John Wiley & Sons, Inc. Canada.
[2] Ramsey-Musolf, Michael Physics 715 - Statistical Mechanics Class Notes, University of
Wisconsin - Madison. Spring 2010.
21