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# PHY303  Statistical Thermodynamics  Fall 2012  Prof. D.

Garanin
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Assignment 2, with solutions
1 Entropy change in the isobaric-isochoric cycle of an ideal gas

Show that the entropy change in the cyclic process of an ideal gas, that is represented by a rectangle in the (P, V ) diagram, is
zero.

## Figure 1: Isobar-isochore cycle.

Solution : In the isobatic process of an ideal gas, the innitesimal amount of heat is given by
δQ = dU + P dV = CV dT + P dV.
From the equation of state of the ideal gas
P V = νRT
follows PV P dV
T = , dT =
Substituting this into
νR νR

δQ
dS = ,
one obtains
T
CV P dV /(νR) + P dV dV dV
dS = = (CV + νR) = CP .
P V /(νR) V V
In the isochoric process of the ideal gas, is given by
δQ
V dP
δQ = CV dT = CV ,
νR
thus δQ V dP dP
dS = = CV = CV .
In our cyclic process,
T PV P

ˆ P2
dP P2
∆SAB = CV = CV ln >0
P1 P P1
P1
∆SCD = CV ln = −∆SAB
P2
ˆ V2
dV V2
∆SBC = CP = CP ln >0
V1 V V1
V1
∆SDA = CP ln = −∆SBC .
V2
The total entropy change
∆S = ∆SAB + ∆SBC + ∆SCD + ∆SDA = 0,
as it should be.
2 Entropy change in the isobaric-isochoric-isothermic cycle of an ideal gas

Show that the entropy change in the cyclic process of an ideal gas that include an isobar, an isochor, and an isotherm is zero.

## Figure 2: Isobar-isochor-isotherm cycle.

Solution : Using the results of the solution of the previous problem, one nds
V2 P1
∆SBC = CP ln > 0, ∆SCD = CV ln < 0.
V1 P2
In the isothermal process of an ideal gas dU = 0 thus δQ = P dV and
δQ P dV dV
dS = = = νR .
T T V
This yields V1
∆SDB = νR ln < 0.
V2
Using the equation of state of the ideal gas, on the ends of the isotherm one has
P1 V1 V1
= ⇒ ∆SCD = CV ln .
P2 V2 V2
The total entropy change over the cycle is
V2
∆S = ∆SBC + ∆SCD + ∆SDB = (CP − CV − νR) ln = 0,
V1
as it should be.
3 Entropy of a perfect gas

Calculate the entropy of a perfect gas as a function of (V, T ) by integration using S = ´ δQ/T .
Solution : Dene S(V , T ) = S as a reference point and calculate the entropy S(V, T ) via the integral of δQ/T over a path
(V , T ) ⇒ (V, T ), that is,
0 0 0
0 0
ˆ )
(V,T
δQ
S(V, T ) = S0 + .
T
(V0 ,T0 )

As the the entropy is a state function, its value does not depend on the path. Thus one can choose the most convenient path,
for instance, (V , T ) ⇒ (V , T ) ⇒ (V, T ). At the rst stage only the temperature is changing while the work is zero, thus
0 0 0
( )
∂U
δQ = dU = dT = CV dT.
∂T V

## Integration for the perfect gas (C V = const ) proceeds as follows:

ˆT
CV dT T
S(V0 , T ) = S0 + = S0 + CV ln .
T T0
T0
At the second stage T = const. As for the ideal gas U = U (T ), it does not change and δQ is only due to work,
δQ = P dV.

Using the equation of state of the ideal gas P V = νRT this can be rewritten as
dV
δQ = νRT .
V
Now integration with T = const proceeds as follows:
ˆV
dV T V
S(V, T ) = S(V0 , T ) + νR = S0 + CV ln + νR ln .
V T0 V0
V0

## Here the terms with T and V can be absorbed in the constant:

0 0

S(V, T ) = CV ln T + νR ln V + const.

Using C P − CV = νR (Meyer's relation) and γ = C P /CV , one can rewrite this formula as
S(V, T ) = CV (ln T + (γ − 1) ln V ) + const = CV ln T V γ−1 + const.

The argument of the logarithm is constant in the adiabatic process, S = const, thus the result has an expected behavior and
passes an error check.
4 Internal energy of a perfect gas in natural variables

Express the energy of a perfect gas in the natural variables, U = U (S, V ), and check relations
( ) ( ) ( ) ( )
∂U ∂U ∂T ∂P
T = , −P = , =− .
∂S V ∂V S ∂V S ∂S V

Solution : In the V, T variables the energy of a perfect gas has the form
U = CV T,

where a constant has been dropped for simplicity. The entropy of the perfect gas is given by
S = CV ln T V γ−1 , (1)
where again a constant has been dropped. From here one can express T as a function of S
( )
T =
V γ−1
1
exp
S
CV
. (2)
Thus the energy in its natural variables becomes
( )
U (S, V ) =
CV
V γ−1
exp
S
CV
. (3)
Note that U depends on the volume!
Now, using
dU = T dS − P dV
one can identify ( ) ( )
∂U ∂U
T = , −P = .
∂S ∂V
Let us check these relations. With the help of Eq. (2) one obtains.
V S

( ) ( )
∂U 1 S
= exp = T,
∂S V V γ−1 CV

## as it should be. Further, using γ = C P /CV and C P − CV = νR one obtains

( ) ( ) ( )
∂U (γ − 1) CV S νR S
=− exp =− exp .
∂V S Vγ CV Vγ CV
Using Eq. (2) ( )
∂U νRT PV
=− =− = −P,
∂V V V
as it should be. Thus we have obtained
S

( )
P =
νR

exp
S
CV
(4)
in the V, S variables. This formula also could be obtained from Eq. (1) and the equation of state, similarly to Eq. (2). Now, to
check the Maxwell identity, Using Eq. (2) one calculates
( ) ( )
∂T νR S
=− exp .
∂V S CV V γ CV

## On the other hand, from Eq. (4) one obtains

( ) ( ) ( )
∂P νR S ∂T
− =− exp = ,
∂S V CV V γ CV ∂V S

as expected.
5 Thermodynamic potentials F and G of the perfect gas

Express thermodynamic potentials F and G of the perfect gas in terms of their natural variables and check relations similar to
those in the preceding problem.
Solution : Using the denition of F and the formulas for U and S of a perfect gas, one obtains
F = U − T S = C T − T C ln T V V = −C T ln T V
(
V
)
/e . γ−1
(5)
V
γ−1

Since
dF = −SdT − P dV,
one can identify ( ) ( )
∂F ∂F
−S = , −P = .
∂T V ∂V T

## The entropy follows from Eq. (5) as

( )
∂F
S=− = −CV + CV + CV ln T V γ−1 = CV ln T V γ−1
∂T V

## that is a known result. The pressure is

( ) ( ( )) ( )
∂F ∂ CV T ln V γ−1 ∂ (ln V ) CV T (γ − 1) νRT
P =− = = CV T (γ − 1) = = ,
∂V T ∂V ∂V T V V
T

## also a known result.

The Maxwell relation (
∂S
) (
∂P
)
=
∂V ∂T
is now checked as follows
T V

( )
∂S ∂ ∂ ln V νR
= CV ln T V γ−1 = CV (γ − 1) = .
∂V ∂V ∂V V
On the other hand,
T

( ) ( )
∂P νR ∂S
= = ,
∂T V ∂V
as expected.
V T

For the Gibbs thermodynamic potential G all calculations are parallel to those for F , only one has to express all the formulas
via P instead of V , using the equation of state of the ideal gas.
6 Thermodynamics from F
The Helmholtz free energy of a certain gas has the form
ν2a
F =− − νRT ln (V − νb) + J(T ).
V
Find the equation of state of this gas, as well as its internal energy, entropy, heat capacities C and C and, in particular, their
dierence C − C .
P V

Solution : To nd the eqiation of state, one has to nd P that will ve a function of the native variables V, T :
P V

( )
(6)
2
∂F ν a νRT
P =− =− + .
∂V V V − νb T
2

## Rearranging this formula, one obtains ( )

(7)
2
ν a
P+ (V − νb) = νRT, 2
V
the van der Waals equation of a non-ideal gas.
Next, the entropy is given by ( )
∂F
S=− = νR ln (V − νb) − J ′ (T ).
∂T
Now the internal energy becomes
V

ν2a
U = F + TS = − + J(T ) − T J ′ (T ).
The heat capacity C can be found as
V
V ) (
∂U
CV = = −T J”(T )
∂T V
or as (
∂S
)
CV = T = −T J”(T ).
∂T V
Finding ( )
∂S
CP = T
∂T
requires more work. An explicit way to do this is to express V in the form V = V (P, T ) everywhere with the help of Eq. (7).
P

However, this V is a solution of a cubic equation that is better to avoid. Also this method is inconvenient to study C − C
because both heat capacities have to be functions of the same variables. Thus it is better to use the implicit method considering
P V

## S = S(V, T ) but with V = V (P, T ). Then one obtains

( ) ( ) ( ) ( ) ( )
∂S ∂S ∂V ∂S ∂T
CP = T +T = CV + T / .
∂T V ∂V T ∂T P ∂V T ∂V P

In this formula (
∂S
)
νR
= ,
∂V V − νb
whereas
T
( ) ( ) [ ( )]
∂T 1 ∂ ν2a 1 2ν 2 a ν2a
= P + 2 (V − νb) = − 3 (V − νb) + P + 2 .
∂V νR ∂V V νR V V
Here one can eliminate P using Eq. (6) that yields
P

( ) [ ]
∂T 1 2ν 2 a νRT
= − 3 (V − νb) + .
∂V P νR V V − νb
Gathering the terms, one obtains 2 [ ]
(νR) T 2ν 2 a νRT
CP − CV = / − 3 (V − νb) + ,
V − νb V V − νb
further νRT
CP − CV = νR 2
νRT − (2ν 2 a/V 3 ) (V − νb)
and, nally, νR
CP − CV = 2ν 2 a(V −νb)2
> νR.
1−
One can see that at high temperatures and large volumes the additional term in the denominator becomes small and the Meyer's
νRT V 3