Thermodynamics: Examples for chapter 3.

1. Show that (C
V
/V ) = 0 for a) an ideal gas, b) a van der Waals gas
and c) a gas following P =
nRT
V nb
. Assume that the following result
holds:
_
U
V
_
T
= T
_
P
T
_
V
P
Hint: In b) and c), dierentiate with respect to both temperature and
volume and recall that for exact dierentials the order of dierentiation
can be exchanged.
Solution:
The lecture notes give: C
V
=
_
U
T
_
V
. Dierentiate this equation with
respect to volume:
_
C
V
V
_
T
=
_

V
_
U
T
_
V
_
T
=
_

T
_
U
V
_
T
_
V
By using the relation given in the problem, we can write this as:
_
C
V
V
_
T
=
_

T
_
U
V
_
T
_
V
=
_
(P +T (P/T)
V
)
T
_
V
= T
_

2
P
T
2
_
V
Next we consider the various equations of state:
a) Ideal gas. P = nRT/V from which the second derivative of pres-
sure (see above) is zero and therefore
_
C
V
V
_
T
= 0.
b) For a van der Waals gas we have: P =
nRT
V nb

n
2
a
V
2
. Dierentiation
of P with respect to T once just gives nR/(V nb). This does
not depend on T and hence
_
C
V
V
_
T
= 0.
c) Dierentiation of P twice with respect to T again gives zero and
hence
_
C
V
V
_
T
= 0.
1
2. Show that q
rev
is not a state function (i.e. dq
rev
is not exact) for a gas
obeying the equation of state P =
RT

V b
, but that d
qrev
/T is. Assume a
reversible process and consider only PV -work. Hint: you may proceed
as follows:
(a) Use the previous problem to calculate (U/V )
T
.
(b) Use dU =
_
U
T
_
V
dT +
_
U
V
_
T
dV to calculate dU.
(c) Use the rst law of thermodynamics to get an expression for dq.
(d) Substitute the equation of state into the above expression.
(e) Apply the exactness test for dierentials (dq = M(V, T)dT +
N(V, T)dV ). Use results from the previous problem to dierenti-
ate M with respect to V .
(f) Repeat the same calculation for dq/T.
Solution:
By using the result given in the rst problem, we can obtain
_
U
V
_
T
= 0.
The total dierential for dU now gives dU =
_
U
T
_
V
dT and hence dU =
C
V
dT. The rst law of thermodynamics, dU = dq + dw, gives dq =
C
V
dT dw. Considering PV -work, we can write: dq = C
V
dT +P
ext
dV .
Because the process is reversible, P
ext
= P and dq = C
V
dT +PdV . For
dq to be exact we should have:
_
C
V
V
_
T
=
_
P
T
_
V
From the rst problem we know that the left hand side is zero. The
right hand side, however, is not zero:
_
P
T
_
V
=
nR
V nb
= 0
Thus dq is inexact. For dq/T we have:
dq
T
=
C
V
T
dT +
P
T
dV . Now the
exactness test gives:
_
C
V
/T
V
_
T
= 0 (T is constant)
2
_
(nR/(V nb))
T
_
V
= 0 (the expression does not depend on T)
Thus dq/T is exact.
3. An ideal gas initially at (P
1
, V
1
, T
1
) undergoes a reversible isothermal
expansion to (P
2
, V
2
, T
1
) (path 1). The same change in state of the gas
can be achieved by allowing it to expand adiabatically from (P
1
, V
1
, T
1
)
to (P
3
, V
2
, T
2
) and then heating it at constant volume to (P
2
, V
2
, T
1
)
(path 2). Note that T
2
has not been specied and you should nd
an equation that determines it. Show that the entropy change for
the reversible isothermal expansion (path 1) is the same as the sum
of the entropy changes in the reversible adiabatic expansion and the
reversible heating (path 2). Because the two paths give the same result,
it is probable that the integral is independent of path. This is not a
complete proof why?
Solution:
Path 1: First we recall that for an ideal gas U =
3
2
nRT (see lecture
notes). The temperature is constant along this path and thus change
in internal energy must be zero. The rst law of thermodynamics now
states that U = q
rev
+ w
rev
and hence q
rev
= w
rev
. Recall the
following equation from the lecture notes:
w
rev
= nRT
1
ln
_
V
2
V
1
_
q
rev
= nRT
1
ln
_
V
2
V
1
_
Using the denition of entropy gives:
S =
q
rev
T
1
= nRln
_
V
2
V
1
_
Path 2: First consider the rst segment from (P
1
, V
1
, T
1
) to (P
3
,
V
2
, T
2
). The expansion is adiabatic (i.e. no heat exchange with the
surroundings) and hence q
rev
= 0. For this reason the change in entropy
is also zero (S = q
rev
/T = 0). The nal temperature in an adiabatic
expansion is determined by integrating C
V
dT
T
= nR
dV
V
(see lecture
notes):
3
T
2
_
T
1
C
V
T
dT = nR
V
2
_
V
1
dV
V
= nRln
_
V
2
V
1
_
Along the second segment (P
3
, V
2
, T
2
) to (P
2
, V
2
, T
1
), we have a con-
stant volume process. The lecture notes now give dq
rev
= C
V
dT. The
denition of entropy is dS =
dqrev
T
and thus:
dS =
C
V
dT
T
S =
T
1
_
T
2
C
V
dT
T
=
T
2
_
T
1
C
V
dT
T
Comparison of this with the expression determining T
2
along the rst
segment, gives the nal result:
S = nRln
_
V
2
V
1
_
This is the same result that was obtained along path 1. For a complete
proof of exactness, one would have to use the exactness test or consider
innitely many paths (or rather, the exactness test).
4. Water is vaporized reversibly at 100

C and 1.01325 bar. The heat
of vaporization is 40.69 kJ mol
1
. a) What is the value of S for
the water? b) What is the value of S for the water plus the heat
reservoir at 100

C? The heat reservoir is thermally isolated from its
surroundings.
Solution:
a) S
H
2
O
=
q
T
=
40.69 kJ mol
1
373.13K
= 109.04 J K
1
mol
1
. Note that +
sign means that water receives heat.
b) The reservoir loses heat to water exactly the same amount as
above. The change in entropy for the heat reservoir is q/T =
109.04 J K
1
mol
1
.
4
Note: Since water + heat reservoir is isolated from the rest of the world,
the total change its entropy is 0. The total entropy in the system is
conserved.
5. Assuming that CO
2
is an ideal gas, calculate H

and S

for the
following process:
CO
2
(g, 298.15 K, 1 bar) CO
2
(g, 1000 K, 1 bar)
Consider 1 mol of gas and a reversible process. Given:

C

P
(T) =
26.648 + 42.262 10
3
T 142.4 10
7
T
2
(units: J K
1
mol
1
).
Solution:
Here

refers to the standard state. For gases this is 1 bar pressure
but note that this does not specify temperature. The overbar denotes
that these are molar quantities (i.e. per mole). To calculate change in
enthalpy, we integrate the heat capacity over temperature (see lecture
notes):

=
T
2
_
T
1

P
dT =
1000 K
_
298.15 K
_
26.648 T +
_
42.262 10
3
2
_
T
2
+
_
142.40 10
7
3
_
T
3
_
= 33.34 kJ mol
1
Furthermore, at constant pressure we can apply equations: dq = C
P
dT
and dS = dq
rev
/T = C
P
/TdT:

=
T
2
_
T
1

P
T
dT =
1000 K
_
298.15 K
_
26.648 ln(T) + 42.262 10
3
T
_
142.4 10
7
2
_
T
2
_
= 55.42 J K
1
mol
1
5
6. Ammonia (considered to be an ideal gas) initially at 25

C and 1 bar
pressure is heated at constant pressure until the volume has trebled.
Assume reversible process. Calculate: a) q per mole, b) w per mole, c)

H, d)

U, e)

S given

C
P
= 25.895+32.99910
3
T 30.4610
7
T
2
(in J K
1
mol
1
).
Solution:
Tripling of the ideal gas volume (PV
1
= nRT
1
) leads to T = P(3V
1
)/(nR),
which means that the temperature will be three times higher; T
2
= 3T
1
.
Note that pressure is constant.
a) q =
T
2
_
T
1

C
P
dT =
894 K
_
298 K
(25.895 + 32.999 10
3
T 30.46 10
7
T
2
) dT =
26.4 kJ mol
1
.
b) w = P

V = RT =
_
8.314 J K
1
mol
1
_
(596 K) =
4.96 kJ mol
1
.
c) Because pressure is constant, we have

H = q
P
= 26.4 kJ mol
1
.
d)

U = q +w = (26.4 4.96) kJ mol

1
= 21.4 kJ mol
1
.
e)

S =
T
2
_
T
1

C
P
T
dT =
894 K
_
298 K
_
25.895
T
+ 32.999 10
3
30.46 10
7
T
_
dT =
46.99 J K
1
mol
1
.
7. Three moles of an ideal gas expand isothermally and reversibly from
90 L to 300 L at 300 K. a) calculate U, S, w and q for this system,
b) calculate

U,

S, w per mole and q per mole, c) If the expansion

is carried out irreversibly by allowing the gas to expand into and evac-
uated container, what are the values of

U,

S, w per mole and q per

mole?
Solution:
a) Change in internal energy is zero because the gas is ideal. Recall
that the internal energy for an ideal gas depends only on temper-
ature. Here we have an isothermal process and hence no change
6
in internal energy occurs, U = 0. Note also that the 1st law now
states that q = w. For an isothermal process (see the lecture
notes) we have:
w
rev
= nRT ln
_
V
2
V
1
_
q
rev
= nRT ln
_
V
2
V
1
_
= (3 mol)
_
8.314 J K
1
mol
1
_
(300 K) ln
_
300 L
90 L
_
= 9.01 kJ
and q = 9.01 kJ. By using the denition of entropy, we can calcu-
late the change in entropy:
S =
q
rev
T
=
9.01 kJ
300 K
= 30.03 J K
1
b) Divide everything by 3 mol to get per mole quantities:

U = 0 kJ mol
1
,

S = 10.01 J K
1
mol
1
,
w = 3.00 kJ mol
1
, q = 3.00 kJ mol
1
c) Since the temperature is constant, we have

U = 0 . Since the
gas is expanding into vacuum, P
ext
= 0 and thus w = 0. By the
rst law, q = 0. The entropy is the same as in b) because its
value depends only on endpoints of the path. Note that q along
the present irreversible path cannot be used in calculating entropy
one must always use a reversible path (for example that in b)
above). For this reason

S = 10.01 J K
1
mol
1
, which is the
same value as in b).
8. An ideal gas at 298 K expands isothermally from a pressure of 10 bar to
1 bar. What are the values of w per mole, q per mole,

U,

S in the
following cases? a) The expansion is reversible, b) The expansion is free
(irreversible), (c) The gas and its surroundings form an isolated system,
and the expansion is reversible and d) The gas and its surroundings
form an isolated system, and the expansion is free (irreversible).
Solution:
7
a) This is a reversible process and constant temperature implies that

U = 0. Also the enthalpy change for an ideal gas depends only

on temperature

H = 0. By using the 1st law and the expression
for reversible expansion (see lecture notes), we get:
w
rev
= RT ln
_
V
2
V
1
_
= RT ln
_
P
2
P
1
_
= q
rev
By plugging in the values, we get w
rev
= 5.71 kJ mol
1
and
q
rev
= 5.71 kJ mol
1
. Now the denition of entropy gives the
entropy change:

S =
q
rev
T
= 19.1 J K
1
mol
1
b) Irreversible process (free expansion). No external pressure no
work done (w = 0). Thus by the rst law q = 0 (i.e. no heat
exchanged with the surroundings) since

U = 0 and

H = 0.
Entropy depends only on the endpoints of the path and hence

S =
qrev
T
= 19.1 J K
1
mol
1
, where q
rev
is from part a). Note
that only reversible paths can be used in calculating entropy!
c) Isolated system, which here means that system + surroundings
is isolated from the rest of the world. For a reversible process we
have dS
tot
= dS
syst
+dS
surr
= 0. For the system we have:
dS
syst
=
dq
rev
T
and for the surroundings dS
surr
=
dq
rev
T
Since temperature is constant, U = 0 and H = 0. Therefore:
q
rev
= w = RT ln
_
P
2
P
1
_
(from previous calculations)
Thus S
syst
= Rln(P
2
/P
1
) and S
surr
= Rln(P
2
/P
1
). Thus
the total change of entropy (system + surroundings) is zero. Also
q
tot
= q
sys
+ q
surr
= RT ln(P
2
/P
1
) RT ln(P
2
/P
1
) = 0. For the
same reason, the total work w
tot
= w
sys
+ w
surr
= 0. Note that
the system + surroundings is isolated from the rest of the world
and therefore the total change in heat (q
tot
) and work (w
tot
) must
clearly be zero.
8
d) If we want to calculate the entropy change for the system, we
need a reversible path for the calculation. Above this was done:
S
syst
= Rln(P
2
/P
1
). In free expansion, no work is done, w
sys
=
0 (and w
surr
= 0). Since U = w
sys
+q
sys
and U = 0, q
sys
= 0 as
well (also then q
surr
= 0). Thus the system is not interacting with
the surroundings at all in this process. This means that the en-
tropy of the surroundings does not change either, S
surr
= 0. The
total entropy is then S
tot
= S
syst
+ S
surr
= Rln(P
2
/P
1
) =
19.1 J K
1
mol
1
.
9. One mole of gas A at 1 bar and one mole of gas B at 2 bar are sep-
arated by a partition and surrounded by a heat reservoir (i.e. the
temperature is constant). When the partition is withdrawn, how much
does the entropy change? Both gases behave according to the ideal
gas law. Hint: consider the calculation in three steps: (I) the initial
entropy dierence from standard state, (II) change in entropy due to
expansion/compression of gases at constant temperature and nally
(III) entropy change due to mixing of the gases.
Solution:
Note that the pressures of the two gases are dierent and thus the
results in the lecture notes cannot be directly applied.
I The initial (i.e. before mixing) entropies for the gases are:
S
A
= S

A
nRln
_
P
ini
A
P

A
_
= S

A
nRln
_
1 bar
1 bar
_
= S

A
S
B
= S

B
nRln
_
P
ini
B
P

B
_
= S

B
nRln (2)
II Let both gases expand from their initial pressures to the nal
pressure at constant temperature. This changes entropy of both
gases according to:
S
A
= S

A
nRln
_
P
total
P

A
_
and S
B
= S

B
nRln
_
P
total
P

B
_
9
where P
total
is the nal pressure after mixing. The nal volume
after mixing is:
V
total
= V
A
+V
B
=
nRT
P
A
+
nRT
P
B
=
nRT
P
A
+
nRT
2P
A
=
3nRT
2P
A
The total pressure after mixing is then:
P
total
=
2nRT
V
total
=
4
3
P
A
=
4
3
bar
The entropy change due to expansion for both gases is:
S
A
= S

A
nRln
_
4
3
_
and S
B
= S

B
nRln
_
4
3
_
Combining 1 and 2, we have: S
A
= n
A
Rln
_
4
3
_
and S
B
=
n
B
R
_
ln
_
4
3
_
ln(2)
_
.
III Finally we must include the entropy change due to mixing (n = 1):

mix
S = Rln
_
1 mol
2 mol
_
Rln
_
1 mol
2 mol
_
= 2Rln
_
1
2
_
The total entropy change is then (1 + 2 + 3):
S
total
= S
A
+S
B
+S
mix
= 2Rln
_
4
3
_
+Rln(2)2Rln
_
1
2
_
= 12.51 J K
1
mol
1
10. Calculate the change in molar entropy of aluminum that is heated from
600

to 700

C. The melting point of aluminum is 660

C, the heat of
fusion is 393 J g
1
(the molar mass for aluminum is 27 g mol
1
), and
the heat capacities at constant pressure of the solid and the liquid may
be taken as 31.8 J K
1
mol
1
and 34.4 J K
1
mol
1
(independent of
temperature), respectively.
10
Solution:
Note that 600

C is 873 K, 660

C is 933 K, and 700

C is 973 K. Use
the following equation (see lecture notes):

S =
T
fusion
_
T
initial
C
P
(s)
T
dT +
H
fusion
T
fusion
+
T
final
_
T
fusion
C
P
(l)
T
dT
= C
P
(s) ln
_
T
fusion
T
initial
_
+
H
fusion
T
fusion
+C
P
(l) ln
_
T
final
T
fusion
_
= (31.8 J K
1
mol
1
) ln
_
933 K
873 K
_
+
(27 g mol
1
)(393 J g
1
)
933 K
+(34.3 J K
1
mol
1
) ln
_
973 K
933 K
_
= 19.92 J K
1
mol
1
11. Steam is condensed at 100

C, and the water is cooled to 0

C and frozen
to ice. What is the molar entropy change of the water? Consider that
the average specic heat of liquid water is 4.2 J K
1
g
1
(the molar
mass of water is 18.016 g mol
1
). The enthalpy of vaporization at the
boiling point and the enthalpy of fusion at the freezing point are 2258.1
J g
1
and 333.5 J g
1
, respectively.
Solution:
Use the same cycle as in the previous problem (note that the cycle
goes from high temperature to low temperature and thus the signs are
reversed!):

S =
H
vap
T
vap

373.15 K
_
273.15 K
C
P
(l)
T
dT
H
fus
T
fus
=
_
2258.1 J g
1
_ _
18.016 g mol
1
_
373.15 K
11

_
4.2 J K
1
mol
1
_

_
18.016 g mol
1
_
ln
_
373.15 K
273.15 K
_

_
333.5 J g
1
_ _
18.016 g mol
1
_
273.15 K
= 154.4 J K
1
mol
1
12. Calculate the increase in the molar entropy of nitrogen when it is heated
from 25

C to 1000

C at constant pressure with:

C
P
= 26.9835 +
5.9622 10
3
T 3.377 10
7
T
2
in J K
1
mol
1
.
Solution:
Nitrogen is gaseous in the temperature range. The entropy change is
then given by:

S =
1273.15 K
_
298.15 K
C
P
(g)
T
dT =
1273.15 K
_
298.15 K
_
26.9835 ln(T) + 5.9622 10
3
T
3.377 10
7
2
T
2
_
= 44.73 J K
1
mol
1
12