CBE 231 - Thermodynamics of Fluids

Assignment #3 Solution
1.
1.a.
Use the cyclic rule
_
P
T
_
v
_
v
P
_
T
_
T
v
_
P
= 1
Apply the denitions of and
_
v
T
_
P
= v
_
v
P
_
T
= v
Substitute in these expressions
_
P
T
_
v
=
_
P
v
_
T
_
v
T
_
P
=
_
v
v
_
=

= 15.9
bar

C
We can use this to nd T
T =
P
_
P
T
_
v
=
(121 bar 1 bar)
15.9
bar

C
= 7.5

C
1
1.b.
Rearrange the provided expression for C
P
C
P
C
v
= T
_
P
T
_
v
_
v
T
_
P
= T
_
P
v
_
T
_
v
T
_
2
P
= Tv

Find the change in internal energy

u =
_
C
v
dT
=
_
T
2
T
1
_
C
P
Tv

_
dT
= C
P
(T
2
T
1
)
v
2
2
(T
2
2
T
2
1
)
= 938
J
mol
432
J
mol
= 506
J
mol
where v =
MW

= 7.35 10
5 m
3
mol
. Use this value to nd h
h = u + (Pv)
= u +vP
= 1388
J
mol
Now, nd the change in entropy
ds =
_
s
T
_
v
dT +
_
s
v
_
T
dv
=
_
s
T
_
v
dT =
C
v
T
dT
s =
_
T
2
T
1
1
T
_
C
P
Tv

_
dT
= C
P
ln
_
T
2
T
1
_

v
2

T
= 1.70
J
mol K
2
1.c.
Perform an energy balance
u = Q = 506
J
mol
3
2.
Begin with the dierential for internal energy
du = C
v
dT +
_
u
v
_
T
dv
Thus
_
u
T
_
v
= C
v
_
u
T
_
P
= C
v
+
_
T
_
P
T
_
v
P
_ _
v
T
_
P
_
u
T
_
P

_
u
T
_
v
=
_
T
_
P
T
_
v
P
_ _
v
T
_
P
2.a.
For an ideal gas, P =
RT
v
.
T
_
P
T
_
v
P = T
_
R
v
_

RT
v
= 0
Therefore
_
u
T
_
P

_
u
T
_
v
= 0
2.b.
For a van der Waals gas
P =
RT
v b

a
v
2
Use this to nd that
_
P
T
_
v
=
R
v b
So that
T
_
P
T
_
v
P =
a
v
2
Also realize that
4
dP =
R
v b
dT
RT
(v b)
2
dv +
2a
v
3
dv
Rearrange this and solve for
_
v
T
_
P
_
v
T
_
P
=
R
(vb)
RT
(vb)
2

2a
v
3
=
_
T
(v b)

2a(v b)
Rv
3
_
1
Therefore
_
u
T
_
P

_
u
T
_
v
=
a
v
2
T
vb

2a(vb)
Rv
=
aRv(v b)
RTv
3
2a(v b)
2
5
3.
3.a.
Recall the following denitions
=
1
v
_
v
T
_
P
=
1
v
_
v
P
_
T
Use them to nd

=
_
v
T
_
P
_
v
P
_
T
=
_
v
T
_
P
_
P
v
_
T
Apply the cyclic rule
1 =
_
v
T
_
P
_
P
v
_
T
_
T
P
_
v
Thus,

=
_
P
T
_
v
3.b.
Write T = T(v, P) and write
dT =
_
T
v
_
P
dv +
_
T
P
_
v
dP (3.1)
We can also write
ds =
C
v
T
dT +
_
P
T
_
v
dv =
C
P
T
dT
_
v
T
_
P
dP
Rearrange this equation and solve for dT. Then, set it equal to Equation 3.1 and group
terms
_
T
v
_
P
dv +
_
T
P
_
v
dP =
T
C
P
C
v
_
P
T
_
v
dv +
T
C
P
C
v
_
v
T
_
P
dP
__
T
v
_
P

T
C
P
C
v
_
P
T
_
v
_
dv +
__
T
P
_
v

T
C
P
C
v
_
v
T
_
P
_
dP = 0
6
In order for this to be true, both terms in square brackets must be equal to zero. There-
fore, we can write
_
T
v
_
P
=
T
C
P
C
v
_
P
T
_
v
C
P
C
v
= T
_
P
T
_
v
_
v
T
_
P
= T

_
v
T
_
P
=
Tv
2

7
4.
Determine the ideal gas heat capacity from Table A.2.1
C
P
R
= 1.213 + 28.785 10
3
T 8.824 10
6
T
2
This process is isentropic, so construct a solution so that the sum of the entropy changes
for each step is equal to zero.
4.a.
Choose two steps as follows
Write the dierential of entropy
ds =
_
s
T
_
v
dT +
_
s
v
_
T
dv = 0
=
C
v
T
dT +
_
P
T
_
v
dv
For this system, use
P =
RT
v b

a
v
2
_
P
T
_
v
=
R
v b
to nd the entropy change for the rst step
8
s
1
=
_
ds
=
_
v
2
v
1
_
P
T
_
v
dv
=
_
v
2
v
1
R
v b
dv
= Rln
_
v
2
b
v
1
b
_
Because P
2
is low, we can assume that the gas at this state behaves as an ideal gas
s
1
= Rln
_
RT
2
P
2
b
v
1
b
_
Next, calculate s
1
s
2
=
_
T
2
T
1
C
v
T
dT = R
_
T
2
623.15 K
0.213 + 28.785 10
3
T 8.824 10
6
T
2
T
dT
Add both of the entropy changes and set them equal to zero
s = s
1
+ s
2
= 0
Substitute in the expressions from above and solve for T
2
= 448.3 K .
9
5.
Perform an energy balance to nd that u = 0. The gas is not ideal under the stated
conditions, so we must create a path that connects the initial to the nal state through
three steps into a region where we can assume the gas behaves as an ideal gas, as shown
below
First, nd u
1
u
1
=
_
v=
v
i
_
u
v
_
T
dv
=
_
v=
v
i
_
T
_
P
T
_
v
P
_
dv
For the van der Waals equation of state
_
P
T
_
v
=
R
v b
+
a
T
2
v
2
Plug this into the expression for u
1
u
1
=
_

v
i
=2.510
4
_
RT
v b
+
a
Tv
2
P
_
dv =
_

v
i
=2.510
4
2a
T
i
v
2
dv = 1120
J
mol
Perform a similar procedure for the third step
u
3
=
_
v
f
=510
4

_
RT
v b
+
a
Tv
2
P
_
dv =
_
v
f
=510
4

2a
T
f
v
2
dv =
168000
T
f
J
mol K
The molar volume is innite for step 2, so we can use the ideal gas heat capacity to nd
u
2
10
u
2
=
3
2
R(T
f
300 K)
Sum the internal energies
u = u
1
+ u
2
+ u
3
= 1120
J
mol
+
3
2
_
8.314
J
mol K
_
(T
f
300 K)
168000
T
f
= 0
Solve for T
f
= 262 K .
11