CBE 231 - Thermodynamics of Fluids

Assignment #5 Solution
1.
1.a.
Add the Raoults Law expressions for both species
x
1
P
sat
1
(T) + x
2
P
sat
2
(T) = (y
1
+ y
2
)P
x
1
P
sat
1
(T) + (1 x
1
)P
sat
2
(T) = P
(1.1)
The Antoine equation allows us to express P
sat
1
and P
sat
2
in terms of T
P
sat
1
= exp
_
A
1

B
1
T + C
1
_
P
sat
2
= exp
_
A
2

B
2
T + C
2
_ (1.2)
where the constants A
i
, B
i
, and C
i
are material properties. Plug Eqns. 1.2 into Eqn.
1.1 to obtain one function in terms of one unknown (T). Solve the equation to nd
T = 382 K . Then, use this value to nd x
1
= 0.173 from Eqn. 1.1.
1.b.
In this part, we have T and can solve directly for the saturation pressures. Use this
information and Eqn. 1.1 to nd x
1
= 0.433 . Then, use the Raoults Law expression
for one of the components to nd y
1
= 0.650 .
1
2.
2.a.
Add the Raoults Law expressions for both species
x
1

1
P
sat
1
+ x
2

2
P
sat
2
= (y
1
+ y
2
)P
x
1

1
P
sat
1
+ (1 x
1
)
2
P
sat
2
= P
x
1
exp{0.85(1 x
1
)
2
}P
sat
1
+ (1 x
1
) exp{0.85(x
1
)
2
}P
sat
2
= P
(2.1)
The nal line is a single equation with one unknown (P). Plug in all of the known values
to nd P = 47.2 kPa . Then, rearrange Raoults Law for one of the components to nd
y
1
y
1
=
x
1
exp{0.85(1 x
1
)
2
}P
sat
1
P
= 0.182
2.b.
Rearrange Raoults Law for the rst component
P =
x
1
exp{0.85(1 x
1
)
2
}P
sat
1
y
1
(2.2)
Set this expression equal to Eqn. 2.1
x
1
exp{0.85(1 x
1
)
2
}P
sat
1
y
1
= x
1
exp{0.85(1 x
1
)
2
}P
sat
1
+ (1 x
1
) exp{0.85(x
1
)
2
}P
sat
2
Here, the only unknown is x
1
. Solve this equation to nd x
1
= 0.011 . Then, plug x
1
into Eqn. 2.2 to nd P = 40.4 kPa .
2.c.
At the azeotrope, x
1
= y
1
. Therefore, we can rewrite Raoults Law as P =
1
P
sat
1
. Set
this equation equal to Eqn. 2.1
2
P =
1
P
sat
1
= x
1

1
P
sat
1
+ (1 x
1
)
2
P
sat
2
(1 x
1
)
1
P
sat
1
= (1 x
1
)
2
P
sat
2
P
sat
1
P
sat
2
=

2

1
=
exp{0.85(x
1
)
2
}
exp{0.85(x
2
)
2
}
= exp{0.85[x
2
1
(1 x
1
)
2
]}
ln
_
P
sat
1
P
sat
2
_
= 0.85[x
2
1
(1 2x
1
+ x
2
1
)]
= 0.85[2x
1
1]
x
1
=
1
2
_
1
0.85
ln
_
P
sat
1
P
sat
2
_
+ 1
_
Plug in the known values of the saturation pressures to nd x
1
= y
1
= 0.900 .
3
3.
Make two assumptions:
1. At 1500 K, silver acts as an ideal gas
2. The molar volume of the vapor molar volume of the liquid
With these two assumptions, we can write
dP
sat
P
sat
=
h
vap
dT
RT
2
Rearrange this expression
dP
sat
dT
=
h
vap
P
sat
RT
2
(3.1)
Dierentiate the expression for P given in the problem statement
dP
sat
dT
=
_
14260
T
2

0.458
T
_
exp
_
14260
T
0.438 ln(T) + 12.23
_
=
_
14260
T
2

0.458
T
_
P
sat
Set this expression equal to Eqn. 3.1
_
14260
T
2

0.458
T
_
=
h
vap
RT
2
Finally, solve for h
vap
h
vap
= R(14260 0.458T)
= 112.8
kJ
mol
4
4.
From Problem 6.13, we know that
_
g
T
_
Sr(s)
=
_
g
T
_
Sr(l)
and
_
(g/T)
T
_
P
=
h
T
2
(4.1)
Since h =
_
C
p
dT, we can nd the enthalpies of the liquid and solid phases as functions
of temperature
h
l
(T) = 49179 +
_
T
1500 K
35.146dT = 35.146T 3540
h
s
(T) = 20285 +
_
T
900 K
37656dT = 37.656T 16305.4
Next, calculate reference
_
g
T
_
values for both phases. Use the values provided in the
problem statement to calculate g = h Ts. Then, divide by T to nd
_
g
l
T
_
ref
= 83.85
J
mol K
_
g
s
T
_
ref
= 68.68
J
mol K
Now we can write a general expression for
_
g
T
_
using Eqn. 4.1
_
d
_
g
T
_
=
_ _
(g/T)
T
_
P
dT =
_
h
T
2
dT
Substitute in the expressions we obtained for enthalpies and the reference
_
g
T
_
values to
nd
_
g
l
/T
83.85
d
_
g
T
_
=
_
T
1500 K

_
35.146T 3540
T
2
_
dT
_
g
l
T
_
= 35.145 ln T
3540
T
+ 176.04
_
g
s
/T
68.68
d
_
g
T
_
=
_
T
900 K

_
37.656T 16305.4
T
2
_
dT
_
g
s
T
_
= 37.646 ln T
16305.4
T
+ 205.5
5
Now, set
_
g
s
T
_
=
_
g
l
T
_
and solve for T to nd
T
melt
= 1060 K
Use the following denition to nd the enthalpy of melting
h
fus
= h
s
(T
melt
) h
l
(T
melt
)
= 26.30
kJ
mol
33.71
kJ
mol
= 7.41
kJ
mol
6
5.
5.a.
The range of pressures is from the bubble point to the dew point. First, nd the bubble
point pressure. At this point, x
1
= z
1
= 0.65
P(x
1
, x
2
) = x
1

1
(x
1
, x
2
)P
sat
1
+ x
2

2
(x
1
, x
2
)P
sat
2
P
bubble
= 0.65 exp[0.67(1 0.65)
2
](32.27 kPa) + (1 0.65) exp[0.67(0.65)
2
](73.14 kPa)
= 56.75 kPa
At the dew point, y
1
= z
1
= 0.65. Write two equations to nd the two unknowns P
dew
and x
i
P
dew
=
x
1
y
1

1
P
sat
1
P
dew
= x
1

1
P
sat
1
+ x
2

2
P
sat
2
Guess and check or use Excel to force these two equations to have the same output value
of P
dew
= 43.86 kPa. Thus, the pressure range is [43.86 kPa, 56.75 kPa] .
5.b.
Perform a BUBL P calculation
P = 0.7 exp[0.67(10.7)
2
](32.27 kPa)+(10.7) exp[0.67(0.7)
2
](73.14 kPa) = 54.46 kPa
5.c.
First, nd y
1
y
1
=
x
1

1
P
sat
1
P
= 0.441
Then, nd the vapor composition
=
z
1
x
1
y
1
x
1
= 0.193
7