Milo Koretsky
Wyatt Tenhaeff
School of Chemical, Biological, and Environmental Engineering
Oregon State University
milo.koretsky@oregonstate.edu
7.1
The fugacity in the liquid is greater. At equilibrium, the fugacities are equal. For this to be the
case, the air in the room would have to be saturated (100% relative humidity). Since the air
contains less water than saturation, water will spontaneously evaporate, and the fugacity of the
vapor is smaller.
7.2
hmix = 0. The molecular basis for the Lewis fugacity rule is that all the intermolecular
interactions are the same. Therefore, the energy of the mixture is equal to that of the sum of the
pure species.
7.3
Mixture A. The molecular basis for the Lewis fugacity rule is that all the intermolecular
interactions are the same. n-pentane and n-hexane both have dispersion interactions and they are
approximately the same size (polarizability is similar)
7.4
The van der Waals parameter b approximates repulsive interactions with a hard sphere model
that is determined by the size of the molecules. Hence it is the weighted average of the size of
each of the species in the mixture. That can be seen in the form for a binary mixture:
b y1b1 y2b2
The parameter a represents van der Waals attractive interactions and is a two-body
interactions. Thus, you must sum together all the possible pair-wise interactions. That can be
seen in the form for a binary mixture:
a y1 y1a1 y1 y2 a12 y2 y1a21 y2 y2 a2
y12 a1 2 y1 y2 a12 y22 a2
7.5
There are many ways to approach this problem. One approach is shown below. If we assume an
ideal solution, for water (species 1), we get:
y1P x1P1sat
y1 P
0.9
P1sat
Since we are at 90% RH. If we calculate the mole fraction of water for 96.55 mass % water, we
get x1 = 0.99 in sweat. Since x1 x1eq , water will have a tendency to evaporate so the fugacity of
water in the liquid is greater than the fugacity of water in the vapor.
7.6
(a)
The magnitude of the Henrys Law constant is governed by the unlike (1-2) interactions. In the
case of acetone and water, strong intermolecular attraction exists due to dipole-dipole
interactions and hydrogen bonding. With methane and water, only dispersion is present.
Therefore, the interactions between methane and water are weaker, and the fugacity is greater.
There is a greater partial pressure for the methane-water system. The Henrys Law constant is
greater for this system.
(b)
The Henrys Law constant describes the unlike interactions. Since the unlike interactions result
in a fugacity that is equal to the pure fugacity of a, the unlike and like interactions are equal in
magnitude. Therefore, the solution is ideal for the entire composition range.
Activity Coefficient vs. Composition
1.2
1
ga
0.8
0.6
0.4
0.2
0
0
0.2
0.4
0.6
xa
0.8
7.7
(a)
First, we must realize that
h E hmix
Since
gE
hmix
T2
P, ni
E
we see that g
gE
Ax x
a b
P, ni T P, ni
g E
v E vmix
T , n i
Substituting the two suffix Margules equation in for the excess Gibbs energy, we find
Ax a xb
0
T , ni
Therefore, we can see that the A parameter is independent of pressure at constant temperature
and moles.
7.9
(a) See graph below. Since the Henrys law constant which represents a-b interactions is less
than the pure species fugacity, the tendency to escape of a-b is lower and the a-b interactions
are stronger.
200
fa xa f a
150
[bar] 100
fa xa a
50
0
0
0.5
xa
(b) Both lnga and lngb go to 1 and xi goes to 0. Therefore the Henrys law reference state is being
used. Since gi> 0 the tendency to escape for some a-a or b-b interactions is greater than all a-a
interactions. Therefore the a-b interactions are stronger.
1.6
1.2
lng b
0.8
0.4
0
0
0.5
xa
7.10
7.11
200 oC and 1.56 MPa (Pisat = 1.55 MPa) ( isat 1 ) so
fi
1
Pi sat
fi
1
Pi sat
fi
1
Pi sat
7.12
Initially the system contains water and nitrogen in vapor liquid equilibrium at 1 atm. The
liquid is mostly water and the vapor contains a mole fraction of water where the fugacity of
the vapor equals the fugacity of the liquid. When the third component is added to the liquid,
the mole fraction of water in the liquid decreases, so its fugacity also decreases. To maintain
equilibrium, the fugacity of water in the vapor must also decrease to the point where it equals
the fugacity of water in the liquid. Therefore, some water will condense and the number of
moles of water in the vapor will decrease.
7.13
7.14
(a)
Use Equation 7.7:
fv
g i g i RT ln i
Plow
kJ
kJ
kJ
Plow 10 kPa : g i 3489.0 773.15K 9.8977
4163.4
kg
kg K
kg
kJ
kJ
kJ
P 2 MPa : g i 3467.6 773.15K 7.4316
2278.1
kg
kg K
kg
Therefore,
2278.1
fi v 10 kPa exp
kJ
kJ
kg 4163.4 kg 1000 J/kJ 0.0180148 kg/mol
i 0.985
(b)
For 500 C and 50 MPa, we obtain the following from the steam tables
kJ
kJ
kJ
g i 2720.1 773.15K 5.1725
1279.0
kg
kg K
kg
Using data from Part (a), we can calculate the fugacity and fugacity coefficient:
1279.0
v
fi 10 kPa exp
v
fi 32.4 MPa
and
i 0.648
kJ
kJ
kg 4163.4 kg 1000 J/kJ 0.0180148 kg/mol
J
8.314
773.15
K
mol K
7.15
(a)
Equation 7.8 states
f iv P
v dP
RT ln
Plow i
Plow
However, the Berthelot equation is not explicit in molar volume, so the integral must be
transformed.
RT
2a
dP
dv
vi b 2 Tvi3
f iv vi RTvi
2a
RT ln
dv
2
2
Plow
Tv
RT i
Plow
To determine the integral of the first term above, we use decomposition by partial fractions:
v b
1
b
v b v b2
so
vi
RT
Plow
2 dv lnv i b
vi b
v i b
vi
vi
RT
Plow
and
i
f iv b
2a
ln
ln(vi b)
2
Plow vi b
RT
v
i RT
Plow
f iv 1
1
ln
ln
b
Plow vi b RT
Plow
vi b 2a
RT 2
RT
b
Plow
1 Plow
vi RT
Since
RT
b , the expression simplifies to
Plow
f iv 1
P
P v b 2a
b
ln
low ln low i
Plow vi b RT
RT
RT 2
1 Plow
vi RT
lnf iv
v b
b
2a
ln i
2
vi b
RT RT v i
Therefore,
f iv
b
RT
2a
exp
vi b vi b RT 2 vi
To obtain an expression for iv , we divide our expression for fugacity by total pressure:
iv
b
f iv
RT
2a
exp
P P v i b v i b RT 2v i
(b)
From Problem 4.29, we got
v c 3b
3RTc
8Pc
and
9
a v c RTc2
8
iv
1
f iv
8Tr
9
exp
2
P Pr 3v i,r 1 3v i,r 1 4Tr v i,r
7.16
Equation 7.8:
f iv
vi dP RT ln Plow
Plow
P
RT
a
1/ 2
v b T v v b
so
RT
a
a
dP
2
2 dv
1/ 2 2
v b T v v b T1/ 2v v b
Therefore,
RT
Plow
vRT
v b
f iv
a
a
dv
RT
ln
T1/ 2v v b T1/ 2 v b2
Plow
To determine the integral of the first two terms term above, we use decomposition by partial
fractions. For the first term,
v b
1
b
v b v b2
so
RT
Plow
b
v
dv lnv b
2
v b
v b
1
1 1
1
v v b b v v b
so
v
RT
Plow
RT
Plow
1
1 v
dv ln
v v b
b v b
v
RT
Plow
Thus, we get
fv
b
v
a
a
RT ln i RT lnv b RT
1/ 2 ln
1/ 2
v b T b v b T v b
Plow
If we note that
RT
Plow
RT
b and let Plow 0 , we obtain
Plow
a
a
RT
b
v
RT ln f iv RT ln
RT
1 / 2 ln
1/ 2
vb
vb T b vb T
v b
Therefore,
f iv
RT
a
a
v
exp
ln
vb
v b RT 3 / 2 b v b RT 3 / 2 v b
iv
v
f iv
RT
a
a
exp
ln
P P v b v b RT 3 / 2b v b RT 3 / 2 v b
and
7.17
Equation 7.8:
f iv
vi dP RT ln Plow
Plow
P
RT
a (T)
2
v b v 2vb b2
Thus,
2a (T)v b
RT
dP
dv
v b2 v 2 2vb b 2 2
Therefore,
RT
Plow
f iv
2a (T)v b
RT
v
dv
RT
ln
v b2 v 2 2vb b 2 2
Plow
Simplifying, we get
v
fi v
v
2a (T )
ln
dv
2
RT
RT v b
Plow
Plow
v v b
RT
Plow
2vb b
2 2
dv
(1)
To determine each of the integrals in Equation 1, we use decomposition by partial fractions. For
the first integral:
v b
1
b
v b v b2
so
RT
Plow
b
v
dv lnv b
2
v b
v b
v
RT
Plow
(2)
v v b
2vb b
so
RT
Plow
1
v b
b
2
2
v 2vb b
v 2 2vb b2
v v b
2 2
2vb b 2
dv
RT
Plow
v
1
v b dv
dv b
2
2
2
2 2
v 2vb b
RT v 2vb b
(3)
Plow
We again use partial fractions. For the first term in Equation (3):
1
v 2 2vb b 2
1
1
1
2 2b v 1 2 b v 1 2 b
so
v
1
v 1 2 b
v 2 2vb b 2 dv 2 2b ln v 1 2 b RT
RT
1
(4)
Plow
Plow
v b
v 2 2vb b
2 2
v b
v 2 2vb b
2 2
2b
(5)
v 2 2vb b2
Equation (5) can be substituted into Equation (3) to give two terms. The first term gives:
RT
Plow
v b
b
dv
2
2
2
v 2 2vb b2 2v 2vb b RT
(6)
Plow
1
1
1
4b v 1 2 b v 1 2 b
2
2 2
v 2vb b
2b
or
2
2
1
1
1
1
1
v 1 2 b v 1 2 b v 1 2 b
4b v 1 2 b
2
2 2
v 2vb b
(7)
2b
1
1
v 1 2 b dv 4 v 1 2 b RT
4 RT
(8)
Plow
Plow
and
2
1
1
dv
v 1 2 b
4 v 1 2 b RT
4 RT
(9)
Plow
Plow
1
1
1
v 1 2 b
v 1 2 b v 1 2 b 4 2b ln v 1 2 b RT
2 RT
(10)
Plow
Plow
Substituting Equations (4). (6). (8), (9) and (10) into Equation (3) gives:
vv b
1
v 1 2 b
b
dv
ln
2
2
2
2 2b v 1 2 b RT 2 v 2vb b 2 RT
RT v 2vb b 2
Plow
Plow
v
Plow
1
1
1
v 1 2 b
ln
4 v 1 2 b RT 4 v 1 2 b RT 4 2b v 1 2 b RT
Plow
Plow
Plow
RT
Plow
v 1 2 b
v
1 ln
dv
2
2
2
2
2 2
RT
4
2b
2
v
2vb
b
v
1
2
b
2vb
b
v v b
Plow
(12)
(11)
v 1 2 b
f iv
b
2a (T) 1
v
ln
ln
RT lnv b RT
2
2
RT
P
v
b
RT
4
2b
2
v
2vb
b
low
v 1 2 b
RT
Plow
Plow
If we note that
RT
b and let Plow 0 , we obtain
Plow
v 1 2 b
RT b a (T) 1
v
ln f i ln
ln
v b v b
RT 2 2b v 1 2 b v 2 2vb b 2
and
RT b a (T) 1
v 1 2 b
v
ln ln
ln
2
P
v
b
v
b
RT
2
2b
v
2vb
v 1 2 b
v
i
7.18
(a)
We can calculate the fugacity from the steam tables using the following equations
fv
g i g io RT ln i
Plow
g i hi Tsi
We can take the reference state to be 374 C and 10 kPa. Using enthalpy and entropy values
from the steam tables, interpolation gives:
kJ
g io 2934.5
kg
kJ
g i 890.9
kg
Therefore,
J
g io 52864
mol
J
g i 16049
mol
16049 J 52864 J
mol
mol
f iv 10 kPa exp
9382 kPa
8.314
647 K
mol
f iv 9.38 MPa
(b)
Following the development in Example 7.2, we can use the following equation to calculate the
fugacity from the van der Waals EOS,
b
v b 2a
f iv exp
ln i
RT RTvi
vi b
J m3
a 0.554
mol
b 3.05 10
m3
mol
The molar volume can be found from the van der Waals equation using the solver function on
a calculator.
m3
vi 3.80 10 4
mol
Substituting these values into the expression for fugacity, we get
f iv 9.77 MPa
(c)
The reduced temperature and pressure can be calculated from data in Table A.1.2:
Tr 1
0.344
Pr 0.52
log 0 0.08
log 1 0.0152
Calculate :
0.82
Therefore,
7.19
The solution method will be illustrated for parts A and F only. The answers only will be given
for the remaining parts. The generalized correlation tables can be used to answer each part,
except Part F, for which we can use the van der Waals EOS.
(a) CH4
The reduced temperature and pressure can be found using data from Appendix A:
Tr 4.06
Pr 3.26
0.008
Using reduced temperature and pressure, the fugacity coefficient can be found from Tables C.7
and C.8:
iv 1.04
Calculate fugacity:
f iv 156 bar
(b) C2H6
iv 1.02
f iv 153 bar
(c) NH3
iv 0.98
f iv 147 bar
(d) (CH3)2CO
iv 0.842
f iv 126.3 bar
(e) C6H12
iv 0.803
f iv 120.5 bar
(f) CO
Following the development in Example 7.2, we can use the following equation to calculate the
fugactity from the van der Waals EOS
b
v b 2a
f iv exp
ln i
RT RTvi
vi b
J m3
a 0.147
mol
m3
b 3.95 10 5
mol
The molar volume can be found from the van der Waals equation using the solver function on
a calculator.
m3
vi 4.48 10 4
mol
Substituting these values into the expression for fugacity, we get
f iv 156.5bar
Calculate the fugacity coefficient:
iv
f iv
1.04
P
As the strength of intermolecular forces between molecules increases, the fugacity coefficient
and fugacity decreases.
7.20
Use the virial equation expanded in pressure to express z as a function of pressure.
z 1 B' P
Calculate B:
z 0.9 1 B ' 30 105 Pa
RT
1 B' P
P
fv
P
B' P Plow ln i
ln
Plow
Plow
f iv P exp B' P
Therefore,
f iv 27.1 bar
and
iv
27.1 bar
0.903
30 bar
7.21
(a)
Equation 7.8:
P
f
RT ln i vi dP
Plow Plow
Manipulate the fugacity expression given in the problem statement to obtain:
f
f
P
ln i ln i ln low CP
P
P
Plow
30
P
RT CP ln low RT 0.065 P ln Plow ln P vi dP
T
P
P
low
(b)
Substitute numerical values:
vi 8.314 10 5
m 3 bar
30
1
353.15 K 0.065
353.15 K 30 bar
mol K
m3
vi 3.93 10 4
mol
7.22
Equation 7.8:
f iv P
v dP
RT ln
Plow i
Plow
The equation from the problem statement can be rearranged to yield
1 T
0.422Tc1.6
c
vi RT
0.083
P PcT
T 1.6
Substitute the above expression into Equation 7.8 and integrate (constant T):
fv
P Tc
0.422Tc1.6
P Plow
ln i ln
0.083
1.6
Plow
P
P
T
T
low
c
or
f v T
0.422Tc1.6
ln i c 0.083
P Plow
T1.6
P PcT
Let Plow go to zero gives:
P
T P
0.422Tc1.6
0.422
c
r
f i P exp
P
exp
0.083
0.083
T1.6
Tr1.6
PcT
Tr
v
and
P
T P
0.422Tc1.6
0.422
c
r
0.083
PcT
Tr
iv exp
Tc 373.2 K
Pc 89.37 bar
At 300 K and 20 bar, the expressions for fugacity and the fugacity coefficient provide
f iv 17.33 bar
iv 0.867
7.23
We are given the Schrieber volume-explicit equation of state:
RT kP 2 c
v
b
P
T
RT ln i vi dP
b dP
P
T
Plow Plow
Plow
fv
kP3 cP
RT ln i RT ln P
bP
3T T
Plow
Plow
Expand the logarithm terms, so that we can cancel the ln Plow terms.
RT ln f
v
i
RT ln Plow RT ln P RT ln Plow
kP3 cP
bP
T
3T
Plow
Collect the log terms on the left-hand side, and use the definition of the fugacity coefficient for a
pure species:
P
fi v
kP3 cP
v
RT ln
RT ln i
bP
P
3T T
P
low
Now, since we are free to choose an arbitrary pressure for Plow, we will choose a pressure
vanishingly close to 0. Thus, as Plow 0 ,
RT ln iv
kP3 cP
bP
3T
T
1 kP3 cP
P
b
2
RT
RT
iv exp 3
7.24
For an ideal gas reference state
fv P
gi gio RT ln i vi dP
Plow Plow
v
v2
v3
So
RT 13.40 106 14.49 108
dP 2
dv
v3
v4
v
And
fv
RT ln i
Plow
vi
RT
Plow
v
dv
v2
v3
Integrating:
fi v
vi 13.40 106 13.40 106 7.245 108 7.245 108
RT ln
RT ln RT
RT
2
2
P
v
v
RT
i
i
low
Plow
P
low
Plow
Canceling out ln(Plow) subtracting ln(P), and letting Plow ->0, we get
fv
Pv 13.40 106 7.245 108
RT ln i RT ln i RT ln i
RT
v1
vi2
P
6.70 106 4.83 108 13.40 106 7.245 108
ln i ln 1
RTvi
RTvi2
RTv1
RTvi2
Substituting in numbers
7.25
We need to pick an equation of state. We will use the virial expansion in pressure:
z
Pvi
1 B' P C ' P 2
RT
State 1
State 2
P
Pa
1.50 106
4.00 106
T
K
373.15
373.15
R
J/mol K
8.314
8.314
z
0.90
0.79
f v P 1
P
C'
2
ln i B' C ' P dP ln
B' P Plow P 2 Plow
Plow
2
Plow Plow P
Canceling out ln(Plow) subtracting ln(P), and letting Plow ->0, we get
fv
C'
ln i ln i B' P P 2
2
P
Substituting in numerical values gives:
i 0.736
and
fi v 36.8 bar
7.26
To determine the fugacity of pure methane at 220 K and 69 bar accurately, we can use the
generalized correlations. The reduced temperature and pressure can be found using data from
Appendix A:
Tr
T
220
1.15
Tc 190.6
Pr
P 69
1.5
Pc 46
0.008
Using reduced temperature and pressure, the fugacity coefficient can be found from Tables
C.7 and C.8:
iv 0.69
Calculate fugacity:
f1v 1P 47.7 bar
7.27
The data in the problem of the first printing are incorrect and should read
P [bar]
1.0
5.1
10.1
15.2
20.2
25.3
30.3
35.4
40.4
45.5
50.5
v [m3/mol]
2.45 x10-2
4.78 x10-3
2.32 x10-3
1.50 x10-3
1.08 x10-3
8.34 x10-4
6.66 x10-4
5.44 x10-4
4.52 x10-4
3.78 x10-4
3.17 x10-4
Equation 7.9:
ln iv
Pideal
zi 1
dP
P
-2
-3
-4
-5
-6
-7
-8
0.0
10.0
20.0
30.0
40.0
50.0
P (bar)
ln iv 0.3
Therefore,
iv 0.74
f iv iv P 37.5 bar
and
60.0
7.28
Rearrangement of Equation 7.9 yields
ln i zi 1
P
P
We can approximate the derivative at 500 bar by drawing a tangent line to the plot provided in
the problem statement and calculating the slope.
ln i
0.001 bar -1
P
zi
Pvi
0.001P 1
RT
J
-1
8.314
373.15 K 0.001 bar 500 bar 1
mol
vi
500 105 Pa
or
m3
vi 3.1 10 5
mol
7.29
If a gas obeys the Lewis fugacity rule, all the intermolecular interactions are the same. Therefore,
hmix 0
So
g mix T smix RT x1 ln x1 x2 ln x2 1, 730
J
mol
7.30
We want to calculate the fugacity coefficient of pure n-butane. The reduced temperature and
pressure can be found using data from Appendix A:
Tr
T 318.9
0.75
Tc 425.2
Pr
P 3.79
0.1
Pc 37.9
0.193
Using reduced temperature and pressure, the fugacity coefficient can be found from Tables
C.7 and C.8:
0.91
v
i
Calculate fugacity:
f1v y11P 0.41 bar
7.31
(a)
f1v 1P
The reduced temperature and pressure can be found using data from Appendix A:
Tr
190.6
1.0
190.6
Pr
32.2
0.70
46.00
0.008
Using reduced temperature and pressure, the fugacity coefficient can be found from Tables C.7
and C.8:
0.77
v
i
Calculate fugacity:
fi v 24.8 bar
(b)
f1v y11P 19.8 bar
7.32
(a)
Pure Species:
fv P
RT ln 1 v1dP
Plow Plow
To acquire an expression for v1, set the mole fraction of species 1 equal to unity.
A B
1
v1 RT P
RT
P
Substituting this expression into the integral and integrating, we get
2
fv
P A B P 2 Plow
ln 1 ln
Plow
RT 2
2
Plow
lnf1v lnP
A B P 2
RT
Therefore,
f v A B P2
ln1v ln 1
P RT 2
A B P 2
5
5 50
RT 2
1v exp
1v 0.93
Species in a mixture:
f v P
RT ln 1 V1dP
yP
1 low Plow
The expression for the extensive volume is
V n1 n2 n3
RT
PAn1 n2 Bn1 n2 n3
P
Therefore,
V1
RT
PA B
P
Substituting this result into the above integral and integrating, we obtain the following after
simplifiction
P2 A
B
v
ln 1
2 RT RT
P2 A
B
v
1 exp
2 RT RT
50 atm 2
v
5 1
5 1
1 exp
9.0
10
3.0
10
atm2
atm2
2
1v 0.93
(b)
When the vapor and liquid are in equilibrium,
f1v f1l
Hence,
f1v 15 atm
We also know the value of the fugacity coefficient from part (a). This can be used to calculate
the mole fraction in the vapor.
f1v
0.93
y1 P
15 atm
y1
0.322
0.9350 atm
1v
7.33
(a)
The Lewis fugacity rule:
1v 1v
From Example 7.2
ln iv
v b P 2a
b
ln i
vi b
RT RTvi
m3
v1 1.15 10 3
mol
Now, the fugacity coefficient can be computed by substituting values.
1v 0.89
The fugacity is calculated using the fugacity coefficient.
RT
1
nT bmix nT amix
P
RT
n12
n22
RT
1
V n1 n2
n1b1 n2b2 n3b3
a1
a
n1 n2 n3 2
P
RT n1 n2 n3
n32
2n1n3
2n2 n3
2n1n2
a3
a12
a13
a23
n1 n2 n3 n1 n2 n3
n1 n2 n3
n1 n2 n3
f v P
RT ln 1 V1dP
yP
1 low Plow
Find V1 :
V
RT
1
b1
P
RT
dn1 T , P, n2 , n3
f v
P b1
1
ln 1 ln
P Plow
2 y1a1 2 y2 a2 2 y3a13 amix P Plow
2
yP
P
RT
RT
1
low
low
By subtracting ln Plow and ln P from both sides and then letting Plow 0 , we obtain
f v b
1
ln 1v ln 1 1
2 y1a1 2 y2 a2 2 y3a13 amix P
2
y P
1 RT RT
ln 1v 0.10
1v 0.906
Calculate fugacity:
f1v y11v P 0.2 0.906 30 bar
7.34
(a)
Equation 7.14:
V
f v
P
RT ln a
dV
yP
nRT na T ,V , n
a low
i a
Plow
P RT
2
V
Therefore,
P
1 2n B 2nb Bab 2nc Bac
RT a aa
V2
V
na T ,V , ni a
Substitute the above equation into Equation 7.14 and integrate
f v
2n B 2nb Bab 2nc Bac
nRT 2na Baa 2nb Bab 2nc Bac Plow
ln a ln V a aa
ln
yP
V
Plow
nRT
a low
Canceling the ln Plow from both sides and then allowing Plow to go to zero, we obtain
f v
2n B 2nb Bab 2nc Bac
nRT 2na Baa 2nb Bab 2nc Bac
ln a ln V a aa
ln nRT ln
y
V
V
V
f v
nRT 2na Baa 2nb Bab 2nc Bac
ln a ln av ln
y P
PV
V
av exp
z
y P
2 y B 2 yb Bab 2 yc Bac
fav a exp a aa
v
z
(b)
For this system
y a 0.2
yb 0.3
yc 0.5
Bmix 2.392 10
m3
mol
Therefore,
B
Pv
1 mix
RT
v
m3
v 1.36 10 3
mol
(Note: There are two solutions to the equation, but the other value is not sensible.)
z
av 1.04
fav 0.215 bar 1.04 3.12 bar
(c)
The EOS reduces to the following expression for pure methane:
Pv a
B
1 aa
RT
va
1 2B
dP RT 2 3aa dv a
va
va
Develop an expression for the fugacity coefficient similar to the method in Example 7.2
f av
v
dP
RT
ln
a
Plow
RT
va
Plow
RT
RT
Plow
1 2 Baa
2
va
va
f av
dv
RT
ln
a
Plow
f av
2Baa RT 2Baa
ln
lnv a
ln
v a Plow RT
Plow
Plow
Cancel the logarithmic terms containing Plow and then let Plow go to zero:
lnf av
v
2Baa
ln a
RT
va
Therefore,
2B
RT
exp aa
va
va
2B
1
av exp aa
za
va
f av
2B
1
exp aa
za
va
2B
y RT
fav y a f av a exp aa
va
va
av av
To calculate the fugacity and fugacity coefficient, we will need to find the pure species molar
volume:
m3
v a 1.61103
mol
Substituting values into the above expressions, we obtain
av 0.975
7.37
Calculate fugacity and fugacity coefficient of phenol in a mixture of 20 mole % phenol (1) and
80 mole % oxygen (2) at 694.2 K and 24.52 bar using the following:
(a) Ideal gas law
For an ideal gas, we assume the fugacity coefficient is 1.
Next fugacity is calculated by:
(b) The Lewis Fugacity Rule (choose the method that gives you as accurate an answer as
possible).
Options:
1) Ideal gas definitely not the most accurate!
2) E.O.S The van der Waals E.O.S is more accurate than the ideal gas assumption,
however, the van der Waals equation is not as accurate as more modern cubic equations
of state. (Text pg 310)
3) Generalized Correlations as noted in class on 2-6-08, the Lee-Kesler tables (utilized in
the generalized correlations) are more accurate than the van der Waals E.O.S.
From the above information, we can choose a more modern cubic equation of state (as will be
demonstrated with the Redlich-Kwong E.O.S. in part c) or we can choose the Generalized
Correlations. For variety, lets use the Generalized Correlations.
To use the tables in the book, we utilize the form of the generalized correlations:
Pr
P
Pc
Tr
T
Tc
From Appendix A.1 we find Pc and Tc for phenol, which we can then use to get Pr and Tr.
Pc 61.3
Pr bar
0.4
Tc
Tr
694.2
K
1
0.440
1 1 0.86
f1v y11v P 0.2 0.86 24.52 bar
f1v 4.2 bar
We can also look at results for fugacity coefficient using the Peng Robinson E.O.S. via
ThermoSolver:
Note: For the Peng Robinson E.O.S. we would use the pure species fugacity coefficient given in
the right column with the Lewis Fugacity Rule, but ThermoSolver gives both the pure species
fugacity coefficient as well as the fugacity coefficient of species i in the mixture.
(c) The Redlich-Kwong Equation of State, See Table 7.1
From Table 7.1 we get
a
1 b1a
b
RT
b
ln(1v ) ln
ln 1 b1
2 a 1 a ln 1
1.5
1.5
Pv
v
v
v b bRT (v b) bRT b
Note: In this equation a represents amix and b represents bmix.
We need to find a1, a2, a, b1, b2, b and v
b 1/ 2 (i) (i)
P
PT v v b
Start with the ideal gas law:
RT
m3
v (0)
2.35 103
P
mol
then
RT
m3
RT
m3
: and v (2)
v (1)
2.34 103
2.34 103
P
mol
P
mol
Now use the equation from Table 7.1 to find the fugacity coefficient.
1
a
1 b1a
b
RT
b
ln(1v ) ln
ln 1 b1
2 a 1 a ln 1
1.5
1.5
Pv
v
v
v b bRT (v b) bRT b
v
0.943
1
7.38
(a)
f1v P
RT ln
v1dP
Plow Plow
v1
RT RT Pr ,1
P
P 8Tr ,1
f v P RT RTc ,1
RT ln 1
dP
P
P
8
P
low
c
,1
Plow
fv
P RTc ,1
RT ln 1 RT ln
P Plow
Plow
Plow 8Pc ,1
P
fv
ln 1 ln 1v r ,1
8Tr ,1
P
Tr
219
0.6
365
ln 1v
Pr
27.72
0.6
46.2
1
8
1v 1.13
f1v y11v P 7.85 bar
(b)
f v P
RT ln 1 V1dP
yP
1 low Plow
V n1 n2
RT RT n1Pr ,1 n2 Pr ,2
P
P 8Tr ,1 8Tr ,2
V
RT RTc ,1
V1
P 8Pc ,1
dn1 T , P ,n2 ,n3
f v P RT RTc ,1
RT ln 1
dP
yP
P
8
P
1
low
c
,1
Plow
f v
P RTc ,1
RT ln 1 RT ln
P Plow
yP
P
8
P
c ,1
low
1 low
f v
P
ln 1 ln 1v r ,1
y P
8Tr ,1
1
Tr
219
0.6
365
ln 1v
1v 1.13
Pr
27.72
0.6
46.2
1
8
(c)
Values are the same so all the intermolecular interactions are the same
7.39
(a)
n1 n2 RT
P
RT
n12 B11' 2n1n2 B12' n22 B22'
n1 n2
V
RT
'
V1
P
n1 T , P ,n2
V
RT
V1
P
n1 T , P ,n2
P
f1v P
1
RT ln
V dP RT B ' 2 y1 B11' 2 y2 B12' dP
y P 1
P
Plow
1 low Plow
P
'
'
'
ln
2 y1 B11 2 y2 B12 B P Plow
P
low
f v
ln 1
yP
1
v
'
'
'
ln 1 2 y1B11 2 y2 B12 B P
(b)
y1 = 0.4
B11'
B12'
'
B22
- 1.9 x 10-7
[Pa-1]
- 3.6 x 10-8
[Pa-1]
- 2.0 x 10-9
[Pa-1]
So
1v 0.84
And
f1v y11v P 4.0 bar
(c)
Since B11' and B11' are very different, we do not expect the Lewis rule to be a good approximation.
7.40
Using the Lewis fugacity rule for n-pentane (1):
f1v y11P
The reduced temperature and pressure can be found using data from Appendix A:
Tr
495
1.0
469.6
Pr
18
0.70
38.74
0.251
Using reduced temperature and pressure, the fugacity coefficient can be found from Tables C.7
and C.8. After interpolation, we get:
iv 0.81
Calculate fugacity:
7.41
From the definition of fugacity:
V
f v P
P
RT ln i Vi dP
dV
yP
nT RT n1 T ,V , n , n
1 low Plow
2 3
Plow
Differentiating
2
3
n
V
V
n
c
n
c
1 T ,V ,n2 ,n3
1 1 2 2
V n1c1 n2c2
Into the equation above:
V
V
V
2c1 n12 a1 n22 a2 2n1n2 a12
fi v
2n1a1 2n2 a12
RT
dV
dV
RT ln
2
3
dV
y P
V
n
c
n
c
V
n
c
n
c
n
RT
n
RT
n
RT
1
low
T
T
T
1 1
2 2
1 1
2 2
Plow
Plow
Plow
Integrating we get
V
fi v
RT ln
RT ln
yP
nT RT
1 low
Plow
1
1
2n1a1 2n2 a12
V n1c1 n2c2 nT RT n c n c
1 1
2 2
Plow
1
1
2
2
c1 n1 a1 n2 a2 2n1n2 a12
2
2
V n1c1 n2 c2 nT RT n c n c
1 1
2 2
Plow
Taking and
nT RT
n1c1 n2c2
Plow
V
fi v
RT ln
RT ln
yP
nT RT
1 low
Plow
1
1
2n1a1 2n2 a12
V n1c1 n2c2 nT RT
Plow
1
1
2
2
c1 n1 a1 n2 a2 2n1n2 a12
2
2
V n1c1 n2c2 nT RT
Plow
Canceling out ln(Plow) subtracting ln(P), and letting Plow ->0, we get
f v
1
RT ln i RT ln z 2n1a1 2n2 a12
yP
V n1c1 n2 c2
1 low
Simplifying:
RT ln 1 RT ln z 2
y1a1 y2 a12
c1a
2
vc
v c
7.42
From the definition of fugacity:
V
f v P
P
RT ln i Vi dP
dV
yP
nT RT n1 T ,V , n , n
1 low Plow
2 3
Plow
Differentiating
b1 n1 n2 n3 RT
P
RT
2
n1 T ,V ,n2 ,n3 V n1b1 n2b2 n3b3 V n1b1 n2b2 n3b3
V n c n c
1 1
2 n3c3
V n c n c
1 1
2 2
n3c3
V
f v
RT
RT ln i
dV
yP
V
n
b
n
b
n
b
n
RT
1
low
1
1
2
2
3
3
T
Plow
b n n n RT
1
1
2
3
dV
2
P
V
low
2n a 2n a 2n a
1 1
2 12
3 13
dV
2
nT RT V n1c1 n2 c2 n3c3
P
V
low
n
c
n
c
n
c
nT RT
1 1 2 2 3 3
P
V
low
Integrating we get
V n b n b n b
fi v
1 1
2 2
3 3
RT ln
RT ln
y P
n
RT
T
1 low
n1b1 n2b2 n3b3
Plow
1
1
RTb1 n1 n2 n3
Plow
1
1
Plow
c1 n12 a1 n22 a2 n32 a3 2n1n2 a12 2n1n3a13 2n2 n3a23
1
1
2
2
V n1c1 n2 c2 n3c3 nT RT n c n c n c
1 1
2 2
3 3
Plow
Taking
nT RT
n RT
n1b1 n2b2 n3b3 and T
n1c1 n2c2 n3c3
Plow
Plow
V n b n b n b
fi v
1 1
2 2
3 3
RT ln
RT ln
y P
n
RT
T
1 low
Plow
1
1
RTb1 n1 n2 n3
Plow
1
1
2n1a1 2n2 a12 2n3a13
Plow
c1 n12 a1 n22 a2 n32 a3 2n1n2 a12 2n1n3a13 2n2 n3a23
1
1
2
2
Plow
Canceling out ln(Plow) subtracting ln(P), and letting Plow ->0, we get
fi v
PV P n1b1 n2b2 n3b3
RT ln
RT ln
y P
nT RT
1
RTb1 n1 n2 n3
1
2n1a1 2n2 a12 2n3a13
V n1c1 n2 c2 n3c3
Simplifying:
y a y2 a12 y3a13
c1a
bP RTb1
RT ln 1 RT ln z
2 1 1
RT v b
vc
v c
7.43
Let a refer to methane and b refer to hydrogen sulfide. From Example 7.4
2 ya aa yb aa ab
P v bmix
ba
ln av ln
RT
RTv
v bmix
In the above expression, v and bmix depend on mole fractions. First, calculate a a , ab , ba , and
bb :
27 RTc 2
a
64 Pc
RTc
8Pc
m3
mol
J m3
aa 0.230
2
mol
ba 4.31 10
J m3
ab 0.454
2
mol
m3
bb 4.34 10 5
mol
a
RT
mix
v bmix
v2
Once the molar volume is calculated, the molar fugacity coefficient can be found using the
expression from Example 7.4. The following table can be created:
ya
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
yb
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
amix
0.454
0.428
0.403
0.379
0.355
0.333
0.311
0.289
0.269
0.249
0.230
bmix
4.34 x 10-5
4.34 x 10-5
4.33 x 10-5
4.33 x 10-5
4.33 x 10-5
4.33 x 10-5
4.32 x 10-5
4.32 x 10-5
4.32 x 10-5
4.31 x 10-5
4.31 x 10-5
v
0.000437
0.000447
0.000456
0.000465
0.000473
0.000481
0.000488
0.000494
0.000500
0.000506
0.000512
ln(a)
0.001
-0.007
-0.013
-0.018
-0.023
-0.026
-0.029
-0.031
-0.032
-0.033
-0.033
a
1.001
0.993
0.987
0.982
0.978
0.974
0.972
0.970
0.968
0.967
0.967
yb
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
a
1.033
1.02
1.008
1.000
0.992
0.986
0.982
0.978
0.977
0.975
0.975
Plot the activity coefficient versus the mole fraction of methane for both methods on the same
graph:
a vs. ya From the van der Waals EOS
Compared to Thermosolver Results
1.050
1.025
1.000
0.975
0.950
0
0.1
0.2
0.3
0.4
0.5
0.6
ya (mole fraction)
0.7
0.8
0.9
7.44
Let a refer to methane and b refer to hydrogen sulfide. From Problem 7.5:
a
1 ba a
b
RT
b
ln av ln
2 aa a ln 1
ln 1 ba
1.5
1.5
Pv
v
v
v b bRT v b bRT b
(Note: a is short for amix and b is short for bmix)
In the above expression, v , amix, and bmix depend on mole fractions. First, calculate a a , ab , ba ,
and bb :
R 2Tc2.5
a 0.42748
Pc
b 0.08664
RTc
Pc
J m 3 K1/2
a a 3.22
2
mol
ba 2.99 10
J m 3 K1/2
ab 8.90
2
mol
m3
bb 3.01 10 5
mol
m3
mol
amix
RT
1
/
2
v bmix T vv bmix
Once the molar volume is calculated, the fugacity coefficient can be found by substituting the
appropriate values into the expression from Problem 7.5. The following table can be created:
ya
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
yb
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
amix
8.900
8.205
7.538
6.899
6.289
5.707
5.153
4.627
4.130
3.661
3.220
bmix
3.01 x 10-5
3.01 x 10-5
3.01 x 10-5
3.00 x 10-5
3.00 x 10-5
3.00 x 10-5
3.00 x 10-5
3.00 x 10-5
2.99 x 10-5
2.99 x 10-5
2.99 x 10-5
v
0.000437
0.000449
0.000460
0.000470
0.000479
0.000487
0.000495
0.000502
0.000508
0.000514
0.000520
yb
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
a
1.033
1.02
1.008
1.000
0.992
0.986
0.982
0.978
0.977
0.975
0.975
ln a
0.036
0.024
0.013
0.005
-0.002
-0.007
-0.011
-0.014
-0.016
-0.018
-0.018
a
1.037
1.024
1.013
1.005
0.998
0.993
0.989
0.986
0.984
0.982
0.982
1.025
Redlich-Kwong EOS
1.000
Thermosolver
0.975
0.950
0
0.2
0.4
ya
0.6
0.8
Clearly, the results from the two solution methods agree well. The Redlich-Kwong EOS
provides a fugacity coefficient that is slightly larger over the entire composition range.
7.45
Let a refer to methane and b refer to hydrogen sulfide.
(a)
From Example 7.4,
2 xa aa xb aa ab
P v bmix
ba
ln av ln
RT
RTv
v bmix
27 RTc 2
64 Pc
J m3
aa 0.230
2
mol
J m3
ab 0.454
2
mol
RTc
8Pc
m3
ba 4.31 10 5
mol
m3
bb 4.34 10 5
mol
J m3
amix ya2 aa 2 ya yb aa ab yb2 ab 0.333
2
mol
m3
bmix y a ba yb bb 4.325 10 5
mol
Using these expressions we can find the molar volume with the van der Waals EOS:
P
so
a
RT
mix
v bmix
v2
m3
v 4.81104
mol
Substituting these values into the equation for the fugacity coefficient, we get
av 0.974
(b)
From Problem 7.5:
a
1 ba a
b
RT
b
ln av ln
2 aa a ln 1
ln 1 ba
1.5
1.5
Pv
v
v
v b bRT v b bRT b
(Note: a is short for amix and b is short for bmix)
a 0.42748
R 2Tc2.5
Pc
J m3
aa 3.22
2
mol
J m3
ab 8.90
2
mol
b 0.08664
RTc
Pc
m3
ba 2.99 10 5
mol
m3
bb 3.0110 4
mol
mol
Using these expressions we can find the molar volume with the Redlich-Kwong EOS:
P
amix
RT
1
/
2
v bmix T vv bmix
m3
v 4.871 10 4
mol
Substituting these values into the expression for the fugacity coefficient, we get
av 0.993
(c)
Using Kays mixing rules, we have the following expressions:
T pc yaTc, a ybTc, b
pc 0.054
Therefore,
Tr 1.58
Pr 1.03
log 1 0.0371
Therefore,
log v 0.0336 0.0540.0371
v 0.930
(d)
av 0.986
A summary of the results for each solution method is provided in the following table. The
percent differences are based on the fugacity coefficient found using ThermoSolver.
Solution Method
(a)
(b)
(c)
(d)
av
% Difference
0.974
0.993
0.930
0.986
1.22
0.71
5.68
0
Clearly, all of the solution methods agree reasonably well with the Peng-Robinson EOS. The
fugacity coefficient calculated with the Redlich-Kwong EOS agrees the best.
7.46
For the virial equation, we have
B P
z 1 mix
RT
where
cm 3
cm 3
Baa 16
and Bbb 101
mol
mol
Solve for volume:
P
P
na nb
To get the partial molar volume, we differentiate with repect to na.
V
Va
na
2
2
P
na nb
na nb 2
T , P,nb
or
Va
RT
2 ya Baa 2 yb Bab ya2 Baa 2 ya yb Bab yb2 Bbb
P
fav
RT
2
2
2
y
B
2
y
B
y
B
2
y
y
B
y
B
dP
=
RT
ln
a aa a b ab b bb
so
a aa
b ab
P
Plow
pa ,low
P
fav
P
2
2
RT ln
2 ya Baa 2 yb Bab ya Baa 2 ya yb Bab yb Bbb dP =RT ln
Plow Plow
ya Plow
P
Rearranging
Plow
f v
2 ya Baa 2 yb Bab ya2 Baa 2 ya yb Bab yb2 Bbb dP =RT ln a RT ln av
ya P
Integrating, we get
2y B
a
aa
2Bab Bbb P RT ln a
RT
ln a Bbb
Bab P
34.5
2
cm3
mol
cm 3
Bab Baa Bbb 40.2
mol
This problem can also be solved using the form of the virial equation:
z 1
Bmix
v
cm3
v vP
Bab ln a 55.9
2 RT
mol
7.47
(a)
We can start with Equation 7.14 to find the fugacity coefficient:
V
fv
P
RT ln 1
dV
n
y1 Plow
1
T ,V , n 2
nRT
Plow
amix
n n2 RT n1a1 n2 a2 n1 n2 1 / 2
RT
v
V
v 3 / 2T 1 / 2
V 3 / 2T 1 / 2
Differentiate:
P
RT
1
1 / 2 n a n2 a 2
a1 n1 n2 1 1
V V 3 / 2T 1 / 2
2n1 n2 1 / 2
n1 T ,V , n 2
Substitute this expression into Equation 7.14 and integrate to obtain
f1v
n1a1 n2 a2
2
1/2
VPlow
RT ln
RT ln
1/2 1/2 a1 n1 n2
1/2
nRT V T
2 n1 n2
y1 Plow
1/2
n a n a2
2
1/2
P
low
a1 n1 n2 1 1 2 1/2
1/2
nRT T
2 n1 n2
This expression can be simplified by canceling the terms containing Plow and then taking the
limit as Plow goes to zero. This results in
f1v
n1a1 n2 a2
2
1/2
nRT
RT ln RT ln
1/2 1/2 a1 n1 n2
1/2
V V T
2 n1 n2
y1
f v
2
1
RT
RT ln 1 RT ln
a
y1a1 y2a2
1
2
vT
v
y1
If we subtract the natural log of pressure from both sides of the equation and rearrange, we
obtain
2
RT
ln 1v ln
Pv RT vT
a1 2 y1a1 y2 a2
Now, find the numerical value of the fugacity coefficient by substituting values for all of the
variables.
2
1
800
0.33
800
0.66
500
2
1.78 106 0.002 8.314 500 0.002 500
1v exp ln
8.314 500
1v 0.689
Note: The pressure was calculated prior to substitution using the given EOS.
(b)
The Lewis fugacity rule states
1v 1v
Start with Equation 7.26 to find 1v :
fv P
RT ln 1 v1dP
Plow
Plow
RT 3
a1
dv1
dP
2 T 1 / 2v5 / 2
v12
1
Substitute the above expression into Equation 7.8 and change the limits of integration:
f v v1 RT 3
a1
dv
RT ln 1
1/ 2 3 / 2 1
Plow
2
T
v
v
1
RT 1
Plow
fv
3a
v P 3a1
RT ln 1 RT ln 1 low
1
Plow
Tv1
T
RT
Plow
RT
If we cancel the natural log terms containing Plow and then let Plow go to zero, the above equation
simplifies to
RT
ln f1v ln
v1
3a1
RT Tv1
Now subtract the natural log of P from both sides of the equation:
ln
f1v
RT
3a1
ln 1v ln
P
Pv1 RT Tv1
v1 is the molar volume of species 1 at the temperature and pressure of the mixture in Part (a) We
can calculate it from the given EOS.
1.87 10 6 Pa
8.314500
v1
800
500v13
m3
v1 0.00187
mol
Substitute values into the expression for the fugacity coefficient and evaluate:
8.314 500
3 800
exp ln
v
1
1v 0.687
The fugacity coefficient calculated using the Lewis fugacity rule is equal to the fugacity
coefficient in Part (a)
7.48
Gibbs energy can be written as
dg i si dT vi dP
Therefore,
g i
s T vi P
i
vi
P
P T
T
Equation 7.8 states
f
g i g i RT ln i g i RT ln f i RT ln Plow
Plow
Differentiate:
gi RT ln fi RT ln Plow
ln f i
gi
RT
P
P
P T
T
Hence,
ln fi
gi
RT
i
P
P T
7.49
It can be shown that
ln f i
RT
vi
P T
To solve this problem, we can assume the molar volume of liquid water at 300 C is independent
of pressure. Therefore,
fi
RT
d ln
fi
f i vil
sat
dP
P sat
fi vil
ln sat
P P sat
fi RT
We need to calculate f isat , but before we can do that, we must choose a reference. Use
T 300 C and P 10 kPa as the reference. From the steam tables
kJ
kg K
kJ
h 3076.5
kg
s 9.2812
kJ
g 3076.5 573.15 K 9.2812
kg
kJ
kg K 2243.0
kJ
kg 40407.2
J
mol
For P sat 8.5810 MPa and T 300 C , the steam tables allow us the calculate the Gibbs
energy:
kJ
kJ
kJ
J
520.6 9378.5
g sat 2748.9 573.15 K 5.7044
mol
kg
kg K
kg
Once we find vil , we can calculate the fugacity. From the saturated steam tables,
m3
5
visat 0.001404
0.0180148 kg/mol 2.53 10
kg
m3
mol
Therefore,
2.53 105
8.314 573.15
7.50
(a)
From Equation 7.35 we have the following relationship
f il iv Pisat
Since the system pressure is low (1 bar), the fugacity coefficient is unity. Calculate the
saturation pressure using Antoine Equation data in Appendix A.1:
2154.9
v
f il isat Pisat exp i dP
sat RT
Pi
Since Pisat 0.610 bar , the saturation fugacity coefficient of n-butane is unity. From the
problem statement, we can obtain vi:
vi
MW i
i
0.058123 kg/mol
579 kg/m3
m3
1.00 104
mol
Since the density is constant with respect to pressure, we can substitute numerical values into
Equation 7.36 and integrate:
J
8.314 mol K 260 K
l
fi 1.53 bar
7.51
We can use Equation 7.36 to calculate the fugacity of pure liquid acetone.
f il
isat Pisat
vi
exp
dP
sat RT
Pi
Calculate the saturation pressure using Antoines Equation data in Appendix A.1:
2940.46
382 K
0.75
508.1 K
Prsat
4.64 bar
0.099
47.01 bar
0.309
Use these values in Tables C.7 and C.8 to determine the fugacity coefficient:
isat 0.904
Since the density is constant with respect to pressure, we can substitute numerical values into
Equation 7.36 and integrate:
J
8.314 mol K 382 K
l
fi 5.23 bar
7.52
We can use Equation 7.36 to calculate the fugacity of pure liquid acetone.
f il
isat Pisat
vi
exp
dP
sat RT
Pi
Calculate the saturation pressure using Antoines Equation data in Appendix A.1:
1872.46
333 K
0.9
370 K
Prsat
20.53 bar
0.48
44.24 bar
0.152
Use these values in Tables C.7 and C.8 to determine the fugacity coefficient:
isat 0.767
Since the density is constant with respect to pressure, we can substitute numerical values into
Equation 7.36 and integrate:
Taking the Poynting correction to be negligible, we get
7.53
We can use Equation 7.36 to calculate the fugacity of pure liquid acetone.
f il
isat Pisat
vi
exp
dP
sat RT
Pi
so
isat 1
and
vi 1.8 105
m3
mol
Taking vi to be constant
v
7.54
(a)
Begin by drawing a line tangent to the plot for fal as xa 0 . Then, extend the line to xa 1 .
The Henrys constant is equal to the intercept of the vertical gridline when xa 1 . Therefore,
H a 19.5 kPa
(b)
The activity coefficient is defined as
ga
fal
x f o
a a
ga
fal
xaH a
g a xa 0.4
g a xa 0.8
12 kPa
1.54
1.99
31 kPa
(c)
From the Gibbs-Duhem Equation, we know
xa
d ln g a
d ln g b
xb
0
dxa
dxa
d ln g b
must be negative. Since the activity coefficient is based on a Lewis-Randall
dxa
reference state, ln g b 0 as xa 0 . Therefore, at xa 0.4 , ln g b is negative and g b 1 .
Therefore,
(d)
Since g bL / R 1 , the a-b interactions are stronger than the pure species interactions.
(e)
When a gas is in equilibrium with a liquid, the fugacities of each phase are equal. For an ideal
gas, fav ya P . Setting fugacities equal, we get
ya P fav fal
Therefore,
ya
fal 12 kPa
P 20 kPa
ya 0.6
7.55
(a)
Both species are based on the Lewis-Randall reference state because
ln g a 0 as xa 1
ln g b 0 as xb 1
(b)
The Gibbs-Duhem equation states
xa d ln g a xb d ln g b 0
d ln g a
d ln g b
xb
0
dxa
dxa
Therefore,
ln g a 2.5
ln g b 1.5
From Table 7.2:
J
RT ln g a 8.314
300 K 2.5 A B
mol K
J
RT ln g b 8.314
300 K 1.5 A B
mol K
Solve simultaneously:
A 4988.4 J mol-1
B 1247.1 J mol -1
Therefore,
(d)
The mixture will not separate into two phases. The system is more stable as a mixture as shown
by the activity coefficients being less than one. Furthermore, g mix is always negative because
gE is always negative. (This becomes apparent by examining the magnitude of the A and B
parameters in the three-suffix Margules equation.) Therefore, it is thermodynamically favorable
for the system to mix.
7.56
(a)
The activity coefficient for species A is based on the Lewis-Randall reference state. For the
Lewis-Randall reference state, the natural log of the activity coefficient of species A goes to zero
as the mole fraction of A goes to one since all interactions are a-a interactions.
(b)
Equation 7.84 can be used to calculate the fugacity of species a. It states
P l
v
f al asat Pasat exp a dP
sat RT
Pa
However, asat is assumed equal to one since the saturation pressure is low. The Poynting
correction can also be assumed equal to one since the system pressure is low. Therefore,
f al Pasat
f al 80 kPa
(c)
The value of H a can be calculated using Equation 7.75. It states
g a
Ha
fa
ln ya 2.5
Using the value from Part (b), we can calculate Ha:
H a 80 kPaexp 2.5
H a 975 kPa
(d)
From Table 7.1,
RT ln g a Axb2
As xb 1 , ln g a 2.5 . Therefore,
2.5RT
A 6235.5 J mol -1
(e)
We first calculate the mole fraction of a in the liquid mixture.
xa
na
2 mol
0.4
ntot 5 mol
g a 2.40
This allows us to fugacity of species a in the liquid which is equal to the fugacity of species a in
the vapor phase.
fav ya P
ya
76.8 kPa
0.768
100 kPa
(f)
In part D, the Margules parameter was calculated for the mixture based on a Lewis-Randall
reference state. From Equation 7.56:
Ax a2 RT ln g b
1.49
g b exp
8.314 J mol-1 K -1 300 K
7.57
(a)
Assume the two-suffix Margules equation represents the excess Gibbs energy data well.
Therefore, for any of the data points in the provided graph, the following relationship should be
true
g E Ax1 x2
gE A
x1 x2
R
R
When x2 0.5 :
A
32 K
128 K
R 0.50.5
To calculate the activity coefficients of cyclohexane, we can use the following equations
Ax12 RT ln g 2
A 2
R x1
g 2 exp
T
(i).
128 K 0.752
g 2 exp
343 K
g 2 1.23
(ii).
g 2
128 K 12
exp
343 K
g 2 1.45
(b)
From Equation 7.75:
g 2
H2
f2
where
f 2 P2sat
Calculate the saturation pressure of cyclohexane using data from Appendix A.1:
2766.63
Therefore,
H 2 1.450.722 bar
H 2 1.05 bar
(c)
Since A>0, gE is always greater than one. Therefore, like interactions are stronger.
7.58
To find the activity coefficients, we can use the following two equations:
RT ln g a GaE
RT ln g b GbE
The derivations of expressions for g a will be shown below. The method for finding g b is
analogous, and the final expressions can be found in Table 7.2.
(a)
The excess Gibbs energy:
GE
na nb
na nb
na nb
A B
n
a
b
Find GaE :
dG E
GaE
dna
xb xa xb A Bxa xb 2 Bx a xb2
T ,V , nb
Substitute xa 1 xb :
(b)
Rewrite excess Gibbs energy as
na nb
G E AB
An a Bnb
Find GaE :
dG E
GaE
dna
B 2 nb2
Ana Bnb 2
T ,V , nb
Divide the numerator and denominator of the right-hand side of the above expression by na nb
:
B 2 xb2
GaE A
Ax a Bxb 2
Therefore,
A
RT
g a exp
B 2 xb2
2
Ax a Bxb
(c)
Rewrite excess Gibbs energy as
n ab nb
n ba na
nb ln b
G E RT na ln a
na nb
na nb
Find GaE :
x 1 xa xb ab ba xb xa ba
GaE RT ln xa ab xb a
xa xb ab
xb xa ba
xb xa ba
1 x 1 x 1
E
b
ab b ba
Ga RT ln xa ab xb xb
xb xa ba
xa xb ab
1 xb xb 1 ab
GaE RT ln xa ab xb
xa xb ab
ab
ba
GaE RT ln xa ab xb xb
xa xb ab xb xa ba
ab
ba
g a exp ln xa ab xb xb
xa xb ab xb xa ba
na nb
na nb
G E RT ba G ba
ab G ab
na nb G ba
nb na G ab
Find GaE :
GaE
dG E
dna
ba G 2 n 2
ab G ab nb2
ba
b
RT
2
2
n
G
n
n
G
T ,V , nb
b ba
b
a ab
a
G2
ab G ab
ba ba
GaE RTxb2
xa xb G ba 2 xb xa G ab 2
Therefore,
xa xb G ba 2
g a exp xb2
ba G 2ba
2
xb xa G ab
ab G ab
7.59
Three-suffix Margules:
At infinite dilution:
RT ln g a RT ln 2 A B
RT ln g b RT ln 3 / 2 A B
Solving simultaneously,
A RT ln 3
B RT ln 3 / 2
RT ln g a RT ln
RT ln g b
Solving, we obtain
g a 1.11
g b 1.19
Van Laar:
At infinite dilution:
RT ln g a RT ln2 A
RT ln g b RT ln3/2 B
ln 3 / 20.5
RT ln g a RT ln 2
ln 20.5 ln 3 / 20.5
2
ln20.5
RT ln g b RT ln3/2
ln20.5 ln3/20.5
2
Solving, we obtain
g a 1.10
g b 1.18
Wilson:
At infinite dilution:
RT ln g a RT ln2 RT ln ab ba 1
RT ln g b RT ln3/2 RT lnba ab 1
Solve simultaneously:
ab 0.407
ba 1.21
1.21
0.407
ln g a ln0.5 0.50.407 0.5
0.407
1.21
ln g b ln0.5 0.51.21 0.5
g a 1.10
g b 1.17
7.60
The problem statement provides the following information:
x
a 0.9
xa 0.2
xb 0.1
xb 0.8
At equilibrium:
x
a g a xa g a
xb g b xb g b
x
ln a
x
a
x
ln b
x
b
ln g ln g
a
a
ln g ln g
b
b
Use the composition data provided in the problem statement and the expressions from Table 7.1:
1
0.9
A 3B 0.82 0.12 4 B 0.8 3 0.13
ln
A 10100 J mol -1
B 1300 J mol -1
7.61
Let the subscript a represent water and b represent ethanol. Since the activity coefficients at
infinite dilution are different for water and ethanol, the two suffix Margules equation cannot be
used. Instead, employ the three suffix Margules equation:
g E xa xb A Bxa xb
From Table 7.2, we have
RT ln g a A 3B xb2 4Bxb3
RT ln g b A 3B xa2 4Bxa3
Substituting infinite dilution data, we obtain a system of equations that can be solved for A and
B:
2
3
J
RT ln g a 8.314
343.15 K ln 2.62 A 3B 1 4 B 1
mol K
2
3
J
RT ln g b 8.314
343.15 K ln 7.24 A 3B 1 4 B 1
mol K
-1
A 4200 J mol and B 1450 J mol -1
To obtain the fugacity of liquid water, we use the following equation
fal xag a f ao
Since the activity coefficient for water as xa 0 is greater than one, the activity coefficient is
based on the Lewis-Randall reference state. Therefore, f ao is the fugacity of pure water at 70
C. The following relationship also holds since the saturation pressure at 70 C is so low that the
water vapor behaves as an ideal gas and the Poynting correction can be neglected.
f ao Pasat
From the steam tables,
(70 C)
Using the values of A and B calculated above, we can calculate the coefficient for a mixture of
40 mole % water and 60 mole % ethanol at 70 C:
g a exp
7.62
To find expressions for ln g a and ln g b , we can use Equations 7.55 and 7.56:
GaE RT ln g a
GbE RT ln g b
The expression for the excess molar Gibbs energy can be rewritten as
gE
ABx a xb
Cxa xb xa xb 2
Ax a Bxb
By multiplying the above expression by the total number of moles and rewriting mole fractions
in terms of moles, we obtain
GE
ABn a nb
Cna nb na nb 2 na nb 3
Ana Bnb
Differentiation provides
2
GaE
Bxb
Cxb2 2 xb 16 xb 5
A
Ax
Bx
b
a
GbE
Ax a
Cxa2 2 xa 16 xa 5
B
Ax a Bxb
Bxb
2
A
Cxb 2 xb 16 xb 5
Ax a Bxb
1
ln g b
RT
Ax a
2
B
Cxa 2 xa 16 xa 5
Ax a Bxb
7.63
Applying Equation E6.4E to the property k = (gE/RT) gives:
gE
gE
E
m
g
RT dT RT dP Gi dx
i
T
P
ni 1 RT
RT
P ,ni
T ,ni
Substituting the following equations into the above expression
gE
hmix
RT
T RT 2
P,n i
E
g
v mix
RT
P RT
T ,n i
(Equation 7.75)
(Equation 7.74)
we obtain
m
gE hmix
v mix
d
dT
dP
ln g idxi
2
RT
RT RT
n i 1
For isobaric binary data, the pressure is constant, and the expression can be reduced to
g E hmix
hmix
d
dT ln g 1dx1 ln g 2 dx2
dT ln g 1dx1 ln g 2 d 1 x1
2
RT
RT
RT 2
g
hmix
dT ln 1 dx1
RT 2
g2
hmix dT ln g 1 dx1
g 2
RT 2
T x1 1
hmix
T x1 0 RT
x1 1
dT
x1 1
g
ln 1 dx1
g
x 0 2
T x 1
1
g1
hmix
ln
dx
g 2 1 RT 2 dT
x1 0
T x1 0
dT
1
d
T
T2
Hence,
x1 1
T x1 1
1
x1 1
T
hmix
g
hmix
ln 1 dx1
dT
2
g2
R
RT
1
x1 0
T x1 0
x1 0
1
d
T
7.64
(a)
Since the activity coefficients are approximately equal, we can assume the two-suffix Margules
equation sufficiently models excess Gibbs energy. Calculate the A parameter for both activity
coefficients, and use the average value for subsequent calculations:
J
J
A RT ln g a 8.314
303.15 K ln 1.27 602.4
mol K
mol
J
J
A RT ln g b 8.314
303.15 K ln 1.34 737.6
mol K
mol
J
A 670
mol
Equation 7.32:
fal xag a f al
Calculate the fugacity of pure hexane (a) at 30 C and 1 bar assuming the saturated hexane vapor
acts ideally since its saturation pressure is low at 30 C:
f al Pasat
f al 0.25 bar
6700.82
1.19
8.314303.15
g a exp
Therefore,
6700.52
1.07
8.314303.15
g a exp
Therefore,
6700.12
1.00
8.314303.15
g a exp
Therefore,
7.65
We are given the density and the Henrys law constant for 1-propanol in water:
1l 0.80
g
, and H a 0.61 bar
cm 3
(a)
Noting that the system pressure is high (100 bar), we begin with Equation 7.85 from the text:
v1l
P P1sat
sat sat RT
1
1
f1l P e
The specific molar volume of 1-propanol is found from the given density:
v1l
MW1
1l
60.1 g/mol
cm 3
75
.
1
0.80 g/cm 3
mol
The saturation pressure is found using the Antoine equation, and the appropriate constants given
in Appendix A:
B
3166.38
10.9237
T C
298 80.15
sat
P1 0.027 bar
ln P1sat A
Since the saturation pressure is very low, we can assume that 1-propanol acts ideally. Thus,
1sat 1 (ideal)
And we can now find the fugacity of 1-propanol in the liquid:
3
6 m
75.1
10
5
5 J
mol
0.027 bar exp
100
10
0.027
10
m3
8.314 J 298K
mol K
v1l
P P1sat
sat RT
f1l P e
Now, we can calculate the activity coefficient from the pure-species fugacity and the given
Henrys law constant.
g 1
H1 0.61 bar
16.70
f1l 0.037 bar
Now we can use a model for the free Gibbs energy to determine the solution fugacity. Since the
two species are similar in size and polarity, we can expect the two-suffix Margules (2SM) model
to fit it adequately. From Table 7.1, we know that:
RT ln g 1 Ax 22
Since at infinite dilution, x2 = 1, we can easily determine the 2SM parameter, A :
A
ln g 1 2.81
RT
Now, use the same model to determine the activity coefficient in the given mixture (i.e. x2 = 0.6):
A 2
2
x2 2.810.6 1.01
RT
g 1 2.75
ln g 1
And finally, we can find the solution fugacity of 1-isopropanol in the given mixture:
7.66
You have the parameters for this system from the van Laar (vL) equation:
AvL 3000
J
,
mol
BvL 5040
and
J
mol
(a)
Find the 3SM parameters A and B :
From Table 7.2, the van Laar parameters are related to the activity coefficients by:
2
Bx b
RT ln g a A
, and
Ax a Bx b
Ax a
RT ln g b B
Ax a Bx b
From these values, we can calculate the infinite-dilution activity coefficients for the two species,
and calculate the 3SM parameters from these. Note that for species a at infinite dilution, species
b is pure (i.e. xa = 0, and xb = 1). The bracketed terms in the expressions above then equal one.
RT ln g a A 3000
J
, and
mol
RT ln g a B 5040
J
mol
J
, and
mol
RT ln g b A B 5040
J
.
mol
J
, and
mol
B 1020
J
mol
(b)
Calculate the fugacity of liquid benzene (a) in a 30 mole% mixture in 1-propanol at 81kPa.
Start with Equation 7.77 from the text:
fal xag a f a xag a Pasat
Calculate the activity coefficient using either the vL or 3SM model. We will use the 3SM model,
the results are slightly different if you choose the vL model (can you explain why?)
From Table 7.2, we find the expression for the activity coefficient of a in the 3SM model:
J
mol
g a 2.04
Now, we need to find the saturation pressure of benzene. Turning to the Antoine equation and
the tables in Appendix A, we calculate:
ln Pasat A
B
0.147
T C
(c)
Determine the mole fraction of vapor in the mixture, assuming the system is in equilibrium.
Since the system is in equilibrium, we know that
y a av P xa g a f fav fal 0.53 bar
Solving for ya, and substituting the system pressure (0.81 bar) :
ya
0.53 bar
0.65
0.81 bar
7.67
We are asked to determine the fugacity of a, and the Henrys Law constant Ha in a mixture of a
and b at 30 kPa and 20C. The saturation pressure of a and an equation for the excess Gibbs
energy of the mixture is given:
Pasat 50 kPa , and
gE
0.25 xa 0.5 xb xa xb
RT
(a)
Looking in Table 7.1, we find that the given equation for gE is a variant of the Margules 3-suffix
equation. If we rewrite the given equation and compare it to the Margules equation, the values
for the two coefficients are given by:
g E xa xb Aba xa Aab xb 0.25RTxa 0.5RTxb xa xb
Substitute the values for Aab and Aba, and the mole fraction of each species (xa = 0.2, xb = 0.8):
RT ln g a xb2 0.5RT 20.25 0.5RTxa
g a 1.29
Now use the relation for fugacity of a condensed phase to find the fugacity fal :
fal xa g a Pasat 12.9 kPa
(b)
Now calculate the Henrys law constant. First, find the activity of a at infinite dilution:
ln g a xb2 0.5 0.5 xa
xa 0
0.5
g a 1.68
Now multiply the infinite-dilution activity coefficient by the saturation pressure:
H a g a Pasat 84 kPa
7.68
From the expressions in Table 7.4, we have:
Acetone Water
xi ri
*i
x1r1 x2 r2
xi qi
i
x1q1 x2 q2
i'
li
xi qi'
x1q1' x2 q2'
0.545
0.455
0.417
0.583
0.501
0.499
-0.42
-2.32
1* z
r
q1 ln 1* *2 l1 l2 1 0.236
x1 2
1
r2
and
ln g 2, combinatorial
*2 z
r
ln
q2 ln 2* 1* l2 l1 2 0.116
x2 2
2
r1
For the residual part of the activity coefficients, we calculate the energy parameters
a
a
12 exp 12 0.204
21 exp 21 1.35
and
T
T
With these values, we get:
ln g 1,residual q1' ln 1' 2' 21 2' q1' ' 21' ' 12 ' 0.568
1 2 21 1 12 2
and
ln g 2, residual q2' ln 1'12 2' 1'q2' ' 12 ' ' 21' 0.102
112 2 1 2 21
Summing the combinatorial and residual parts and taking the exponential gives
g 2exp 1.32 .
7.69
From the expressions in Table 7.4, we have:
Ethanol Benzene
xi ri
*i
x1r1 x2 r2
xi qi
i
x1q1 x2 q2
i'
li
xi qi'
x1q1' x2 q2'
0.319
0.681
0.368
0.632
0.214
0.786
-0.41
1.76
1* z
r
q1 ln 1* *2 l1 l2 1 0.063
x1 2
1
r2
and
ln g 2,combinatorial
*2 z
r
ln
q2 ln 2* 1* l2 l1 2 0.022
x2 2
2
r1
For the residual part of the activity coefficients, we calculate the energy parameters
a
a
12 exp 12 1.266
21 exp 21 0.467
and
T
T
With these values, we get:
ln g 1,residual q1' ln 1' 2' 21 2' q1' ' 21' ' 12 ' 0.215
1 2 21 1 12 2
and
ln g 2,residual q2' ln 1'12 2' 1' q2' ' 12 ' ' 21' 0.070
1 12 2 1 2 21
Summing the combinatorial and residual parts and taking the exponential gives
y1 P
1.66
x1P1sat
7.70
From the expressions in Table 7.4, we have:
Acetone Chloroform
xi ri
*i
x1r1 x2 r2
xi qi
i
x1q1 x2 q2
i'
li
xi qi'
x1q1' x2 q2'
0.192
0.808
0.200
0.800
0.200
0.800
-0.42
0.1
1* z
r
q1 ln 1* *2 l1 l2 1 0.008
x1 2
1
r2
and
ln g 2,combinatorial
*2 z
r
ln
q2 ln 2* 1* l2 l1 2 0.001
x2 2
2
r1
For the residual part of the activity coefficients, we calculate the energy parameters
a
a
12 exp 12 1.745
21 exp 21 0.737
and
T
T
With these values, we get:
ln g 1,residual q1' ln 1' 2' 21 2' q1' ' 21' ' 12 ' 0.544
1 2 21 1 12 2
and
ln g 2,residual q2' ln 1' 12 2' 1' q2' ' 12 ' ' 21' 0.051
112 2 1 2 21
Summing the combinatorial and residual parts and taking the exponential gives
y1 P
0.536
x1P1sat
7.71
The fugacity of ethanol in solution is calculated with the following equation:
x x x x x x
1 11
2 12
3 13
1 21
2 22
3 23
ln g 1 1 ln x111 x2 12 x313
x3 31
x x x
3 33
1 31 2 32
Now calculate the saturation pressure of ethanol at 60 C using Antoines Equation data in
Appendix A.1.
3803.98
bar 0.468 bar
P1sat exp 12.2917
333.15 41.68
7.72
First, we need to find the Wilson parameters at 8 C. We can use the following equations:
v
ab b exp ab
va
RT
v
ba a exp ba
vb
RT
Find the energetic parameters (lowercase lambdas) at 60 C, and use them to calculate the
uppercase lambdas at 8 C. The molar volumes for ethanol and 1-propanol can be calculated
using the Rackett EOS. The saturated steam tables provide an estimate for waters molar
volume. Using the above equations with the 60 C data, we obtain:
Pairing
12
21
13
31
23
32
(J/mol)
1.13 x 102
6.83 x 102
1.39 x 103
3.52 x 103
4.73 x 103
5.04 x 103
Now, we can calculate the Wilson parameters at 8 C since the energetic parameters are less
sensitive to changes in temperature. We obtain
Pairing
12
21
13
31
23
32
1.214
0.586
0.204
0.602
0.038
0.400
We will find the fugacity of the ethanol with the following equation
x111
x2 21
x x x x x x
1 11
2 12
3 13
1 21
2 22
3 23
ln g 1 1 ln x111 x2 12 x313
x3 31
x x x
3 33
1 31 2 32
g 1 1.32
We can find the saturation pressure from Antoines Equation data in Appendix A.1.
3803.98
bar 0.028 bar
P1sat exp 12.2917
281.15 41.68
Therefore,
7.73
Equation 7.81 provides
H i hi
ln g i
RT 2
T P , x
Equation 6.26 states that
H
mix
H i hi
Therefore,
H mix
ln g i
RT 2
T P , x
H mix
2
3
3802 n2 n1 1200 n2 n1 1554 n2 n1
n1n2
447.8
2
3
n1 n2
n1 n2
n1 n2
n1 n2
Thus, we find
H x
mix
2
2
H
mix
J
1062.5
1
mol
1
g 1062.5 1
ln 1
7.74
Since we are assuming that the tin and cadmium form a regular solution,
g E hmix
Find the activity coefficient by using the following equation:
E
GCd
RT ln g Cd
E
To find GCd
, start with
G E H mix
13000nCd nSn
nCd nSn
Differentiating provides
E
2
GCd
13000 X Sn
Therefore,
2
130000.6
g Cd exp
J
8.314
773
.
15
K
mol K
g Cd 2.07
7.75
Select the isothermal ethanol/water experimental data set in the Models for gE Parameter
Fitting menu. The temperature, 74.79 C, is automatically selected. We have the capability of
determining the activity coefficients with three different objective functions, but only the
coefficients found using the pressure objective function, OFP, are shown below.
Part (a)
Two
Suffix
Margules
A
3652.3
Part (b)
Part (c)
Part (d)
Part (e)
Three Suffix
Margules
van Laar
Wilson
NRTL
A
3521.0
B
-1102.3
A
B
Gab
Gba
ab
ba
ab
ba
5001.0 2692.8 0.167 0.869 0.979 0.523 0.055 1.683
We can look at the value of each objective function to determine which model fits the data best.
We want the objective function with the smallest value. The values are tabulated below for each
model.
Pressure Objective Function Values (bar2)
Two
Three
van
Suffix
Suffix
Wilson
NRTL
Laar
Margules Margules
1.34E-02
2.77E-04
5.45E05
1.40E04
5.39E05
Part (b)
Three Suffix
Margules
A
B
4365.8
208.7
Part (c)
Part (d)
Part (e)
van Laar
Wilson
NRTL
A
B
ab
ba
Gab
Gba
ab
ba
4150.2 4600.6 0.366 0.226 1.963 2.280 0.573 0.700
We can look at the value of each objective function to determine which model fits the data best.
We want the objective function with the smallest value. The values are tabulated below for each
model.
Pressure Objective Function Values (bar2)
Two
Suffix
Margules
Three
Suffix
Margules
1.69E-03
1.11E-03
van
Laar
Wilson
NRTL
1.08E03
1.73E04
1.00E04
7.77
Select the isothermal chloroform/heptane experimental data set in the Models for gE
Parameter Fitting menu. The temperature, 25 C, is automatically selected. We have the
capability of determining the activity coefficients with three different objective functions, but
only the coefficients found using the pressure objective function, OFP, are shown below.
Part (a)
2 Suffix
Margules
A
1329.8
Part (b)
Three Suffix
Margules
A
B
1235.5
261.6
Part (c)
Part (d)
Part (e)
van Laar
Wilson
NRTL
A
B
ab
ba
Gab
Gba
ab
ba
1028.7 1548.1 1.109 0.478 0.559 0.856 0.519 0.138
We can look at the value of each objective function to determine which model fits the data best.
We want the objective function with the smallest value. The values are tabulated below for each
model.
Pressure Objective Function Values (bar2)
Two
Three
van
Suffix
Suffix
Wilson
NRTL
Laar
Margules Margules
2.66E1.64E9.12E4.39E-05 1.33E-06
07
07
08
7.78
We are given a plot of oxygen content vs. partial pressure of oxygen for an emulsion of 24%
(w/v) perflubron (C8F17Br) in water. Estimate the oxygen capacity of the emulsion, which might
be used as a blood substitute, in units of moles of oxygen per liter of emulsion. Compare this
result with the solubility of oxygen in pure water at the same conditions (25C, atmospheric
pressure). Use these results to determine the value of the Henrys Law constant for oxygen in
pure perflubron (not the emulsion).
a) First, estimate [O2] in the emulsion, as
moles O2/L solution.
We are given a graph showing the
concentration of oxygen in the emulsion at
25C. We are given ambient pressure is 1.0
atm.
At this partial pressure, the oxygen concentration of the emulsion is 1.4 mL/100 cm3. Since the
air acts as an ideal gas, the number of moles of oxygen in the emulsion is:
-6 m3
5 J
1.013 10 3 1.4 mL 10
PO2V
m
mL
nO2
8.314
298K
mol
If we assume that the gas dissolves completely (i.e. there is no volume change when the 1.4 mL
of oxygen is absorbed into the 100 cm3 of emlusion), then
O2
L solution
L solution
b) Compare the result from part A with the oxygen capacity of pure water:
From Table 8.1, we can get the Henrys Law constant H O2 44, 253.9 bar for oxygen in water
at 25C. Since pressure is low and the gas solution is dilute, we can assume ideal behavior, so
Equation 8.30 holds:
xO2
Since xO2
yO2 P
H O2
0.21 bar
4.75 106
44, 253.9 bar
nO2
nO2 nH 2O
nO2
nH 2O
approximately equal to the volume of pure water, we can define the molality of oxygen to be:
O2
nO2
Vsolution
nO2
VH 2O
O2
VH 2O
nH 2O
xO2
vH 2 O
The molar volume of water can be found from the density at 25C and molecular weight:
vH 2O
M H 2O
H O
18 g/mole
L
0.018
1000 g/L
mole
O2
Since VO2
xO2
vH 2 O
mole O2
4.75 106
2.64 104
liter H 2O
liter H 2 O
0.018
mole H 2O
O2 2.64 104
mole O2
.
liter
Thus, the perflubron emulsion can carry approximately 2.2 times as much oxygen as pure
water.
c) Find the value of the Henrys Law constant for oxygen in pure perflubron (PFB).
Previously, we found the mole fraction of oxygen in the emulsion
and in water at the given partial pressure of oxygen. Using the
definition of the Henrys Law constant, we can write (for each of
the two phases in the emulsion):
Xa, yaP
yaP
Ha
xa
Ha
ya P
xa
To find xa, we will first find the number of moles of PFB and water in 100 cm3 of the emulsion.
The emulsion contains 24g of PFB per 100cm3 of solution. This is equivalent to:
1 mole PFB
24g PFB
0.0481 mole PFB , and
498.96 g PFB
1 cm3 PFB
3
24g PFB
12.435 cm PFB .
1.93 g PFB
Since 12.435 cm3 of the total 100 cm3 is taken up by the PFB, the remaining 87.565 cm3 must be
water (since this is an emulsion, we can assume that Vmix 0 ). Therefore, we have
1.00 g H 2O 1 mole H 2O
87.565 cm3 H 2O
4.865 moles H 2O .
cm3
18 g H 2O
Oxygen must be dissolved in either the water or PFB. A simple mole balance on the total oxygen
taken up by the emulsion nO2 ,emulsion allows us to determine the amount of O2 in the PFB phase:
nO2 , PFB nO2 ,emulsion nO2 , H2O
We determined the molar uptake of the emulsion and pure water in Parts (a) and (b), above.
However, recall that we calculated nO2 , H 2O as the moles of O2 taken up by 100 cm3 of water.
Since we have less than 100 cm3 of water, we must scale nO2 , H 2O appropriately:
86.565 cm3
5
nO2 , PFB 5.726 105 moles
2.64 10 moles
3
100
cm
-5
nO2 , PFB 2.64 10 moles O2
Now find the mole fraction of O2 dissolved in the PFB in the 100 cm3 of PFB/H2O emulsion:
xO2 , PFB
nO2
nO2 nPFB
nO2
nPFB
Applying the definition of the Henrys Law constant above, we can compute H O2 , PFB :
H O2 , PFB
H O2 , PFB 300 bar
yO2 P
xO2 , PFB
0.211.01325 bar
297.5 bar
7.153 104