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Milo Koretsky
Wyatt Tenhaeff
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:
y1P x1P1sat
y1 P
x1eq 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 Henry’s 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 Henry’s Law constant is
greater for this system.
(b)
The Henry’s 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.
1.2
0.8
0.6
ga
0.4
0.2
0
0 0.2 0.4 0.6 0.8 1
xa
7.7
(a)
First, we must realize that
h E hmix
Since
gE
hmix
T 0
T T2
P, ni
E
we see that g is independent of temperature when the pressure and number of moles is held
T
constant. Therefore,
gE Ax x
a b
T
P, ni T P, ni
A
T P, ni
(b)
Equation 7.24 provides
g E
v E vmix
P
T , n i
Substituting the two suffix Margules equation in for the excess Gibbs energy, we find
Ax a xb
0
P 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 Henry’s 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
fˆa xa f a
150
[bar] 100
fˆa xa a
50
0
0 0.5 xa 1
(b) Both lnga and lngb go to 1 and xi goes to 0. Therefore the Henry’s 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 1
xa
7.10
7.11
fi
200 oC and 1.56 MPa (Pisat = 1.55 MPa) ( isat 1 ) so 1
Pi sat
fi
70 oC and 1 bar (Pisat = 31.2 kPa) ideal 1
Pi sat
fi
70 oC and 1.56 MPa (Pisat = 31.2 kPa) Poynting correction 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
fv
g i g i¼ RT ln i
Plow
kJ kJ kJ
Plow 10 kPa : gˆ iº 3489.0 773.15K 9.8977 4163.4
kg kg K kg
kJ kJ kJ
P 2 MPa : gˆ i 3467.6 773.15K 7.4316 2278.1
kg kg K kg
Therefore,
kJ kJ
2278.1 kg 4163.4 kg 1000 J/kJ 0.0180148 kg/mol
fi v 10 kPa exp
J
8.314 mol K 773.15 K
f iv 1970 kPa 1.97 MPa
i 0.985
(b)
For 500 ºC and 50 MPa, we obtain the following from the steam tables
kJ kJ kJ
gˆ 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:
kJ kJ
1279.0 kg 4163.4 kg 1000 J/kJ 0.0180148 kg/mol
fi 10 kPa exp
v
J
8.314 mol K 773.15 K
fi 32.4 MPa
v
and
i 0.648
7.15
(a)
Equation 7.8 states
f iv P
RT ln v dP
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
Plow 2 2
RT iv b Tvi
Plow
To determine the integral of the first term above, we use decomposition by partial fractions:
v 1 b
v b v b v b2
2
so
vi
vi
vi b
2 dv lnv i b
RT v i b vi b RT
Plow Plow
and
v
f iv b 2a
i
ln ln(vi b)
Plow vi b 2
RT vi RT
Plow
f iv 1
vi b 2a 1 Plow
ln
1
ln b
Plow vi b RT RT 2
b
RT vi RT
b
Plow
Plow
RT
Since b , the expression simplifies to
Plow
f iv 1 P P v b 2a 1 Plow
ln b
low ln low i
Plow vi b RT RT RT 2 vi RT
b v b 2a
lnf iv ln i
vi b 2
RT RT v i
Therefore,
RT b 2a
f iv exp
vi b vi b RT 2 vi
To obtain an expression for iv , we divide our expression for fugacity by total pressure:
f iv RT b 2a
iv exp
P P v i b v i b RT 2v i
(b)
From Problem 4.29, we got
3RTc
v c 3b
8Pc
and
9
a v c RTc2
8
f iv 8Tr 1 9
iv exp 2
P Pr 3v i,r 1 3v i,r 1 4Tr v i,r
7.16
Equation 7.8:
P f iv
vi dP RT ln Plow
Plow
RT a
P 1/ 2
v b T v v b
so
RT a a
dP
2 dv
v b T v v b T1/ 2v v b
2 1/ 2 2
Therefore,
v f iv
vRT a a
T1/ 2v v b T1/ 2 v b2
dv RT ln
v b
2
RT Plow
Plow
To determine the integral of the first two terms term above, we use decomposition by partial
fractions. For the first term,
v 1 b
v b v b v b2
2
so
v
v
v b
dv lnv b
v b v b
2
RT RT
Plow Plow
so
v
v
1 1 v
v v b
dv ln
b v b RT
RT
Plow Plow
Thus, we get
v
fv b a v a
RT ln i RT lnv b RT 1/ 2 ln 1/ 2
Plow v b T b v b T v b RT
Plow
RT
If we note that b and let Plow 0 , we obtain
Plow
RT b a v a
RT ln f iv RT ln RT 1 / 2 ln 1/ 2
vb vb T b vb T v b
Therefore,
RT b a v a
f iv exp ln
vb v b RT 3 / 2 b v b RT 3 / 2 v b
and
f iv RT b a v a
iv exp ln
P P v b v b RT 3 / 2b v b RT 3 / 2 v b
7.17
Equation 7.8:
P f iv
vi dP RT ln Plow
Plow
RT a (T)
P 2
v b v 2vb b2
Thus,
RT 2a (T)v b
dP dv
v b2 v 2 2vb b 2 2
Therefore,
v
RT 2a (T)v b f iv
v
v b2 v 2 2vb b 2 2
dv RT ln
Plow
RT
Plow
Simplifying, we get
fi v v
v 2a (T )
v
v v b
ln dv dv (1)
RT v b v
2 2 2
Plow RT RT
2
2vb b
Plow Plow
To determine each of the integrals in Equation 1, we use decomposition by partial fractions. For
the first integral:
v 1 b
v b v b v b2
2
so
v
v
v b
dv lnv b (2)
v b v b
2
RT RT
Plow Plow
For the second integral, decomposition leads to:
v v b 1 v b
b
v
2 2 v 2vb b v 2 2vb b2
2 2 2
2
2vb b
so
v
v v b v
1 v
v b dv
dv dv b (3)
v 2vb b 2 v 2vb b RT v 2vb b
2 2 2 2 2 2 2
RT RT
Plow Plow Plow
We again use partial fractions. For the first term in Equation (3):
1 1 1 1
v 2 2vb b 2
2 2b v 1 2 b v 1 2 b
so
v
1
1 v 1 2 b v
v 2 2vb b 2 dv 2 2b ln v 1 2 b RT (4)
RT
Plow
Plow
v b
v b
2b
(5)
v 2 2vb b
2 2
v 2 2vb b 2 2
v 2 2vb b2
2
Equation (5) can be substituted into Equation (3) to give two terms. The first term gives:
v
v
v b b
b dv (6)
v 2 2vb b2 2v 2vb b RT
2 2 2
RT
Plow Plow
2
1
2b 1 1
2
v 2vb b 2 2
4b v 1 2 b v 1 2 b
or
2
2
2b 1 1 1 1 1
2
v 1 2 b v 1 2 b v 1 2 b
2
v 2vb b 2 2
4b v 1 2 b
(7)
v 2 v
1 1 1
4 RT
v 1 2 b dv 4 v 1 2 b RT
(8)
Plow
Plow
and
v 2 v
1 1 1
4 RT
dv
v 1 2 b
4 v 1 2 b RT (9)
Plow
Plow
1
v
1 1 1 v 1 2 b v
2 RT
v 1 2 b v 1 2 b 4 2b ln v 1 2 b RT
(10)
Plow
Plow
Substituting Equations (4). (6). (8), (9) and (10) into Equation (3) gives:
v
vv b
1 v 1 2 b b v v
2 dv
ln
RT v 2vb b 2
2 2 2b v 1 2 b RT 2 v 2vb b 2 RT
2
Plow Plow
Plow (11)
1 1
v
1 v 1 2 b
v
v
ln
4 v 1 2 b RT 4 v 1 2 b RT 4 2b v 1 2 b RT
Plow Plow Plow
v
v 1 2 b
v
v v b 1 ln v
dv (12)
RT
Plow
v 2
2vb b
2 2 4 2b 2
v 1 2 b 2v 2
2vb b 2
RT
Plow
Substituting Equations (12) and (2) into Equation (1) gives
v
f iv v v 1 2 b
b 2a (T) 1 v
ln RT lnv b RT ln
P
low v b RT
Plow
RT
4 2b
v 1 2 b 2v 2
2vb b 2
RT
Plow
RT
If we note that b and let Plow 0 , we obtain
Plow
ln f i ln
v
RT b a (T) 1
ln
v 1 2 b
v
v b v b
RT 2 2b v 1 2 b v 2 2vb b 2
and
RT b a (T) 1
ln ln
v
ln
v 1 2 b
2
v
i
P v b v b RT
2 2b
v 1 2 b v
2vb b 2
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 ºC and 10 kPa. Using enthalpy and entropy values
from the steam tables, interpolation gives:
kJ kJ
gˆ io 2934.5 gˆ i 890.9
kg kg
Therefore,
J J
g io 52864 g i 16049
mol mol
16049 J 52864 J
mol mol
f iv 10 kPa exp 9382 kPa
647 K
J
8.314
mol K
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
vi b RT RTvi
J m3
a 0.554
mol
5
m3
b 3.05 10
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
f iv 9.77 MPa
(c)
The reduced temperature and pressure can be calculated from data in Table A.1.2:
Tr 1 Pr 0.52 0.344
log 0 0.08
log 1 0.0152
Calculate :
log log 0 log 1
0.82
Therefore,
The agreement in values is good for the three methods. However, Part (a) likely provides the
most accurate value since it is based directly on measured data for water.
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:
log iv log i0 log i1 0.0176 0.0080.0614 0.0181
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
vi b RT RTvi
The “a” and “b” parameters for CO are (see Chapter 4 for equations)
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
f iv 156.5bar
f iv
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’:
v
RT
1 B' P
P
P fv
ln B' P Plow ln i
Plow Plow
f iv P exp B' P
Therefore,
f iv 27.1 bar
and
27.1 bar
iv 0.903
30 bar
7.21
(a)
Equation 7.8:
P
f
RT ln i vi dP
Plow Plow
f f P
ln i ln i ln low CP
P Plow P
P
P 30
RT CP ln low RT 0.065 P ln Plow ln P vi dP
P T P
low
1 30
vi RT 0.065
P T
(b)
Substitute numerical values:
m 3 bar 1
vi 8.314 10 5 353.15 K 0.065
30
mol K 353.15 K 30 bar
m3
vi 3.93 10 4
mol
7.22
Equation 7.8:
f iv P
RT ln v dP
Plow i
Plow
1 T 0.422Tc1.6
vi RT c 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
ln i ln
Plow
0.083
1.6
P Plow
Plow Pc T T
or
f v T 0.422Tc1.6
ln i c 0.083 P Plow
P PcT T1.6
PcT T Tr Tr
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
fv P P
RT kP 2 c
RT ln i vi dP b dP
Plow Plow Plow
P T
P
fv kP3 cP
RT ln i RT ln P bP
Plow 3T T Plow
Expand the logarithm terms, so that we can cancel the ln Plow terms.
P
kP3 cP
RT ln f i
v
RT ln Plow RT ln P RT ln Plow bP
3T T 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
RT ln RT ln i
v
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 ,
kP3 cP
RT ln iv bP
3T T
1 kP3 cP P
iv exp 3 2
b
RT RT
7.24
fv P
gi gio RT ln i vi dP
Plow Plow
So
And
RT ln i
Plow
RT
v
v2
v3 dv
Plow
Integrating:
fi v vi 13.40 106 13.40 106 7.245 108 7.245 108
RT ln RT ln RT
RT 2 2
low
P Plow
vi P vi RT
Plow
low
Canceling out ln(Plow) subtracting ln(P), and letting Plow ->0, we get
Substituting in numbers
Pvi
z 1 B' P C ' P 2
RT
Solving we get,
We next solve for fugacity and fugacity coefficient using this equation of state:
fi v P
RT ln vi dP
Plow Plow
f v P 1 C'
B' P Plow P 2 Plow
P
ln i B' C ' P dP ln 2
Canceling out ln(Plow) subtracting ln(P), and letting Plow ->0, we get
fv C'
ln i ln i B' P P 2
P 2
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:
T 220 P 69
Tr 1.15 Pr 1.5
Tc 190.6 Pc 46
0.008
Using reduced temperature and pressure, the fugacity coefficient can be found from Tables
C.7 and C.8:
log iv log i 0 log i1 0.16 0.008 0.034 0.16
iv 0.69
Calculate fugacity:
P [bar] v [m3/mol]
1.0 2.45 x10-2
5.1 4.78 x10-3
10.1 2.32 x10-3
15.2 1.50 x10-3
20.2 1.08 x10-3
25.3 8.34 x10-4
30.3 6.66 x10-4
35.4 5.44 x10-4
40.4 4.52 x10-4
45.5 3.78 x10-4
50.5 3.17 x10-4
Equation 7.9:
P
zi 1
ln iv P
dP
Pideal
-1
-2
(z-1)/P x 1000 [bar]
-3
-4
-5
-6
-7
-8
0.0 10.0 20.0 30.0 40.0 50.0 60.0
P (bar)
ln iv 0.3
Therefore,
iv 0.74 and f iv iv P 37.5 bar
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
J
8.314
mol K
373.15 K 0.001 bar 500 bar 1
-1
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
J
g mix T smix RT x1 ln x1 x2 ln x2 1, 730
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:
T 318.9 P 3.79
Tr 0.75 Pr 0.1
Tc 425.2 Pc 37.9
0.193
Using reduced temperature and pressure, the fugacity coefficient can be found from Tables
C.7 and C.8:
log iv log i 0 log i1 0.035 0.193 0.030 .041
0.91
i
v
Calculate fugacity:
fˆ1v y11P 0.41 bar
7.31
(a)
f1v 1P
The reduced temperature and pressure can be found using data from Appendix A:
190.6 32.2
Tr 1.0 Pr 0.70
190.6 46.00
0.008
Using reduced temperature and pressure, the fugacity coefficient can be found from Tables C.7
and C.8:
log iv log i 0 log i1 0.113 0.008 0.022 0.113
0.77
i
v
Calculate fugacity:
fi v 24.8 bar
(b)
fv P
RT ln 1 v1dP
Plow Plow
To acquire an expression for v1, set the mole fraction of species 1 equal to unity.
1
v1 RT P
A B
P RT
fv P A B P 2 Plow
2
ln 1 ln
Plow Plow RT 2 2
lnf1v lnP
A B P 2
RT 2
Therefore,
f v A B P2
ln1v ln 1
P RT 2
5 50
A B P 2 2
5
1v exp exp 9.0 10 3.0 10
RT 2 2
1v 0.93
Species in a mixture:
fˆ v P
RT ln 1 V1dP
yP
1 low Plow
Therefore,
PA B
RT
V1
P
Substituting this result into the above integral and integrating, we obtain the following after
simplifiction
ˆ
ln 1 v P2 A
B
2 RT RT
ˆ P2 A B
1 exp
v
2 RT RT
50 atm 2 5 1 5 1
ˆ
1 exp atm2
v
9.0 10 atm2 3.0 10
2
ˆ1v 0.93
(b)
When the vapor and liquid are in equilibrium,
fˆ1v fˆ1l
Hence,
fˆ1v 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.
fˆ1v
ˆ1v 0.93
y1 P
15 atm
y1 0.322
0.9350 atm
7.33
(a)
The Lewis fugacity rule:
ˆ1v 1v
v b P 2a
ln iv
b
ln i
vi b RT RTvi
m3
v1 1.15 10 3
mol
1v 0.89
(b)
The truncated virial form of the van der Waals equation for the mixture is
RT 1
V nT nT bmix nT amix
P RT
fˆ v P
RT ln 1 V1dP
yP
1 low Plow
Find V1 :
V
V1
RT
b1
1
2 y1a1 2 y2 a2 2 y3a13 amix
dn1 T , P, n2 , n3 P RT
fˆ v P b1 1
2
ln 1 ln P Plow 2 y1a1 2 y2 a2 2 y3a13 amix P Plow
yP
1 low Plow RT RT
By subtracting ln Plow and ln P from both sides and then letting Plow 0 , we obtain
fˆ v b
ln ˆ1v ln 1 1
y P
1
2 y1a1 2 y2 a2 2 y3a13 amix P
1 RT RT
2
ln ˆ1v 0.10
ˆ1v 0.906
Calculate fugacity:
fˆ v V
P
RT ln a dV
yP nRT na T ,V , n
a low i a
Plow
n n n na2 Baa nb2 Bbb nc2 Bcc 2na nb Bab 2na nc Bac 2nb nc Bbc
P RT a b c
V V 2
Therefore,
fˆ 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
fˆ 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
a
y P 2 y B 2 yb Bab 2 yc Bac
fˆav a exp a aa
z v
(b)
For this system
y a 0.2
yb 0.3
yc 0.5
4
m3
Bmix 2.392 10
mol
Therefore,
Pv B
z 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.)
ˆav 1.04
(c)
The EOS reduces to the following expression for pure methane:
Pv a B
1 aa
RT va
Develop an expression for the fugacity coefficient similar to the method in Example 7.2
va
f av
a
v dP RT ln
Plow
RT
Plow
Substitute the expression for dP into the above integral:
v
1 2 Baa f av
RT
RT
2
va va
a
dv RT ln
Plow
Plow
f av 2Baa RT 2Baa
ln lnv a ln
Plow v a Plow RT
Plow
Cancel the logarithmic terms containing Plow and then let Plow go to zero:
2Baa v
lnf av ln a
va RT
Therefore,
2B
RT
f av exp aa
va va
1 2B
av exp aa
za va
Since we are employing the Lewis fugacity rule
2B
1
ˆ av av exp aa
za va
y RT 2B
fˆav y a f av a exp aa
va va
To calculate the fugacity and fugacity coefficient, we will need to find the pure species molar
volume:
m3
v a 1.61103
mol
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:
(b) The Lewis Fugacity Rule (choose the method that gives you as accurate an answer as
possible).
Options:
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, let’s use the Generalized Correlations.
To use the tables in the book, we utilize the form of the generalized correlations:
P
Pr
Pc
T
Tr
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 694.2
Tr K
1
ω 0.440
ˆ1 1 0.86
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.
RT b 1 a 1 b1a b
ln(ˆ1v ) ln ln 1 b1 1.5
2 a 1 a ln 1
Pv v v b bRT (v b) bRT b v
1.5
b y1b1 y2b2
y1 0.2
y2 0.8
Note: The Redlich-Kwong parameters a and b are different from those for the van der Waals
equation and cannot be interchanged
0.42748R 2Tc2.5
a
Pc
0.08664 RTc
b
Pc
Phenol (subscript 1) Oxygen (subscript 2) Mixture (no subscript)
Tc [K] 694.2 154.6
Pc [bar] 61.3 50.46
3 0.5 2
a [J m K /mol ] 61.2 1.740 6.86
3
b [m /mol] 8.16E-05 2.207E-05 3.40E-05
Now use the equation from Table 7.1 to find the fugacity coefficient.
RT b 1 a 1 b1a b
ln(ˆ1v ) ln ln 1 b1 1.5
2 a 1 a ln 1
Pv v v b bRT (v b) bRT b v
1.5
ˆ 0.943
v
1
f1v P
RT ln v1dP
Plow Plow
RT RT Pr ,1
v1
P P 8Tr ,1
f v P RT RTc ,1
RT ln 1 dP
Plow
Plow P 8 Pc ,1
fv P RTc ,1
RT ln 1 RT ln P Plow
Plow Plow 8Pc ,1
fv
ln 1 ln 1v r ,1
P
P 8Tr ,1
219 27.72
Tr 0.6 Pr 0.6
365 46.2
ln 1v
1
8
1v 1.13
fˆ1v y11v P 7.85 bar
(b)
fˆ v P
RT ln 1 V1dP
yP
1 low Plow
RT RT n1Pr ,1 n2 Pr ,2
V n1 n2
P P 8Tr ,1 8Tr ,2
V RT RTc ,1
V1
dn1 T , P ,n2 ,n3 P 8Pc ,1
fˆ v P RT RTc ,1
RT ln 1 dP
yP P 8 P
1 low Plow c ,1
fˆ v P RTc ,1
RT ln 1 RT ln
yP P Plow
1 low low
P 8 Pc ,1
fˆ v
ln 1 ln ˆ1v r ,1
P
y P 8Tr ,1
1
219 27.72
Tr 0.6 Pr 0.6
365 46.2
ln ˆ1v
1
8
ˆ1v 1.13
fˆ1v y1ˆ1v P 7.85 bar
(c)
Values are the same so all the intermolecular interactions are the same
7.39
(a)
V
n1 n2 RT RT
n12 B11' 2n1n2 B12' n22 B22'
P n1 n2
V
RT y12 B11' 2 y1 y2 B12' y22 B22 RT 2 y1B11' 2 y2 B12'
RT
V1 '
n1 T , P ,n2 P
V
RT B ' RT 2 y1B11' 2 y2 B12'
RT
V1
n1 T , P ,n2 P
fˆ1v P P
1
V dP RT B ' 2 y1 B11' 2 y2 B12' dP
y P 1
RT ln
Plow
1 low Plow P
P
ln 2 y1 B11 2 y2 B12 B P Plow
' ' '
low
P
fˆ v
ln 1 ln ˆ1 2 y1B11 2 y2 B12 B P
v ' ' '
yP
1
(b)
y1 = 0.4
B11' - 1.9 x 10-7 [Pa-1]
B12' - 3.6 x 10-8 [Pa-1]
'
B22 - 2.0 x 10-9 [Pa-1]
So
ˆ1v 0.84
And
(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):
fˆ1v y11P
The reduced temperature and pressure can be found using data from Appendix A:
495 18
Tr 1.0 Pr 0.70
469.6 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:
log iv log i 0 log i1 0.086 0.251 0.019 0.0907
iv 0.81
Calculate fugacity:
fˆ1v 0.137 0.8118 2.00 bar
7.41
From the definition of fugacity:
fˆ v P V
P
RT ln i Vi dP dV
yP nT RT n1 T ,V , n , n
1 low Plow 2 3
Plow
P
n1 n2 RT n12 a1 n22 a2 2n1n2 a12
V n1c1 n2c2
2
V
Differentiating
fˆi v V
RT
V
2n1a1 2n2 a12
V
2c1 n12 a1 n22 a2 2n1n2 a12
RT ln dV
dV dV
y P
2 3
1 low nT RT V nT RT
V n c
1 1 n c
2 2 nT RT
V n c
1 1 n c
2 2
Plow Plow Plow
Integrating we get
fˆi v V 1 1
RT ln RT ln 2n1a1 2n2 a12
yP nT RT V n1c1 n2c2 nT RT n c n c
1 low
Plow Plow
1 1 2 2
c1 n1 a1 n2 a2 2n1n2 a12
1 1
2 2
2
V n1c1 n2 c2 nT RT n c n c
2
2 2
1 1
Plow
nT RT
Taking and n1c1 n2c2
Plow
fˆi v V 1 1
RT ln RT ln 2n1a1 2n2 a12
yP nT RT V n1c1 n2c2 nT RT
1 low
Plow Plow
c1 n1 a1 n2 a2 2n1n2 a12
1 1
2 2
2
V n1c1 n2c2 nT RT
2
Plow
Canceling out ln(Plow) subtracting ln(P), and letting Plow ->0, we get
fˆ v 1
RT ln i RT ln z 2n1a1 2n2 a12
yP
1 low V n1c1 n2 c2
c1 n12 a1 n22 a2 2n1n2 a12
1
V n1c1 n2c2
2
Simplifying:
fˆ v P V
P
RT ln i Vi dP dV
yP nT RT n1 T ,V , n , n
1 low Plow 2 3
Plow
P
n1 n2 n3 RT n12 a1 n22 a2 n32a3 2n1n2a12 2n1n3a13 2n2n3a23
V n1b1 n2b2 n3b3 V n1c1 n2c2 n3c3
2
Differentiating
P RT b1 n1 n2 n3 RT
n1 T ,V ,n2 ,n3 V n1b1 n2b2 n3b3 V n1b1 n2b2 n3b3
2
2n1a1 2n2 a12 2n3a13 2c1 n12 a1 n22 a2 n32 a3 2n1n2 a12 2n1n3a13 2n2 n3a23
V n c n c 2 n3c3 V n c n c n3c3
2 3
1 1 2 1 1 2 2
fˆ v V
RT
RT ln i dV
yP V n b n b n b
1 low nT RT 1 1 2 2 3 3
Plow
V b n n n RT
1 1 2 3
dV
nT RT V n1b1 n2b2 n3b3
2
P
low
V 2n a 2n a 2n a
1 1 2 12 3 13
nT RT V n1c1 n2 c2 n3c3
2
dV
P
low
Integrating we get
fˆi v V n b n b n b
RT ln RT ln
y P
1 1 2 2 3 3
1 low T
n RT
n1b1 n2b2 n3b3
Plow
1 1
RTb1 n1 n2 n3
V n1b1 n2b2 n3b3 nT RT n b n b n b
Plow
1 1 2 2 3 3
1 1
2n1a1 2n2 a12 2n3a13
V n1c1 n2c2 n3c3 nT RT n c n c n c
Plow
1 1 2 2 3 3
c1 n12 a1 n22 a2 n32 a3 2n1n2 a12 2n1n3a13 2n2 n3a23
1 1
2
V n1c1 n2 c2 n3c3 nT RT n c n c n c
2
3 3
1 1 2 2
Plow
nT RT n RT
Taking n1b1 n2b2 n3b3 and T n1c1 n2c2 n3c3
Plow Plow
fˆi v V n b n b n b
RT ln RT ln
y P
1 1 2 2 3 3
1 low n T RT
Plow
1 1
RTb1 n1 n2 n3
V n1b1 n2b2 n3b3 nT RT
Plow
1 1
2n1a1 2n2 a12 2n3a13
V n1c1 n2c2 n3c3 nT RT
Plow
c1 n12 a1 n22 a2 n32 a3 2n1n2 a12 2n1n3a13 2n2 n3a23
1 1
2
V n1c1 n2c2 n3c3 nT RT
2
Plow
Canceling out ln(Plow) subtracting ln(P), and letting Plow ->0, we get
Simplifying:
P v bmix
2 ya aa yb aa ab
ln ˆav ln
RT
ba
v bmix
RTv
In the above expression, v and bmix depend on mole fractions. First, calculate a a , ab , ba , and
bb :
27 RTc 2 RTc
a b
64 Pc 8Pc
J m3 5
m3
aa 0.230 ba 4.31 10
2
mol mol
J m3 m3
ab 0.454 bb 4.34 10 5
2
mol mol
Using these expressions we can find the molar volume with the van der Waals EOS.
RT a
P 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 yb öa
0 1 1.033
0.1 0.9 1.02
0.2 0.8 1.008
0.3 0.7 1.000
0.4 0.6 0.992
0.5 0.5 0.986
0.6 0.4 0.982
0.7 0.3 0.978
0.8 0.2 0.977
0.9 0.1 0.975
1 0 0.975
Plot the activity coefficient versus the mole fraction of methane for both methods on the same
graph:
1.025
a
0.975
0.950
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
ya (mole fraction)
1
RT
ln ˆav ln
b
ln 1 ba
a
1 ba a
1.5
b
2 aa a ln 1
Pv v v b bRT v b bRT b v
1.5
In the above expression, v , amix, and bmix depend on mole fractions. First, calculate a a , ab , ba ,
and bb :
R 2Tc2.5 RTc
a 0.42748 b 0.08664
Pc Pc
J m 3 K1/2 5
m3
a a 3.22 ba 2.99 10
2
mol mol
J m 3 K1/2 m3
ab 8.90 bb 3.01 10 5
2
mol mol
Using these expressions we can find the molar volume with the Redlich-Kwong EOS:
RT amix
P
v bmix T vv bmix
1 / 2
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 yb amix bmix v ln öa öa
0 1 8.900 3.01 x 10-5 0.000437 0.036 1.037
0.1 0.9 8.205 3.01 x 10-5 0.000449 0.024 1.024
0.2 0.8 7.538 3.01 x 10-5 0.000460 0.013 1.013
0.3 0.7 6.899 3.00 x 10-5 0.000470 0.005 1.005
0.4 0.6 6.289 3.00 x 10-5 0.000479 -0.002 0.998
0.5 0.5 5.707 3.00 x 10-5 0.000487 -0.007 0.993
0.6 0.4 5.153 3.00 x 10-5 0.000495 -0.011 0.989
0.7 0.3 4.627 3.00 x 10-5 0.000502 -0.014 0.986
0.8 0.2 4.130 2.99 x 10-5 0.000508 -0.016 0.984
0.9 0.1 3.661 2.99 x 10-5 0.000514 -0.018 0.982
1 0 3.220 2.99 x 10-5 0.000520 -0.018 0.982
ya yb öa
0 1 1.033
0.1 0.9 1.02
0.2 0.8 1.008
0.3 0.7 1.000
0.4 0.6 0.992
0.5 0.5 0.986
0.6 0.4 0.982
0.7 0.3 0.978
0.8 0.2 0.977
0.9 0.1 0.975
1 0 0.975
1.025
Redlich-Kwong EOS
a
1.000
Thermosolver
0.975
0.950
0 0.2 0.4 ya 0.6 0.8 1
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,
P v bmix
2 xa aa xb aa ab
ln ˆav ln
RT
ba
v bmix
RTv
27 RTc 2 RTc
a b
64 Pc 8Pc
J m3 m3
aa 0.230 ba 4.31 10 5
2
mol mol
J m3 m3
ab 0.454 bb 4.34 10 5
2
mol 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:
RT a
P mix
v bmix v2
so
m3
v 4.81104
mol
Substituting these values into the equation for the fugacity coefficient, we get
ˆav 0.974
(b)
From Problem 7.5:
1
RT
ln ˆav ln
b
ln 1 ba
a
1 ba a
1.5
b
2 aa a ln 1
Pv v v b bRT v b bRT b v
1.5
R 2Tc2.5 RTc
a 0.42748 b 0.08664
Pc Pc
J m3 m3
aa 3.22 ba 2.99 10 5
2
mol mol
J m3 m3
ab 8.90 bb 3.0110 4
2
mol mol
Using these expressions we can find the molar volume with the Redlich-Kwong EOS:
RT amix
P
v bmix T vv bmix
1 / 2
m3
v 4.871 10 4
mol
Substituting these values into the expression for the fugacity coefficient, we get
ˆav 0.993
(c)
Using Kay’s mixing rules, we have the following expressions:
T pc yaTc, a ybTc, b
Ppc ya Pc, a yb Pc,b
w pc ya a ybb
T pc 281.9 K
Ppc 67.69 bar
pc 0.054
Therefore,
Tr 1.58
Pr 1.03
Therefore,
(d)
Using the Peng-Robinson EOS in ThermoSolver, we obtain:
ˆav 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.
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
Bmix y a2 Baa 2 y a yb Bab yb2 Bbb
cm 3 cm 3
Baa 16 and Bbb 101
mol mol
2 2
V RT 2na Baa 2nb Bab na Baa 2na nb Bab nb Bbb
Va
na T , P,nb P na nb na nb 2
or
2 ya Baa 2 yb Bab ya2 Baa 2 ya yb Bab yb2 Bbb
RT
Va
P
P
RT fˆav
P 2 y B
a aa 2 y B
b ab a aa a b ab b bb
y 2
B 2 y y B y 2
B dP =RT ln so
Plow pa ,low
fˆav
P
2 ya Baa 2 yb Bab ya Baa 2 ya yb Bab yb Bbb dP =RT ln
P 2 2
RT ln
Plow Plow ya Plow
Rearranging
fˆ v
P
2 ya Baa 2 yb Bab ya2 Baa 2 ya yb Bab yb2 Bbb dP =RT ln a RT ln ˆav
Plow ya P
Integrating, we get
2y Ba aa
2 yb Bab ya2 Baa 2 ya yb Bab yb2 Bbb P RT ln ˆav
cm 3
Bab Baa Bbb 40.2
mol
This problem can also be solved using the form of the virial equation:
Bmix
z 1
v
7.47
(a)
We can start with Equation 7.14 to find the fugacity coefficient:
föv V
P
RT ln 1 dV
y1 Plow n
nRT 1 T ,V , n 2
Plow
Differentiate:
1 / 2 n a n2 a 2
P
a1 n1 n2 1 1
RT 1
n1 T ,V , n 2 V V 3 / 2T 1 / 2 2n1 n2 1 / 2
P
low
1/2
2 n a n a2
a1 n1 n2 1 1 2 1/2
1/2
nRT T 2 n1 n2
1/2
This expression can be simplified by canceling the terms containing Plow and then taking the
limit as Plow goes to zero. This results in
V V T 2 n1 n2
1/2
y1
fˆ v RT 2
y1a1 y2a2
1
RT ln 1 RT ln a1
y1 v vT 2
If we subtract the natural log of pressure from both sides of the equation and rearrange, we
obtain
RT 2 1
ln ˆ1v 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.
8.314 500
ˆ1v exp ln
2
800
1
0.33 800 0.66
500
1.78 106 0.002 8.314 500 0.002 500 2
ˆ1v 0.689
Note: The pressure was calculated prior to substitution using the given EOS.
P
8.314500 0.33800 0.66500 1.78 10 6 Pa
0.002 0.0023 500
(b)
The Lewis fugacity rule states
ˆ1v 1v
fv P
RT ln 1 v1dP
Plow
Plow
RT 3 a1
dP dv1
v12 2 T 1 / 2v5 / 2
1
Substitute the above expression into Equation 7.8 and change the limits of integration:
f v v1 RT 3
RT ln 1
a1
dv
Plow v 2 T 1/ 2 3 / 2 1
v
RT 1 1
Plow
If we cancel the natural log terms containing Plow and then let Plow go to zero, the above equation
simplifies to
RT 3a1
ln f1v ln
v1 RT Tv1
Now subtract the natural log of P from both sides of the equation:
f1v RT
ln
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 800
v1 500v13
m3
v1 0.00187
mol
Substitute values into the expression for the fugacity coefficient and evaluate:
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 T P T
f
g i g i¼ RT ln i g i¼ RT ln f i RT ln Plow
Plow
Differentiate:
Hence,
gi ln fi
v RT
P T
i
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 ºC is independent
of pressure. Therefore,
fi P
RT d ln
sat
f i vil dP
fi 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 ºC and P 10 kPa as the reference. From the steam tables
kJ
s º 9.2812
kg K
kJ
h º 3076.5
kg
kJ kJ kJ J
g º 3076.5 573.15 K 9.2812 kg K 2243.0 kg 40407.2 mol
kg
For P sat 8.5810 MPa and T 300 ¼C , the steam tables allow us the calculate the Gibbs
energy:
kJ kJ kJ
520.6 9378.5
J
g sat 2748.9 573.15 K 5.7044
kg
kg K kg mol
Now use Equation 7.7 to find f sat :
9378.5 40407.2
f sat 10 kPa exp
8.314573.15
f sat 6729 kPa
Once we find vil , we can calculate the fugacity. From the saturated steam tables,
m3 m3
visat 0.001404 0.0180148 kg/mol 2.53 10
5
kg
mol
Therefore,
2.53 105
fi 6729 kPa exp 300 105 Pa-85.18 105 Pa
8.314 573.15
f i 7542 kPa 75.4 bar
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
Pisat exp 9.0580
260 34.42
Pisat 0.610 bar
Therefore,
(b)
Now that the system pressure is high, we can’t simplify the calculation as we did in Part (a).
Instead, we will use Equation 7.36.
P
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:
MW i 0.058123 kg/mol m3
vi 1.00 104
i 579 kg/m3 mol
Since the density is constant with respect to pressure, we can substitute numerical values into
Equation 7.36 and integrate:
P
vi
f il isat Pisat exp dP
sat RT
Pi
Calculate the saturation pressure using Antoine’s Equation data in Appendix A.1:
2940.46
Pisat exp 10.0311
382 35.93
Pisat 4.64 bar
Since the saturation pressure is 4.64 bar, we cannot assume the saturation fugacity coefficient to
be unity. We can use reduced generalized correlation tables to calculate the fugacity coefficient.
From data in Appendix A.1,
Use these values in Tables C.7 and C.8 to determine the fugacity coefficient:
Since the density is constant with respect to pressure, we can substitute numerical values into
Equation 7.36 and integrate:
P
vi
f il isat Pisat exp dP
sat RT
Pi
Calculate the saturation pressure using Antoine’s Equation data in Appendix A.1:
1872.46
Pi sat exp 9.1058
333 25.16
Pi sat 20.56 bar
Since the saturation pressure is 20.56 bar, we cannot assume the saturation fugacity coefficient to
be unity. We can use reduced generalized correlation tables to calculate the fugacity coefficient.
From data in Appendix A.1,
Use these values in Tables C.7 and C.8 to determine the fugacity coefficient:
Since the density is constant with respect to pressure, we can substitute numerical values into
Equation 7.36 and integrate:
P
vi
f il isat Pisat exp dP
sat RT
Pi
so
isat 1
and
m3
vi 1.8 105
mol
Taking vi to be constant
v
fi l isat Pi sat exp i P Pi sat 4557 kPa
RT
7.54
(a)
Begin by drawing a line tangent to the plot for fˆal as xa 0 . Then, extend the line to xa 1 .
The Henry’s 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
fˆal
ga
x fˆ o
a a
fˆal
ga
xaH a
Therefore,
12 kPa
g a xa 0.4 1.54
0.4 19.5 kPa
31 kPa
g a xa 0.8 1.99
0.8 19.5 kPa
(c)
From the Gibbs-Duhem Equation, we know
d ln g a d ln g b
xa xb 0
dxa dxa
d ln g b
Therefore, 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 .
(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, fˆav ya P . Setting fugacities equal, we get
ya P fˆav fˆal
Therefore,
fˆal 12 kPa
ya
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
xa xb 0
dxa dxa
d ln g a
1.33
dxa
d ln g b
2
dxa
Therefore,
ln g a 2.5
ln g b 1.5
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,
gE x a x b 4988.4 1247.1x a x b J mol-1
(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
Ha
g a
fa
ln ya 2.5
(d)
From Table 7.1,
RT ln g a Axb2
As xb 1 , ln g a 2.5 . Therefore,
A
2.5RT
1
2.5 8.314 J mol-1 K 1 300 K
A 6235.5 J mol -1
(e)
We first calculate the mole fraction of a in the liquid mixture.
na 2 mol
xa 0.4
ntot 5 mol
ln g a 0.875
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.
The vapor mole fraction can be determined from the definition of fugacity in the vapor phase if
we assume ideal gas behavior, which is reasonable at 1 bar.
fˆav ya P
76.8 kPa
ya 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
g b exp
6235.5 J mol-1 0.4
2
1.49
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 :
32 K
128 K
A
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).
128 K 12
g 2 exp
343 K
g 2 1.45
(b)
From Equation 7.75:
H2
g 2
f2
where
f 2 P2sat
Calculate the saturation pressure of cyclohexane using data from Appendix A.1:
2766.63
P2sat exp 9.1325
343 50.50
P2sat 0.722 bar
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:
na nb na nb
GE A B
na nb n a nb
Find GaE :
dG E
GaE xb xa xb A Bxa xb 2 Bx a xb2
dna
T ,V , nb
Substitute xa 1 xb :
Therefore,
A 3B x 2 4 Bx 3
g a exp b b
RT
(b)
Rewrite excess Gibbs energy as
na nb
G E AB
An a Bnb
Find GaE :
dG E B 2 nb2
GaE A
dna 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 B 2 xb2
g a exp
RT 2
Ax a Bxb
(c)
Rewrite excess Gibbs energy as
n ab nb n ba na
G E RT na ln a nb ln b
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
xb2 ba 1
1 xb xb 1 ab
GaE RT ln xa ab xb
xa xb ab xb xa ba
1 x 1 x 1
Ga RT ln xa ab xb xb
E b ab b ba
xa xb ab xb xa ba
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
which is consistent with the expression in Table 7.2.
(d)
Rewrite the excess Gibbs energy as
na nb na nb
G E RT ba G ba ab G ab
na nb G ba nb na G ab
Find GaE :
dG E ba G 2 n 2 ab G ab nb2
GaE RT ba b
dna 2
2
T ,V , nb an n G
b ba nb n G
a ab
G2 ab G ab
GaE RTxb2 ba ba
xa xb G ba 2 xb xa G ab 2
Therefore,
ba G 2ba ab G ab
g a exp xb2
xa xb G ba 2 2
xb xa 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
For an equimolar solution:
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
Solving, we obtain
g a 1.10
g b 1.18
Wilson:
At infinite dilution:
Solve simultaneously:
ab 0.407
ba 1.21
1.21 0.407
ln g a ln0.5 0.50.407 0.5
0.5 0.51.21 0.5 0.50.407
0.407 1.21
ln g b ln0.5 0.51.21 0.5
0.5 0.50.407 0.5 0.51.21
Solving, we obtain
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
x
a g a xa g a ln a ln g ln g
x a a
a
x
xb g b xb g b ln b ln g ln g
x b b
b
Use the composition data provided in the problem statement and the expressions from Table 7.1:
0.9
ln
1
A 3B 0.82 0.12 4 B 0.8 3 0.13
0.2 8.314 493.15
0.1
ln
1
0.8 8.314 493.15
A 3B 0.2 2 0.9 2 4 B 0.2 3 0.9 3
Solve simultaneously:
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
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:
J
RT ln g a 8.314 343.15 K ln 2.62 A 3B 1 4 B 1
2 3
mol K
J
RT ln g b 8.314 343.15 K ln 7.24 A 3B 1 4 B 1
2 3
mol K
A 4200 J mol and B 1450 J mol -1
-1
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
ºC. The following relationship also holds since the saturation pressure at 70 ºC is so low that the
water vapor behaves as an ideal gas and the Poynting correction can be neglected.
f ao Pasat
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 ºC:
4198 3 1450 0.6 2 4 1450 0.6 3
g a exp
8.314 J mol-1 K 1 343.15 K
g a 1.90
GaE RT ln g a
GbE RT ln g b
The expression for the excess molar Gibbs energy can be rewritten as
ABx a xb
gE 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
ABn a nb
GE Cna nb na nb 2 na nb 3
Ana Bnb
Differentiation provides
2
Bxb
GaE A Cxb2 2 xb 16 xb 5
a
Ax Bx b
2
Cxa2 2 xa 16 xa 5
Ax a
GbE B
Ax a Bxb
2
ln g a
Bxb
Cxb 2 xb 16 xb 5
1 A 2
RT Ax a Bxb
Ax a
2
ln g b Cxa 2 xa 16 xa 5
1 B 2
RT Ax a Bxb
7.63
Applying Equation E6.4E to the property k = (gE/RT) gives:
gE gE
g
E
RT dT RT dP Gi dx
m E
d
T P
i
RT ni 1 RT
P ,ni T ,ni
gE
RT hmix
T RT 2 (Equation 7.75)
P,n i
g E
RT v mix
P RT (Equation 7.74)
T ,n i
we obtain
gE hmix m
v mix
d
RT RT
2
dT
RT
dP ln g idxi
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
RT 2
RT 2
RT
hmix g
dT ln 1 dx1
RT 2 g2
gE
hmix dT ln g 1 dx1
d RT RT 2 g 2
x1 1 T x 1
g1 1
hmix
g 2 1 RT 2 dT
ln dx
x1 0 T x1 0
1 dT
d
T T2
Hence,
x1 1 T x1 1
1
x1 1
g hmix T hmix 1
ln 1 dx1
g2 2
dT
R
d
T
x1 0 T x1 0 RT 1
x1 0
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:
fˆal xag a f al
Calculate the fugacity of pure hexane (a) at 30 ºC and 1 bar assuming the saturated hexane vapor
acts ideally since its saturation pressure is low at 30 ºC:
f al Pasat
f al 0.25 bar (Used Antoine’s equation and data from Appendix A.)
6700.82
g a exp 1.19
8.314303.15
Therefore,
(b)
Calculate g a when xa 0.5, xb 0.5 :
6700.52
g a exp 1.07
8.314303.15
Therefore,
(c)
Calculate g a when xa 0.9, xb 0.1 :
6700.12
g a exp 1.00
8.314303.15
Therefore,
g
1l 0.80 , 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
f1l P e
1
sat sat RT
1
The specific molar volume of 1-propanol is found from the given density:
The saturation pressure is found using the Antoine equation, and the appropriate constants given
in Appendix A:
B 3166.38
ln P1sat A 10.9237
T C 298 80.15
P1 0.027 bar
sat
Since the saturation pressure is very low, we can assume that 1-propanol acts ideally. Thus,
1sat 1 (ideal)
6 m
3
v1l
P P1sat 75.1 10
5 J
sat RT
f1l P e
0.027 bar exp mol
100 105
0.027 10
8.314 J 298K
1
m3
mol K
Now, we can calculate the activity coefficient from the pure-species fugacity and the given
Henry’s law constant.
Recall that (Equation 7.75):
H1 0.61 bar
g 1 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
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):
x2 2.810.6 1.01
A 2
ln g 1
2
RT
g 1 2.75
And finally, we can find the solution fugacity of 1-isopropanol in the given mixture:
J J
AvL 3000 , and BvL 5040
mol 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 2
Bx b Ax a
RT ln g a A , and RT ln g b B
Ax a Bx 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.
J J
RT ln g a A 3000 , and RT ln g a B 5040
mol mol
J J
RT ln g a A B 3000 , and RT ln g b A B 5040 .
mol mol
J J
A 4020 , and B 1020
mol mol
(b)
Calculate the fugacity of liquid benzene (a) in a 30 mole% mixture in 1-propanol at 81kPa.
fˆal xag a f a xag a Pasat (Note: the system pressure is low, so f al 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
RT ln g a ( A 3B) xb2 4 Bx b3 2070
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:
B
ln Pasat A 0.147
T C
Substituting these values into the original equation, we find the fugacity of liquid benzene in the
mixture:
(c)
Determine the mole fraction of vapor in the mixture, assuming the system is in equilibrium.
y a P 0.53 bar
Solving for ya, and substituting the system pressure (0.81 bar) :
0.53 bar
ya 0.65
0.81 bar
7.67
We are asked to determine the fugacity of a, and the Henry’s Law constant Ha in a mixture of a
and b at 30 kPa and 20°C. The saturation pressure of a and an equation for the excess Gibbs
energy of the mixture is given:
(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:
Reading from the same table (or explicitly evaluating the derivative), we find an expression for
the activity coefficient of a in the mixture:
Substitute the values for Aab and Aba, and the mole fraction of each species (xa = 0.2, xb = 0.8):
Now use the relation for fugacity of a condensed phase to find the fugacity fˆal :
(b)
Now calculate the Henry’s law constant. First, find the activity of a at infinite dilution:
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 0.545 0.455
x1r1 x2 r2
xi qi
i 0.417 0.583
x1q1 x2 q2
xi qi'
i' 0.501 0.499
x1q1' x2 q2'
li -0.42 -2.32
1* z r
ln g 1, combinatorial ln q1 ln 1* *2 l1 l2 1 0.236
x1 2 1 r2
and
*2 z r
ln g 2, combinatorial 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 and 21 exp 21 1.35
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
These values are 3 – 6% lower than the experimentally measured values of g 1exp 2.30 and
g 2exp 1.32 .
7.69
From the expressions in Table 7.4, we have:
Ethanol Benzene
xi ri
*i 0.319 0.681
x1r1 x2 r2
xi qi
i 0.368 0.632
x1q1 x2 q2
xi qi'
i' 0.214 0.786
x1q1' x2 q2'
li -0.41 1.76
1* z r
ln g 1,combinatorial ln q1 ln 1* *2 l1 l2 1 0.063
x1 2 1 r2
and
*2 z r
ln g 2,combinatorial 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 and 21 exp 21 0.467
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
g 1exp 1.66
x1P1sat
7.70
From the expressions in Table 7.4, we have:
Acetone Chloroform
xi ri
*i 0.192 0.808
x1r1 x2 r2
xi qi
i 0.200 0.800
x1q1 x2 q2
xi qi'
i' 0.200 0.800
x1q1' x2 q2'
li -0.42 0.1
1* z r
ln g 1,combinatorial ln q1 ln 1* *2 l1 l2 1 0.008
x1 2 1 r2
and
*2 z r
ln g 2,combinatorial 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 and 21 exp 21 0.737
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
g 1exp 0.536
x1P1sat
7.71
The fugacity of ethanol in solution is calculated with the following equation:
ln g 1 0.192
g 1 1.21
Now calculate the saturation pressure of ethanol at 60 ºC using Antoine’s Equation data in
Appendix A.1.
3803.98
P1sat exp 12.2917 bar 0.468 bar
333.15 41.68
v v
ab b exp ab ba a exp ba
va RT vb RT
Find the energetic parameters (lowercase lambdas) at 60 ºC, and use them to calculate the
uppercase lambdas at 8 ºC. The molar volumes for ethanol and 1-propanol can be calculated
using the Rackett EOS. The saturated steam tables provide an estimate for water’s molar
volume. Using the above equations with the 60 ºC data, we obtain:
Pairing (J/mol)
12 1.13 x 102
21 6.83 x 102
13 1.39 x 103
31 3.52 x 103
23 4.73 x 103
32 5.04 x 103
Now, we can calculate the Wilson parameters at 8 ºC since the energetic parameters are less
sensitive to changes in temperature. We obtain
Pairing
12 1.214
21 0.586
13 0.204
31 0.602
23 0.038
32 0.400
We will find the fugacity of the ethanol with the following equation
x111 x2 21
x x x x x x
ln g 1 1 ln x111 x2 12 x313
1 11 2 12 3 13 1 21 2 22 3 23
x3 31
x x x
1 31 2 32 3 33
g 1 1.32
We can find the saturation pressure from Antoine’s Equation data in Appendix A.1.
3803.98
P1sat exp 12.2917 bar 0.028 bar
281.15 41.68
Therefore,
ln g i H i hi
T P , x RT 2
H mix
i
H i hi
Therefore,
ln g i
H mix i
T P , x RT 2
H mix 447.8
n1 n2 n1 n2 n1 n2 n1 n2
2 3
Thus, we find
H x
mix
1
2
2
28731.8x13 4156.6 x12 x2 13131.4 x1 x22 3708.2 x23
H mix
1
J
1062.5
mol
g 1062.5 1 1
ln 1
1.65 8.314 373.15 333.15
g 1 1.58
7.74
Since we are assuming that the tin and cadmium form a regular solution,
g E hmix
E
GCd RT ln g Cd
E
To find GCd , start with
13000nCd nSn
G E H mix
nCd nSn
Differentiating provides
E 2
GCd 13000 X Sn
Therefore,
130000.6 2
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 ºC, 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) Part (b) Part (c) Part (d) Part (e)
Two
Three Suffix
Suffix van Laar Wilson NRTL
Margules
Margules
A A B A B ab ba Gab Gba ab ba
3652.3 3521.0 -1102.3 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.
7.76
Select the isothermal pentane/acetone experimental data set in the Models for gE – Parameter
Fitting menu. The temperature, 25 ºC, 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) Part (b) Part (c) Part (d) Part (e)
2 Suffix Three Suffix
van Laar Wilson NRTL
Margules Margules
A A B A B ab ba Gab Gba ab ba
4371.1 4365.8 208.7 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.
Part (a) Part (b) Part (c) Part (d) Part (e)
2 Suffix Three Suffix
van Laar Wilson NRTL
Margules Margules
A A B A B ab ba Gab Gba ab ba
1329.8 1235.5 261.6 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.
atm.
PO = 160 mmHg
2
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:
5 J -6 m3
1.013 10 3 1.4 mL 10
PO2V m mL
nO2 5.726 105 moles O2
J
298K
RT
8.314
mol K
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
b) Compare the result from part A with the oxygen capacity of pure water:
From Table 8.1, we can get the Henry’s Law constant H O2 44, 253.9 bar for oxygen in water
at 25°C. Since pressure is low and the gas solution is dilute, we can assume ideal behavior, so
Equation 8.30 holds:
yO2 P 0.21 bar
xO2 4.75 106
H O2 44, 253.9 bar
nO2 nO2
Since xO2 , we can write nO2 xO2 nH2O . Assuming the solution volume is
nO2 nH 2O nH 2O
approximately equal to the volume of pure water, we can define the molality of oxygen to be:
nO2 nO2
O2
Vsolution VH 2O
VH 2O
Substituting the above relation for nO2 , and noting that vH 2O ,
nH 2O
xO2
O2
vH 2 O
The molar volume of water can be found from the density at 25°C and molecular weight:
M H 2O 18 g/mole L
vH 2O 0.018
H O2
1000 g/L mole
Since VO2 VH 2O , the volume of solution is essentially the same as that of the water:
mole O2
O2 2.64 104 .
liter
Thus, the perflubron emulsion can carry approximately 2.2 times as much oxygen as pure
water.
c) Find the value of the Henry’s Law constant for oxygen in pure perflubron (PFB).
xa
ya P
Ha (see the figure at right)
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
12.435 cm PFB .
3
24g 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:
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
nO2 , PFB 5.726 105 moles 3
5
2.64 10 moles
100 cm
nO2 , PFB 2.64 10 moles O2
-5
Now find the mole fraction of O2 dissolved in the PFB in the 100 cm3 of PFB/H2O emulsion:
Applying the definition of the Henry’s Law constant above, we can compute H O2 , PFB :
yO2 P 0.211.01325 bar
H O2 , PFB 297.5 bar
xO2 , PFB 7.153 104
H O2 , PFB 300 bar (Note that a smaller Ha implies a larger xa for a given Pa)