Professional Documents
Culture Documents
Solutions Koretsky ch04
Solutions Koretsky ch04
Wyatt Tenhaeff
Milo Koretsky
Department of Chemical Engineering
Oregon State University
koretsm@engr.orst.edu
4.1.
(a)
Yes, the form of the equation is reasonable. This can be rewritten:
PA+ =
RT
a
n
v A+ v A+
It is equivalent to Pv = RT , except the pressure term has been corrected to account for the ions
intermolecular forces. The coulombic forces between the gas molecules affect the system
pressure. This modification is similar to the van der Waals equation. Since we are limited to 1
parameter, we need to choose the most important interaction. Since net electric point charges
exert very strong forces, this effect will be more important than size.
(b)
The sign should be negative for a because the positively charged gas molecules repel each other
due to coulombic forces. Therefore, the system pressure increases, i.e.,:
n=
1
3
a must have must have the following units to maintain dimensional homogeneity with the
pressure term:
a N J
v1/ 3 = m 2 = m 3
so
[a] =
1/3
m mol
2
4.2
The attractive interactions are described by van der Waals forces. For both O2 and propane, the
dipole moments are zero. Therefore, the expression for the interactions reduce to
=
3 i j
2 r6
Ii I j
Ii + I j
[ ]) (1.933 10
3 16 10 25 cm 3
aa =
2
r6
aa =
3.71 10 59
r
ab =
ab =
[cm
[cm
[ ]) (1.753 10
bb =
[ ]) (1.933 10
erg
3 62.9 10 25 cm 3
bb =
2
r6
5.20 10 58
r
[cm
erg
3 16 10 25 cm 3 62.9 10 25 cm 3
2
r6
1.39 10 58
)(
11
erg + 1.933 10 11 erg
1.933 10
[ ])(
11
erg
11
11
)(
)(
(b)
Calculation:
5.20 10 58
3.71 10 59
6
cm erg
cm 6 erg
aa bb =
r6
r6
aa bb =
1.39 10 58
[cm
erg
r
Note: Disregarded the positive value.
The value of
aa bb is equal to ab . The values are equal because the ionization energies are
similar.
(c)
An expression for the average intermolecular attraction in the mixture can be found using the
mixing rules
mix = y a2 aa + 2 y a yb ab + yb2 bb
3.71 10 59 y a2 + 1.39 10 58 y a yb + 5.20 10 58 yb2
mix =
cm 6 erg
6
r
)[
4.3
(a)
300 K, 10 atm. The intermolecular distance of molecules is greater at lower pressures.
Therefore, fewer intermolecular interactions exist, which cause less deviation from ideality.
(b)
1000 K, 20 atm. At higher temperatures, the kinetic energy of the molecules (speed) is greater.
The molecules interact less; thus, the compressibility factor is closer to unity.
(c)
Let subscript 1 denote BClH2 and 2 denote H2. For the mixture, we calculate the
compressibility factor as follows
B
z = 1 + mix
v
where
zH2 close to 1
1
0.9
zBClH2 lowest
0.8
0.7
0.6
0
0.2
0.4
0.6
yBClH2
0.8
4.4
(a)
The intermolecular attractions and volume occupied by the styrene monomers will contribute to
the deviations from ideality. Since styrene monomers are essentially non-polar, the order of
importance is as follows
J
8.314
(647.15 K )
3
mol K
27 (RTc )
27
= 3.13 J m
=
a=
2
64 Pc
64
39 105 [Pa ]
mol
b=
RTc
=
8 Pc
J
(647.15 K )
8.314
mol K
8 39 105 [Pa ]
m3
= 1.72 10 4
mol
Now we can use the van der Waals EOS to solve for temperature.
P=
RT
a
v b v2
J
8.314
T
mol K
5
10 10 [Pa ] =
3
4 m
3.0 10
1.72 10 4
mol
T = 550.8 K = 277.65 C
m3
mol
J m3
3.13
2
mol
3.0 10 4
m3
mol
J m3
a = 15.65
2
mol
m3
b = 8.6 10 4
mol
(d)
We must realize that if we initially believed there were 100 moles of styrene in the reactor, then
there can only be 20 moles of the 5-monomer long polymer chain. Therefore,
m3
v = 1.5 10 3
mol
and
J m3
J
15
.
65
8.314
T
mol 2
mol K
10 10 [Pa ] =
2
3
3
3
m
m
4
3 m
1.5 10 3
8
.
6
10
mol 1.5 10
mol
mol
T = 612.41K = 339.26 C
4.5
There are many ways to solve this problem, and the level of complexity varies for each method.
To illustrate the principles in Chapter 4, two of the simplest solution methods will be illustrated.
Method 1. Polarizability of each atom
The polarizability of a molecule scales with the number of atoms; the polarizabilities of
individual atoms are additive. Using the first two molecules, solution of the following system of
equations
1 C + 4 H = 1 CH 4
2 C + 6 H = 1 C2 H 6
gives
[ ]
[cm ]
C = 11.4 10 25 cm 3
H = 3.65 10 25
Now, the polarizability of the chlorine atom can be found. For chloroform,
1 C + 4 Cl = 1 CCl 4
Therefore,
[ ]
Cl = 23.4 10 25 cm 3
The values of C3 H 8 , CH 3Cl , CH 2Cl2 , and CHCl3 are calculated with the polarizabilities found
above as follows, and compared to the values given.
Species
C3H8
CH3Cl
CH2Cl2
CHCl3
calculated
(x 1025 cm3)
63.4
45.8
65.5
85.3
reported
(x 1025 cm3)
62.9
45.6
64.8
82.3
% Difference
0.8
0.3
1.1
3.6
All agree reasonably well. Now, the polarizabilities of C 4 H10 and C 2 H 5Cl will be calculated.
H 10
[ ]) (
[ ])
[ ]
H 5 Cl
[ ]) (
[ ]) (
[ ])
[ ]
[ ]
[ ]
26 10 25 cm 3
= 6.5 10 25 cm 3
4
C H =
[ ] (
[ ])
[ ]
The C-C and C-H polarizability calculated above predict the given polarizability of propane well.
The polarizability of C-Cl bonds is calculable with the polarizability of chloroform.
4 C Cl = 1 CCl 4
C Cl =
[ ]
[ ]
105 10 25 cm 3
= 26.25 10 25 cm 3
4
The values of C3 H 8 , CH 3Cl , CH 2Cl2 , and CHCl3 are calculated with the polarizabilities found
above as follows, and compared to the values given.
Species
C3H8
CH3Cl
CH2Cl2
CHCl3
calculated
(x 1025 cm3)
63.4
45.8
65.5
85.3
reported
(x 1025 cm3)
62.9
45.6
64.8
82.3
% Difference
0.8
0.3
1.1
3.6
All agree reasonably well. This value predicts the polarizabilities of the other species in the table
reasonably well. Now, the polarizabilities of C 4 H10 and C 2 H 5Cl will be calculated.
1 C 4 H 10 = 3 C C + 10 C H
H 10
[ ]) (
[ ])
[ ]
1 C 2 H 5 Cl = 1 C C + 5 C H + 1 C Cl
H 5 Cl
[ ]) (
[ ]) (
[ ])
[ ]
Note both the atom method and the bond method yield identical results. More accurate values
for the polarizabilities can be calculated using more of the data given in the problem.
10
4.6
(a)
increases with molecular size. Therefore,
I > S > O
2
scales with magnitude of van der Waals interactions. Because these are non-polar, diatomic
molecules, only dispersion forces are present. Dispersion forces depend on the first ionization
potential and polarizability. Ionization energy is approximately equal for each molecule. The
polarizability scales with molecular size, so
I > S > O
2
(b)
increases with molecular size. Diethylether and n-butanol have the same atomic formula and
similar spatial conformations. Therefore, they should be about equal in size. Methyl ethyl
ketone has fewer atoms, but has two exposed electron pairs on the double-bonded oxygen. The
size of the molecular electron orbital of methyl ethyl ketone is approximately equal to the sizes
of diethyl ether and n-butanol, so
11
4.7
(a)
At 30 bar, the water molecules are in closer proximity than they are at 20 bar. Intermolecular
attractions are greater, so the magnitude of molecular potential energy is greater. The potential
energy has a negative value for attractive interactions. The molecular kinetic energy is identical
since the temperature is the same. Hence, the internal energy, the sum of kinetic and potential
energies, is less at 30 bar.
(b)
The key to this phenomenon is hydrogen bonding. At 300 K and 30 bar, isopropanol and npentane are both liquids. The hydrogen bonding and dipole-dipole interactions are present in
isopropanol, and dispersion is present in n-pentane. The intermolecular forces are greater in the
isopropanol, so the compressibility factor is smaller for isopropanol.
At 500 K and 30 bar, both species are gases. In the gas phase, hydrogen bonding does not play a
significant role. The dispersion forces in n-pentane are stronger than the dipole-dipole forces of
isopropanol. Therefore, the compressibility factor is smaller for n-pentane.
12
4.8
(a)
Ideal: For ideal NH3, the compressibility factor is equal to one. For real NH3, the strong
intermolecular forces (dipole-dipole and dispersion) cause the molar volume to decrease. They
outweigh the volume displaced by the physical size of NH3; thus, z will be less than one.
(b)
Internal energy will be greater for the ideal gas. In the real gas, intermolecular attractions are
present. Internal energy value is the sum of potential and kinetic energies of the molecules. The
absolute values of the kinetic energies are identical at identical temperature: however, the
potential energy decreases for real NH3 due to attractive interactions - so the internal energy is
less for the real NH3.
(c)
The entropy will be greater for the ideal gas. Entropy is a measure of possible molecular
configurations or randomness. Ammonia has an electric dipole in which positive and negative
charge are separated. The intermolecular forces in the real gas cause the molecules to align so
that the positive charge in one molecule is adjacent to a negative charge in a neighboring
molecule to reduce potential energy. Therefore, fewer possible configurations exist, which
creates less randomness and lower entropy.
13
4.9
(a)
We can determine which case has the higher compressibility factor by comparing the molar
volumes at constant T and P. With Ne, very weak intermolecular attractions are present, so
volume displacement becomes important. The compressibility factor will be slightly greater than
one. In NH3, the strong intermolecular attractions decrease the molar volume, so z is less than
one. The compressibility factor is greater for Ne.
(b)
Entropy is a measure of randomness. Both species are gases at these conditions. The
intermolecular attractions present in NH3 reduce the number of possible configurations. The
weak forces present in Ne have a much smaller effect. However, NH3 is asymmetrical, while Ne
is symmetrical. The asymmetry of NH3 results in more possible configurations that NH3 can
have. Therefore, it is difficult to qualitatively show for which case the entropy is greater. Since
both species are gases, intermolecular interactions are relatively weak, and we can guess that
entropy is greater in NH3.
14
4.10
(a)
To find the average distance between the two atoms of Ar, we can find the volume that each
atom occupies. The molar volume can be found from the compressibility factor. At 300 K and
25 bar,
Tr = 1.99
Pr = 0.513
From the generalized compressibility charts:
z = 0.9859
Therefore,
v = 0.9859
J
8.314
(300 K )
mol K
25 105 [Pa ]
= 9.84 10
m3
mol
m3
v = 1.63 10 27
atom
The second number was found by dividing the molar volume by Avogadro's number. To
estimate the distance between each atom, we note that the distance between molecules can be
related to the volume by:
r3 v
Consider the geometry shown below:
3
Ar
Ar
A rough estimate of r is
r = 1.63 10 27 m 3
r = 11.8 [A ]
(b)
The potential energy due to gravity can be calculated as follows
G =
G m 2Ar
r
m2
where G is the gravitation constant G = 6.67 10 11
and mAr is the mass of an argon
2
kg s
1 [kg ]
39.948 [g Ar]
1 [mol]
kg
= 6.633 10 - 26
m Ar =
23
atom
1 [mol Ar ] 6.023 10 [atoms] 1000 [g ]
Using the distance calculated in Part (a), we get
G = 2.49 10 -52 [J ]
(c)
Equation 4.13 quantifies the potential energy due to London interactions
Ar Ar =
3 Ar Ar
2 r6
I Ar I Ar
I Ar + I Ar
[ ]
Ar = 16.6 10 25 cm 3
16
4.11
We want to compare the Lennard-Jones potential to one with an exponential repulsion term. As
provided in the text, Equation 4.19, the Lennard-Jones potential is
12 6
= 4
r
r
To simplify further analysis, we can rewrite the equation in dimensionless quantities:
* =
1
1
=
4 (r *)12 (r *)6
r* =
where
c2
1
= c1 exp
r * r * 12
( )
We have two adjustable parameters, c1 and c2, to match the first (LJ) potential to the second
(exp) potential. We need to choose reasonable criteria to specify. For this solution we choose
equal well depths and equal values at =1. Other choices may be just as valid; you should
realize that you have two parameters to fit and so must specify two features.
Using the above criteria, we iterate on a spreadsheet, to get the solution:
c1 = 143,000 and
c2 = 11.8
This solution is shown at two magnifications in the plots on the following page:
17
Potential functions
0.3
0.2
Lennard-Jones
exponential
0.1
0
0.9
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
2.1
-0.1
-0.2
-0.3
Potential functions
20
Lennard-Jones
15
exponential
10
0
0.7
1.3
1.6
1.9
-5
18
4.12
(a)
The bond strength of a sodium ion can be viewed as the amount of energy it would take to
remove the sodium ion from the crystal lattice. The interaction between the chlorine and sodium
ions is Coulombic attraction.
)(
QNa QCl
4.803 10 10 esu 4.803 10 10 esu
=6
= 5.01 10 11 [erg ]
r
2.76 10 -8 cm
= 31.3 [eV ]
=6
(b)
=6
QNa QCl
Q Q
+ 12 Na Na
r
r
= 5.01 10 11 [erg] + 12
(4.803 10
10
(c)
QNa QCl
Q Q
Q Q
+ 12 Na Na + 8 Na Cl
r
r
r
4.803 10 10 esu 4.803 10 10 esu
= 2.089 10 11 [erg] + 8
4.78 10 -8 cm
= 1.77 10 11 [erg] = 11.1 [eV]
=6
)(
(d)
QNa QCl
Q Q
Q Q
Q Q
+ 12 Na Na + 8 Na Cl + 6 Na Na
r
r
r
r
10
4.803 10 esu 4.803 10 10 esu
11
= 1.77 10 [erg ] + 6
5.52 10 -8 cm
= 7.37 10 12 [erg] = 4.60 [eV]
=6
)(
19
4.13
The boiling points of the halides depend upon the strength of intermolecular attractions. The
stronger the intermolecular attraction, the higher the boiling point. Dispersion and dipole-dipole
interactions are present in all five species listed. The magnitude of the dipole-dipole interactions
is similar so the pertinent intermolecular force in these molecules is dispersion. The molecular
size increases from left to right. Polarizabilities are greater in larger molecules, which manifests
in larger dispersion forces. Therefore, the boiling point increases from left to right.
20
4.14
van der Waals forces hold the Xe atoms together in a molecule of Xe2. The potential energy can
be quantified with the Lennard-Jones potential function. The bond length is the r value where
the potential is a minimum. From Table 4.2:
k
and
= 229 K
= 4 .1 A
or
r = 6 2 = 1.12 = 4.60 A
21
4.15
The data in the following table were taken from Table A.1.1
Species
Tc [K ]
He
CH4
NH3
H2O
5.19
190.6
405.6
647.3
Pc 10 -5 [Pa ]
2.27
46.00
112.77
220.48
The van der Waals a parameter can be calculated using Equation 4.39.
27 (RTc )2
a=
64 Pc
The van der Waals b parameter can be calculated using Equation 4.40.
b=
RTc
8 Pc
Using the data table and equations listed above, the following table was created; the values of
dipole moment and polarizability reported in Table 4.1 are also included.
Species
He
CH4
NH3
H2O
J m3
a
2
mol
0.00346
0.230
0.425
0.554
m3
b 105
mol
2.38
4.31
3.74
3.05
[D]
[cm x 1025]
0
0
1.47
1.85
2.1
26
22.2
14.8
The values of a for helium is two orders of magnitude less than the other species since it only has
weak dispersion forces (small atom, small ). The values of a for methane, ammonia, and water
are of the same magnitude because the sums of the intermolecular attractions for each molecule
are similar. All three molecules have comparable dispersion forces; although slightly weaker in
the ammonia and water. However, unlike methane, these two molecules also have dipole-dipole
and induction forces. In fact, the strong dipole in water gives it the largest value
The values of b are all of the same magnitude, as expected since b scales with size according to
the number of atoms in the molecule.
Size of Molecules:
Value of b:
22
4.16
The van der Waals b parameter can be calculated using Equation 4.40.
b=
RTc
8 Pc
Critical point data can be found in Table A.1.1. The following table was made:
Tc [K ]
Species
Pc 10 -5 [Pa ]
CH4
C6H6
CH3OH
190.6
46.00
562.1
48.94
512.6
80.96
J
Note: Used R = 8.314
for calculation of a.
mol K
m3
b 10 5
mol
4.306
11.94
6.58
=3
3b
2N A
The table listed below was created using this equation, and data from Table 4.2 are included
along with the percent difference.
Species
1010 [m]
CH4
C6H6
CH3OH
3.24
4.56
3.74
23
Percent
Difference
14.7
13.5
3.8
4.17
The van der Waals a parameter can be calculated using Equation 4.39. The values for the above
equation were taken from Table A.1.1, and the following table was made:
Tc [K ]
Species
J m3
a
2
mol
0.2303
1.883
0.9464
Pc 10 -5 [Pa ]
CH4
C6H6
CH3OH
190.6
46.00
562.1
48.94
512.6
80.96
J
Note: Used R = 8.314
for calculation of a.
mol K
The equation from page 187 can be used to find C6.
a=
2N a2C6
3 3
3a 3
C6 =
2N a2
The values can be found in Table 4.2. The following table can now be created
Species
1010 [m]
CH4
C6H6
CH3OH
3.8
5.27
3.6
C 6 10 77 J m 6
1.66
36.3
5.82
To compare the values obtained from Equation 4.13, first calculate the potential energy with
Equation 4.13:
3 i j
2 r6
Ii I j
Ii + I j
II
3
i j i j
2
Ii + I j
Therefore
C6 =
We obtain the following values using this equation, and the corresponding percent differences
were calculated.
24
Species
CH4
C6H6
CH3OH
C 6 10 77 J m 6
Page 187
Equation 4.13
1.66
1.021
36.3
12.0
5.82
1.36
Percent Difference
63
202
328
The values for the van der Waals a constant have the correct qualitative trends and order of
magnitude; however, those values predicted from basic potential theory vary significantly from
corresponding states. The basic potential result presented in the text assumes that the species are
evenly distributed throughout the volume. It does not take into account the structure given to the
fluid through intermolecular forces. In fact, a more careful development includes a radial
distribution function, which describes how the molecular density of the fluid varies with r. The
radial distribution function depends on pressure and temperature of the fluid.
25
4.18
P=
RT
a
v b v2
Redlich-Kwong
P=
RT
a
1/2
v b T v(v + b)
Peng-Robinson:
P=
RT
a(T )
v b v(v + b) + b(v b)
As you may have discovered, these equations are largely empirical with no theoretical
justification. They simply represent experimental data better. We can use our knowledge of
intermolecular forces, however, to explain why these may work better.
If we compare these equations to the van der Waals equation, we note that the first term
on the right hand side of all three equation is identical; we accounted for this term as a correction
for finite molecular size (or alternatively repulsive interaction due to the Pauli Exclusion
Principle). This form represents a hard sphere model.
The second term, that which deals with intermolecular attraction, is different in all three
models. Both of the later equations include a temperature dependence in this term. We have
seen that if attractive forces depend on orientation (dipole-dipole), they fall off with T as a result
of the averaging process (recall discussion of Equation 4.11).
Another explanation goes as follows: as T increases, the molecules move faster, reducing
the effect of intermolecular forces. If we say that the potential energy between two molecules
depends on the amount of time that they spend close to each other, then it would be inversely
related to velocity (The faster molecules are moving, the less time they spend in the vicinity of
other species). In this case, the correction term would go as V-1, where V is the molecular
velocity. If we relate molecular velocity to temperature
2
1
2 mV
= 32 kT
Therefore the correction term goes as T-1/2, as shown in the Redlich-Kwong equation.
The inclusion of a "b" term in the second term may help relax van der Waal's "hard
sphere" model with a more realistic potential function, i.e., something closer to a Lennard Jones
potential (Figure 4.8) than the Sutherland potential (Figure 4.7) upon which the van der Waals
equation is based. It makes sense that this should be included in the force correction since this is
taking into account repulsive forces. One example of a more detailed explanation follows:
If we look at the Redlich-Kwong equation, it says that if we have 2 species with the same
attractive strength (same a -> same magnitude of van der Waals forces), the larger species will
have less of an effect on P. The following sketch illustrates how 2 species could have the same
van der Waals attractive forces:
26
- +
London
= London
+
Dipole
Species 2
larger and non-polar
(larger b, same a)
Species 1
smaller and polar
(smaller b, same a)
In the case above, when the two species are the same distance apart, they have the same
attractive force; however, the smaller species (1) can get closer before its electron cloud
overlaps. Thus it has more opportunity for attractive interactions than the larger species. The
Peng-Robinson equation exhibits the most complicated form in an attempt to better fit
experimental data.
27
4.19
(a)
Work is defined as follows
W = PdV
Substitution of the ideal gas law for P yields
W =
nRT
dV
V
1 [L]
J
W = (2.0 [mol]) 8.314
(1000 [K ])ln
mol K
10 [L]
W = 38.29 kJ
(b)
Instead of substituting the ideal gas law into the definition of work, the Redlich-Kwong equation
is used:
v2
W = n
v1
RT
a
dv
1
/
2
v b T v (v + b)
Substituting
J
R = 8.314
mol K
T = 1000 [K ]
n = 2 [mol]
J K1/2 m 3
a = 14.24
2
mol
3
5 m
b = 2.1110
mol
m3
v1 = 0.0005
mol
m3
v2 = 0.005
mol
28
(c)
Energy balance:
u = q + w
Since the process is reversible
q = Ts
and
w = u Ts
To use the steam tables conveniently, we need the initial and final pressures. We can calculate
these with the Redlich-Kwong EOS:
P1 = 1.65 MPa
P2 = 15.6 MPa
kJ
u1 = 3522.6
kg
kJ
u 2 = 3462.2
kg
kJ
s1 = 8.101
kg K
kJ
s2 = 7.00
kg K
Therefore,
kJ
kJ
kJ
kJ
w = 3462.2 3522.6 (1000 K ) 7.00
8.101
kg
kg
kg
K
kg
kJ
w = 1040
kg
W = 37.5 [kJ ]
The answers from the three parts agree very well. Part (a) is not as accurate as Part (b) and Part
(c) because water is not an ideal vapor. The value from Part (b) is 1.1 % smaller than the value
from Part (c). Clearly, the Redlich-Kwong EOS or steam tables are appropriate for this
calculation.
29
4.20
First, we can obtain an expression for the compressibility factor with the van der Waals equation.
1
a
Pv
v
a
=
b RTv
RT v b RTv
1
v
To put this equation in virial form, we can utilize a series expansion:
1
= 1 + x + x 2 + x 3 + ...
1 x
Therefore,
2
1
b b
= 1 + + + ...
b
v v
1
v
and
a
2
Pv
RT b
= 1+
+ + ...
v
RT
v
This expression can also be expanded in pressure. From Equation 4.58, we know that
B' =
C'=
B
RT
C B2
(RT )2
where
Pv
= 1 + B' P + C ' P 2 + ....
RT
Substituting B and C found above, we get
B' =
b(RT ) a
(RT )2
and C ' =
2ab(RT ) a 2
(RT )4
Therefore,
30
b(RT ) a
Pv
P + 2ab(RT ) a P 2 + ....
= 1+
(RT )2
RT
(RT )4
31
4.21
Using the virial expansion, the pressure can be written as follows
1 B C
P = RT +
+
+ ...
v v 2 v3
The virial expansion in pressure is
P=
RT
1 + B' P + C ' P 2 + ...
v
1 B C
1 B C
RT
1 B C
+
+ ... =
+
+ C ' RT +
+
RT +
1 + B ' RT +
2
v
v v 2 v 3
v
v
v3
v v 2 v3
If we combine like terms on the right side and set them equal to terms on the left, we find
B = B' RT
C = BB' RT + C ' (RT )2
Substitute the expression for B into the expression for C and solve for C:
C' =
CB
(RT )2
and
B' =
B
RT
32
4.22
At the critical point we have:
Pc =
RTc
a
vc b Tc vc2
(1)
RTc
2a
P
+
=0=
2
v Tc
(vc b ) Tc vc3
(2)
2
2 RTc
6a
P
2 =0=
3
Tc vc4
v
(
vc b )
Tc
(3)
4a
vc3
6a(vc b )
vc4
9
vc RTc2
8
Finally, if we plug this back into Equation 1 we can solve for the Berthelot constants in terms of
the critical temperature and the critical pressure:
a=
27 R 2Tc2
64 Pc
and
b=
RTc
8Pc
33
4.23
Before we can find the reduced form, we need to find expressions for a and b in terms of critical
point data (Problem 4.22). We find
vc = 3b
(1)
27 R 2Tc3
a=
64 Pc
RTc
b=
8 Pc
(2)
(3)
RT
a
v b Tv 2
First, substitute Equation 1 into the first term on the right-hand side and rearrange to get
RT
a
P= b
3vr 1 Tv 2
Now, substitute Equation 3:
P=
8 PcTr
a
3v r 1 Tv 2
Substitute Equation 2:
P=
8 PcTr
3v r 1
27 R 2Tc3
64 Pc
Tv 2
From Equation 3:
R 2Tc2 = 64 Pc2 b 2
Substituting this result, we get
P=
8PcTr 27 PcTc b 2
3v r 1
Tv 2
34
3v r 1
Tv 2
8Tr
3
3vr 1 Tr vr2
35
4.24
(a)
The virial equation is:
z=
Pv
D
B C
= 1 + + 2 + 3 +...
RT
v v
v
(1)
(z 1)v =
(2)
PvT data from the steam tables are given in the steam tables and corresponding values of (z-1)v
and 1/v can be calculated. An illustrative plot of (z-1)v vs. 1/v for T = 300 oC is shown below.
Plot to determine the second virial coeff at 300 C
-115
-120
-125
(z -1)v
-130
1.5
0.5
-135
1/v (mol/l )
We see that at pressures above 1.5 MPa (15 bar) we see that the plot reaches a constant value of
around -118 cm3/mol. We may choose to report this value as B. A more careful examination of
Equation 2 suggests another possibility.
If we plot (z-1)v vs. 1/v, we should get a straight line at low to moderate pressures with an
intercept equal to the second virial coefficient, B, and a slope equal to the third virial coefficient,
C. At very low pressures, the curve is indeed linear and gives an intercept of -140 cm3/mol, as
shown on the next page. The slope of this region would yield the third virial coefficient, C.
Can you calculate C?
36
The first value uses much more data while the second method uses limited data in a better range.
What value would you be more apt to use? Water exhibits this odd general behavior at all
temperatures.
Plot to determine the second virial coeff at 300 C
-115
-120
y = 177.058x - 140.373
-125
(z -1)v
-130
lin
1.5
0.5
-135
1/v (mol/l )
If we do this at other values of T, we can compile a set of second virial coefficients vs.
temperature and get an idea of the differences in the two approaches. Temperatures of 200, 250,
300, 350, 400, 500, 600, 700, 800, 900, 1000, and 1200 oC analyzed in this manner. The results
are reported in the table and figure below. Also reported were the average value and the value at
the lowest pressure used. Note that the average value is indicative of the 1st method above while
the value at the lowest pressure used is indicative of the second value used.
T
200
250
300
350
400
500
600
700
800
900
1000
1200
B (Level)
-214
-156
-118
-89
-72
-49
-34
-24
-17
-13
-9
-3
B (Linear)
-226
-173
-140
-102
-103
-83
-73
-68
-66
-51
-50
-51
37
B (AVG)
-215
-157
-120
-92
-76
-54
-39
-30
-24
-19
-16
-11
B(1st value)
-220
-168
-134
-99
-95
-75
-63
-57
-54
-52
-52
-52
B (water) cm 3 /mol
-50
-100
B (average)
B (lowest P)
-150
B (Level)
-200
B (Linear)
CRC
1500
1250
1000
750
500
250
-250
T (K)
For comparison, values of -142.2 cm3/mol and -7160 cm6/mol2 are reported for B and C,
respectively, at 260 oC1. Values of B reported in the CRC are also shown on the summary plot.
They agree most closely with the first (level) method.
(b)
There are several alternatives how to solve this problem, each of which comes up with a slightly
different result:
Alternative 1:
Rewrite the virial equation:
1 BH 2 O
P = RT +
+ ...
v2
v
Take the derivative:
1 2 BH 2 O
P
= 0 = RTc 2
v
v Tc
v 3c
so
cm3
v
BH 2O = c = 28
2
mol
J.H. Dymond and E.B. Smith, The Virial Coefficients of Pure Gases and Mixtures, A Critical Compilation, Oxford
University Press, Oxford, 1980.
38
Alternative 2:
From the virial equation:
cm3
Pv
BH 2O = c c 1vc = 43.2
mol
RTc
Alternative 3:
1 BH 2 O C H 2 O
P = RT +
+
+ ...
v2
v3
v
so
1 2 BH 2O 3C H 2O
P
= 0 = RTc 2
3
v
v Tc
v
v 4c
c
(1)
2P
6B
12C H 2O
= 0 = RTc 2 + H 2O +
4
5
v 2
v3
vc
vc
Tc
(2)
and
2
v 3c
2 BH 2 O
v 4c
=0
so
cm3
BH 2O = vc = 56
mol
39
4.25
A trial-and-error is the easiest method for solving this problem. The general method is as
follows
1. Guess P sat
2. Calculate values of molar volumes that result at the chosen P sat : vlow , vmid , vhigh
3. Find areas under the curves with the following expressions
[P
v mid
sat
f (v ) dv
v low
[ f (v ) P
v high
sat
]dv
v mid
1. Guess P sat :
P sat = 6 [bar ]
P sat =
1
/
2
v b T v (v + b )
J K1/2 m 3
J
41
.
851
8.314
2
(363.15 [K ])
mol
mol
K
6 105 [Pa ] =
m3
3
v 0.0001
(363.15 K )1 / 2 v v + 0.0001 m
mol
mol
m3
m3
m3
=
0
.
000551
=
0
.
00459
vlow = 0.000152
v
v
high
mid
mol
mol
mol
3.
0.000551
a
sat RT
dv = 1157.19
P
v b T 1 / 2 v (v + b )
0.000152
0.00459
a
RT
P sat dv = 1325.78
v b T 1 / 2 v (v + b )
0.000551
40
4. Repeat this process until the areas are equal. This occurs approximately at
P sat = 6.38 [bar ]
(b)
1. Guess Psat :
Psat = 6 [bar ]
2. Calculate molar volume solutions for
P sat =
RT
a (T )
v b v(v + b) + b(v b )
using
m3
J m3
a = 2.066
, b = 9 10 6
, (T ) = 1.188
2
mol
mol
m3
m3
m3
=
0
.
000551
=
0
.
00459
vlow = 0.000152
v
v
high
mid
mol
mol
mol
3.
sat
RT
a (T )
P v b v(v + b) + b(v b ) dv = 1568.48
0.000152
0.000551
RT
a (T )
sat
v b v(v + b) + b(v b ) P dv = 1100.19
0.000551
0.00459
4. Repeat this process until the areas are equal. This occurs approximately at
P sat = 4.945 [bar ]
The value calculated with the Redlich-Kwong EOS is 11.9% greater than the measured value of
5.7 bar. The Peng-Robinson EOS results in a value that is 13.25% less than the measured value.
41
4.26
First, calculate a , b , and (T ) . From Table A.1.1:
Pc = 48.84 [Pa ]
Tc = 305.4 [K ]
w = 0.099
a=
J
(305.4 [K ])
0.45724 8.314
mol K
J m3
= 0.6036
2
mol
J
0.07780 8.314
(305.4 [K ])
mol K
= 4.045 10 5
b=
5
48.84 10 [Pa ]
(T ) = 1.12
m3
mol
243.15 K
3
05.4
K
RT
a (T )
v b v(v + b) + b(v b )
m3
3
3 m
=
,
v
1
.
578
10
mol
mol
The molar volume of saturated ethane liquid is the smallest value from the list above, while the
molar volume of saturated ethane vapor is the largest value. Therefore,
42
g
36.0694
3
(MW )ethane
mol 1 m
= 0.501 g
=
liq =
3
liq
3
3
3 (100 ) cm
v
cm
5 m
7.199 10
mol
g
36.0694
3
(MW )ethane
mol 1 m
= 0.0229 g
=
vap =
3
3 (100 )3 cm 3
v vap
cm
3 m
1.578 10
mol
Both of the densities calculated with the Peng-Robinson EOS are larger than the reported values.
The liquid density is 7.05% larger, and the vapor density is 18.7% greater.
43
4.27
(a)
We will use the Redlich-Kwong EOS in order to obtain an accurate estimate. First, calculate the
a and b parameters:
a=
J m 3 K1 / 2
0.42748R 2Tc2.5
= 1.56
Pc
mol 2
m3
mol
(Note: Critical data for nitrogen obtained in Table A.1.1.)
0.08664 RTc
= 2.69 10 5
b=
Pc
RT
a
1
/
2
v b T v(v + b )
Assume the temperature of the gas is 22 C, substitute values, and find the molar volume with a
solver function:
m3
v = 1.97 10 4
mol
Now calculate the total volume of gas in the 30,000 units:
Vtotal = (30000 units )(43 [liter/unit ]) = 1.29 10 6 liters = 1290 m 3
Therefore, the number of moles is:
n=
1290 m 3
= 6.55 10 6 mol
3
m
1.97 10 4
mol
44
J
(295 K )
8.314
RT
mol K
= 1.98 10 4
=
v=
P
12400000 Pa
m3
mol
J m 3 K1 / 2
0.42748R 2Tc2.5
= 1.74
a=
Pc
mol 2
m3
mol
(Note: Critical data for oxygen obtained in Table A.1.1.)
b=
0.08664 RTc
= 2.21 10 5
Pc
Assume the temperature of the gas is 22 C, substitute values, and find the molar volume with a
solver function:
m3
v = 1.53 10 4
mol
Following the steps presented in Part (a), we find that
Value = $2,428,000
With the ideal gas law, we find
m3
v = 1.64 10 4
mol
which provides
Value = $2,265,000
45
The value found with the ideal gas law is $163,000 less than the value found using the RedlichKwong EOS.
46
4.28
First, rewrite the Redlich-Kwong equation in cubic form.
v3
RT 2 a
RT
ab
v +
b b 2 v
=0
P
P
PT 1 / 2
PT 0.5
RTc 2 a
RT
ab
v +
c b b 2 v
=0
0
.
5
0.5
Pc
P
P
T
P
T
c
c c
c c
Now expand (v vc )3 = 0
v 3 3v 2 vc + 3vvc2 vc3 = 0
Setting the coefficients equal we get the following expressions.
3vc =
RTc
Pc
3vc2 =
vc3 =
(1)
PcTc0.5
ab
RTc
b b2
Pc
(2)
(3)
Pc Tc0.5
RT
a = 3vc2 + C + b 2 Pc Tc0.5
PC
b = 21 / 3 1 vc
(4)
47
b=
0.08664 RTc
Pc
(Equation 4.48)
Now, substitute Equation 1 and Equation 4.48 into the expression for a to get
a=
0.42748RTc2.5
Pc
(Equation 4.47)
Pv
To verify Equation 4.50, substitute Equation 1 into z c = c c
RTc
RT
Pc c
3Pc
zc =
RTc
=1
3
(Equation 4.50)
RT
a
v b T 0.5v(v + b )
3Tr Pc
a
0
.
5
v r 0.2599 T vvc (v r + 0.2599 )
3Tr Pc
0.42748R 2Tc2.5
Pc2 b 2
(0.08664)2
48
3Tr Pc
Pc b 2
0.42748
3Tr Pc
Pc
0.42748 (0.2599 )2
v r 0.2599
Tr0.5 v r (v r + 0.2599)
(0.08664)2
Therefore,
Pr =
3Tr
1
0
.
5
vr 0.2599 0.2599Tr vr (vr + 0.2599)
49
(Equation 4.49)
4.29
Since we are concerned with liquid water, we can base all our calculations on saturated liquid
water since the molar volume of liquids are weakly dependent on pressure. Therefore, our
results are also applicable to sub-cooled water (the pressure is greater than the saturation
pressure). To find the thermal expansion coefficient, we will use the following approximation
v sat (T + 5 C ) v sat (T C )
1 v sat (T + 5 C ) v sat (T C )
=
10 K
v sat (T ) (T + 5 C ) (T 5 C ) v sat (T )
This approximation is valid even though the saturation pressure changes because molar volume
is weakly dependent on pressure. From the steam tables
m3
v sat (15 C ) = 0.001001
kg
m3
v sat (20 C ) = 0.001002
kg
m3
v sat (95 C ) = 0.001040
kg
m3
v sat (100 C ) = 0.001044
kg
m3
v sat (25 C ) = 0.001003
kg
m3
v sat (105 C ) = 0.001047
kg
m3
m3
0
.
001003
0
.
001001
kg
kg
m3
(20 C ) = 0.001002
10 K
kg
m3
m3
0.001040
1 0.001047
kg
kg
m3
(100 C ) = 0.001044
10 K
kg
[ ]
(100 C ) = 6.71 10 [K ]
(20 C ) = 2.0 10 4 K -1
4
-1
The accuracy of these values may be limited since they are based on the small differences
between liquid volumes.
To calculate the isothermal compressibility, a similar approximation will be used. It is
50
dv sat
v sat (T ) dP
1
v = -5E-07*P + 0.001044
R2 = 0.9949
0.001040
0.001050
0.001030
T = 20C
T = 100 C
0.001020
Linear (T = 100 C)
Linear (T = 20C)
0.001010
v = -5E-07*P + 0.001002
R2 = 0.9979
0.001000
0.000990
0
10
15
20
Pressure [MPa]
It is clear that
dv sat
dP
dv sat
=
= 5 10 7
dP
T = 20 0 C
T =100 0 C
m3
kg MPa
Therefore,
m3
(20 C ) = 0.001002
kg
5 10 7
m3
kg
MPa
1
1
= 4.99 10 10
Pa
MPa
(20 C ) = 4.99 10 4
m3
(100 C ) = 0.001044
kg
5 10 7
m3
kg
MPa
1
1
= 4.79 10 10
(100 C ) = 4.79 10 4
MPa
Pa
51
25
4.30
(a)
Substitute critical data into the Rackett equation:
vcalc =
46 10
cm 3
vcalc = 38
mol
Now, calculate the error.
v
calc vexp
Error =
vexp
Error = 0.8%
100 %
(b)
cm 3
vcalc = 54.2
mol
Error = 1.1%
cm 3
vcalc = 161.2
mol
Error = 10.8%
cm 3
vcalc = 20.5
mol
Error = 13.5%
cm 3
vcalc = 68.5
mol
Error = 19.7%
(c)
(d)
(e)
1-hexanol had the largest percent error, while ethane and methane had the smallest percent
errors. The alkenes have low percentile errors due to their nonpolar nature, which the alcohols
and acids had large percentile errors due to being polar substances and exhibiting hydrogen
bonds.
52
4.31
(a)
Since we are given the temperature and pressure, we can make use of the generalized
compressibility charts. Using data from Table A.1.1, the required quantities can be found.
343.15 [K ]
T
=
= 1.12
305.4 [K ]
Tc
30 [bar ]
P
=
= 0.616
Pr =
Pc 48.74 [bar ]
w = 0.099
Tr =
and
Therefore,
V=
znRT
=
P
30 [kg ]
J
8.314
(343.15 [K ])
mol K
0.03007 [kg/mol]
(0.8393)
[ ]
[30 10
[Pa ]]
V = 0.796 m 3
(b)
The Redlich-Kwong EOS should give reasonably accurate results. Room temperature was
assumed to be 25 C. The molar volume is required for the calculations, so
v =V =
( [ ])
V
0.1 m 3
=
= 7.518 10 5
n
40 [kg ]
[
]
0
.
03007
kg/mol
m3
mol
Using data from Table A.1.1 and Equations 4.47 and 4.48,
J m 3 K1 / 2
a = 9.88
2
mol
53
3
5 m
=
b 4.51 10
mol
Substituting these values into the Redlich-Kwong EOS and evaluating gives
P = 191.3 [bar ]
54
4.32
(a)
For propane
n =
50 [kg ]
= 1130 [mol]
kg
0.0441
mol
V =
nRT
=
P
[ ]
J
(50 + 273.15 K )
mol K
35 105 [Pa ]
V = 0.870 m 3
(b)
The Redlich-Kwong EOS is
P=
RT
a
v b T 1 / 2 v(v + b )
a=
J m 3 K1 / 2
0.42748R 2Tc2.5
= 18.33
Pc
mol 2
where
m3
mol
(Note: Critical data for propane obtained in Table A.1.1.)
b=
0.08664 RTc
= 6.28 10 5
Pc
Now that these values are known, there is only one unknown in the Redlich-Kwong EOS: v .
Using a numerical technique, e.g., the solver function on a graphing calculator
m3
v = 0.000109
mol
[ ]
V = 0.124 m 3
55
(c)
The Peng-Robinson EOS is
P=
RT
a (T )
v b v(v + b ) + b(v b )
where
[ (
= 1 + 1 Tr
Tr =
)]2
= 1.081
a=
J m3
0.45724(RTc )2
= 1.02
Pc
mol
0.07780 RTc
b=
= 5.64 10 5
Pc
m3
mol
mol
[ ]
V = 0.107 m 3
(d)
We must calculate the reduce temperature and pressure to use the compressibility charts:
323.15 K
T
=
= 0.873
370 K
Tc
35 bar
P
=
= 0.825
Pr =
Pc 42.44 bar
Tr =
Therefore,
56
Pv
= z = z (0 ) + wz (0 ) = 0.1349 + 0.152( 0.052) = 0.127
RT
m3
0.127 RT
= 0.00009749
v=
P
mol
V = 0.111 m 3
(e)
From ThermoSolver
Using the Peng-Robinson equation,
m3
v = 0.00009429
mol
[ ]
V = 0.107 m 3
mol
Therefore,
[ ]
V = 0.110 m 3
57
4.33
Note: Multiple possibilities exist for which substance to use in the vial. The solution using one
possibility is illustrated below.
(a)
The substance must have a critical temperature above room temperature but below the
temperature of ones hand. From the Appendix A.1.2, we that for carbon dioxide
Tc = 304.2 K = 31.1 C
Clearly, CO2 is a suitable substance, and it is safe to use.
(b)
The vial must be able to withstand the pressure of the substance at its critical point. Therefore,
the vial must withstand 73.76 bar (the critical pressure of carbon dioxide).
(c)
Since the substance passes through its critical point, the molar volume at that state is constrained
by the critical temperature and pressure. To estimate the molar volume, we can use the PengRobinson EOS. Calculate the necessary parameters for the EOS:
2
a = 0.45724
J
8.314
(304.2 K )2
mol K
73.76 10 5 [Pa ]
J m3
= 0.40
2
mol
J
8.314
(304.2 K )
mol K
b = 0.07780
= 3.4 10 4
5
73.76 10 [Pa ]
=1
m3
mol
Substitute the above parameters and solve for the molar volume:
cm 3
m3
vc = 1.18 10 4
118
=
mol
mol
Now, we can calculate the required amount of CO2.
n=
[ ]
100 cm 3
V
=
= 0.847 mol
vc
cm 3
118
mol
58
(d)
If the vial contains less substance than needed, the molar volume will be greater. Therefore, the
substance will not pass through the critical point. As the substance is heated, it will go through a
transition from a saturated liquid and vapor mixture to superheated vapor. Then, it will become a
supercritical fluid once the critical temperature is exceeded.
P
critical
point
liquid
part c
part d
not enough
CO2
vapor
liquid - vapor
59
4.34
Methane:
The following quantities are required to calculate the molar volume with the Peng-Robinson
equation.
[ (
(T ) = 1 + 1 Tr
(T ) = 0.9626
)]2
a=
J m3
0.45724(RTc )2
= 0.25
Pc
mol
b=
0.07780 RTc
= 2.68 10 5
Pc
T = Tr Tc = 209.66 [K ]
m3
mol
P = Pr Pc = 55.2 10 5 [Pa ]
The molar volume is the only unknown in the following equation.
P=
RT
a (T )
v b v(v + b ) + b(v b )
v = 1.83 10
m3
mol
Therefore,
3
4 m
mol
z=
= 0.58
J
8.314
(209.66 [K ])
mol K
Therefore,
z = z (0 ) + wz (1) = 0.5984 + (0.008)0.0897
z = 0.599
60
Methanol:
mol
z = 0.651
Using the compressibility charts:
z (0 ) = 0.5984
z (1) = 0.0897
Therefore,
z = z (0 ) + wz (1) = 0.5984 + (0.559 )0.0897
z = 0.649
Summary:
Methane
z = 0.58 (Peng-Robinson)
z = 0.599 (Compressibility charts)
The value from the Peng-Robinson EOS is 3.2% smaller than the value
from the charts.
Methanol
z = 0.651 (Peng-Robinson)
z = 0.649 (Compressibility charts)
The value from the Peng-Robinson EOS is 0.31% smaller than the value
from the charts.
61
4.35
From Table A.1.1:
Tc = 405.6 K
Pc = 112.77 bar
w = 0.25
Calculate reduced temperature and pressure:
Tr =
z (1) = 0.1351
Therefore,
Pv
= z = z (0 ) + wz (1) = 0.38
RT
and
v=
0.38RT
= 3.76 10 5
P
m3
mol
Since the temperature of the ammonia in this system is below the critical temperature, we know
the ammonia is not a supercritical fluid. The pressure is greater than the critical pressure, so the
ammonia is a liquid.
62
4.36
Let the subscript ace represent acetylene and but represent n-butane. First, convert the given
quantities of acetylene and n-butane into moles.
nace =
nbut =
30 [kg ]
26.038 10
-3
50 [kg ]
58.123 10
-3
kg
mol
kg
mol
= 1152.2 [mol]
= 860.2 [mol]
Therefore,
y ace = 0.573
ybut = 0.427
We can also calculate a and b parameters for pure species using the following equations
0.42748 R 2Tc2.5
a=
Pc
b=
0.08664 RTc
Pc
2
mol
J K1/2 m 3
abut = 29.07
mol
m3
bace = 3.62 10 5
mol
m3
bbut = 8.08110 5
mol
Now, we can use mixing rules to calculate the parameters for the mixture.
amix = y12 a1 + 2 y1 y 2 a12 + y 22 a2
J K1/2 m3
a12 = 8.03 29.07 (1 0.092) = 13.87
2
mol
J K1/2 m 3
amix = 14.72
2
mol
63
m3
mol
Substitution of the mixture parameters into the Redlich-Kwong EOS results in an equation with
one unknown.
m3
v = 0.00111
mol
m3
mol
[ ]
V = 2.23 m 3
64
4.37
First, we need to calculate the a and b parameters for species (1) and (2). From Table A.1.1 and
A.1.2:
CO2 (1):
Toluene (2):
Tc = 304.2 [K ]
Pc = 73.76 [bar ]
a1 =
J m 3 K1/2
0.42748R 2Tc2.5
= 6.466
Pc
mol
b1 =
0.08664 RTc
= 2.97 10 5
Pc
m3
mol
Tc = 591.7 [K ]
Pc = 41.14 [bar ]
J m 3 K1/2
0.42748R 2Tc2.5
a2 =
= 61.17
Pc
mol
b1 =
0.08664 RTc
= 1.036 10 4
Pc
m3
mol
5
mol
3
5 m
bmix = 7.40 10
mol
m 3 3 mol
4
+
1.036 10
mol
5
mol
m3
mol
Now we can substitute the known values into the Redlich-Kwong EOS. Note that the molar
volume can be calculated as follows
v=
[ ]
m3
0.01 m 3
V
=
= 0.002
5 [mol]
ntot
mol
mol
65
Therefore,
J m 3 K1/2
a12 = 16.55
mol
66
4.38
(a)
We can match the species by looking at the b parameter alone. The b parameter is directly
related to the size of the molecule. Because sizeC 2 H 6 > size H 2 O > size H 2 ,
bC 2 H 6 > bH 2 O > bH 2 . Therefore,
J m3
a
mol
0.564
m3
b
mol
Species
6.38 10 5
C2H6 (3)
0.025
2.66 10 5
H2 (1)
0.561
3.05 10 5
H2O (2)
These values are also consistent with what we would expect for the magnitude of van der Waals
interactions given by a.
(b)
The van der Waals parameters for the mixture can be calculated according to the mixing rules.
From Equations 4.81 and 4.82
a mix = y12 a1 + y1 y 2 a12 + y1 y3 a13 + y 2 y1 a21 + y 22 a 2 + y 2 y3 a 23 + y3 y1 a31 + y3 y 2 a32 + y32 a3
a mix = y12 a1 + 2 y1 y 2 a12 + 2 y1 y3 a13 + y 22 a2 + 2 y 2 y3 a 23 + y32 a3
bmix = y1b1 + y 2b2 + y3b3
Since binary interaction parameters are not available, we must use Equation 4.78 to calculate
a12 , a13 , a23 .
J m3
a12 = a1a2 = 0.118
mol
J m3
a13 = 0.119
mol
67
J m3
a23 = 0.562
mol
Now we can find the numerical values for the van der Waals parameters.
J m3
amix = 0.206
mol
m3
bmix = 3.19 105
mol
(c)
For the mixture, the van der Waals equation is
P=
a
RT
mix
v bmix
v2
[ ]
m3
0.0125 m 3
V
=
= 0.00125
10 mol
n1 + n2 + n3
mol
Therefore,
J m3
J
0
.
206
8.314
(300 K )
mol
mol
K
P=
3
3
m3
0.00125 m 3.19 10 5 m
0.00125
mol
mol
mol
P = 1.92 MPa
68
4.39
(a)
To calculate the molar volume of the mixture, we will use the virial expansion in pressure since
it is more accurate at moderate pressures. But first, we must calculate the second virial
coefficient for the mixture.
cm 3
cm 3
cm 3
2
(
)(
)
(
)
0
.
75
110
2
0
.
25
0
.
75
153
Bmix = (0.25)2 625
+
mol
mol
mol
cm 3
Bmix = 158.3
mol
Therefore,
RT Bmix RT
P =
+ Bmix
1 +
P
RT P
cm 3
m3
v = 2445.6
= 0.002446
mol
mol
v=
(b)
We can estimate k12 using an EOS where the a parameter is the only unknown. b can be
calculated as follows
m3
5
+ 0.75 2.97 10
mol
m3
3
5 m
= 3.69 10
mol
mol
Substitute the known properties into the Redlich-Kwong EOS and solve for a.
J K1/2 m 3
amix = 8.693
2
mol
69
J K1/2 m 3
a1 = 28.03
2
mol
J K1/2 m 3
a2 = 6.466
2
mol
J K1/2 m 3
a12 = 8.81
2
mol
70
4.40
During this process the gas in Tank A undergoes an expansion from 7 bar to 3.28 bar. During
this isentropic process, the gas cools. If attractive forces are present, they will manifest
themselves more in state 1 at the higher pressure than in state 2. (While T has some effect to
counter this trend, we expect it will be secondary to the effect of pressure). Thus, in the nonideal case, additional energy must be supplied to pull the molecules apart. Since the tank is
insulated, the only place that this can come from is the kinetic energy of the molecules. Thus,
they slow down even more than in the ideal gas case, and the final temperature is lower. If we
had an equation of state that appropriately described the non-ideal behavior, we could apply the
concepts of the thermodynamic web that we have learned in this chapter to solve for the final
temperature.
71
4.41
Select the Equation of State Solver from the main menu. Enter the pressure and temperature
and solve for the molar volume using the Lee-Kesler EOS. The program provides
m3
v = 1.07 10 4
mol
To calculate the volume occupied by 10 kilograms of butane, we need to know the number of
moles present in 10 kg.
n=
10 [kg ]
= 172.1 [mol]
0.05812 [kg/mol]
Therefore,
V = (172.1 [mol])1.07 10 4
[ ]
m3
3
= 0.018 m
mol
The answers provided in Example 4.9 agree well with this answer. The answer found using the
Redlich-Kwong EOS is 16.7% larger than the answer from ThermoSolver, but the answer from
the compressibility charts is only 5.56% larger.
72
4.42
Using ThermoSolver should be straightforward; thus, only the answers are provided.
(a)
Tc = 305.4 [K ]
Pc = 48.84 [bar ]
kJ
h of ,298 = 84.68
mol
(b)
Tsat = 299.42 [K ]
(c)
The percent difference is calculated as follows
v LK v PR
z LK z PR
% Difference =
or
100 %
v LK
z LK
(i).
Quantity
v
z
mol
0.1383
mol
0.1444
% Difference
mol
0.5859
mol
0.5711
% Difference
4.3
4.4
(i).
Quantity
v
z
73
2.7
2.5