Chapter 4 Solutions Engineering and Chemical Thermodynamics

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.,:

PA+ > Pideal

Coulombic forces are much stronger than van der Waals interactions, so a will be large much larger than a values for the van der Waals EOS. (c) Coulombic repulsion is the primary intermolecular force present in the gas. Coulombic potential energy is proportional to r-1. v is proportional to r3, so the coulombic potential goes as v-1/3. Therefore,

n=

1 3

a must have must have the following units to maintain dimensional homogeneity with the pressure term:
a N J = = 1/ 3 2 3 m m v
so

[a] =

J 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

From Table 4.1:

I a = 12.07 [eV ] = 1.933 10 11 [erg ]

I b = 10.94 [eV] = 1.753 10 11 [erg] Now obtain the requested expressions:

3 16 10 25 cm 3 aa = 2 r6
aa = 3.71 10 59 r
6

[ ]) (1.933 10
2
6

[cm

erg 1.933 10 11 erg 1.933 10 11 erg + 1.933 10 11 erg

11

)(

erg

ab = ab =

3 16 10 25 cm 3 62.9 10 25 cm 3 2 r6
6

[ ])(
6

[ ]) (1.933 10
)(

1.39 10 58 r

[cm

erg

]
11

erg 1.753 10 11 erg 11 erg + 1.753 10 11 erg 1.933 10

11

)(

3 62.9 10 25 cm 3 bb = 2 r6

[ ]) (1.753 10
2

bb =
(b) Calculation:

5.20 10 58 r
6

[cm

erg

erg 1.753 10 11 erg 11 erg + 1.753 10 11 erg 1.753 10

5.20 10 58 3.71 10 59 6 cm erg cm 6 erg aa bb = r6 r6

 erg r Note: Disregarded the positive value.

6

aa bb =

1.39 10 58

[cm

The value of similar.

aa bb is equal to ab . The values are equal because the ionization energies are

(c) An expression for the average intermolecular attraction in the mixture can be found using the mixing rules
2 2 mix = y a aa + 2 y a yb ab + yb bb 2 2 3.71 10 59 y a + 1.39 10 58 y a yb + 5.20 10 58 yb 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
2 Bmix = y12 B1 + 2 y1 y2 B12 + y 2 B2

Since BClH2 is polar and H2 is non-polar and small B1 >> Bmix > B2 Therefore, the plot may look like the following.
zH2 close to 1
1

quadradic, not linear

0.9

0.8

zBClH2 lowest

0.7

0.6 0 0.2 0.4 0.6 0.8 1

yBClH2

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

dispersion > dipole - dipole induction The van der Waals EOS is appropriate since it accounts for the occupied molar volume and intermolecular forces, but it should be noted that more modern EOSs will give more accurate results.
(b) Use critical data to calculate the a and b parameters:
J 8.314 mol K (647.15 K ) 2 3 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 ]
2

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 m3 3.13 2 mol 3.0 10 4 m3 mol
2

J 8.314 mol K T 5 10 10 [Pa ] = 3 4 m 3.0 10 1.72 10 4 mol T = 550.8 K = 277.65 C

m3 mol

The styrene will not decompose at this temperature.

(c) The a parameter is related to attractive intermolecular forces. Dispersion is the controlling intermolecular force in this system, and its magnitude is directly related to the size of the molecules (polarizability component of dispersion). For the 5-monomer long polymer chain, a is 5 times the a value in Part (b). The b parameter is also related to the size of the molecule since it accounts for the volume occupied by the molecules. Again, the b parameter for the reduced polymer chain is 5 times the b value from Part (b).

 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 mol 2 8.314 mol K T 5 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

Decomposition will occur.

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

C = 11.4 10 25 cm 3 H = 3.65 10 25

[ ] [cm ]
3

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

[ ]
calculated (x 1025 cm3) 63.4 45.8 65.5 85.3 reported (x 1025 cm3) 62.9 45.6 64.8 82.3

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 % 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

= 4 11.4 10 25 cm 3 + 10 3.65 10 25 cm 3 = 82.1 10 25 cm 3

[ ]) (

[ ])

[ ]

H 5 Cl

= 2 11.4 10 25 cm 3 + 5 3.65 10 25 cm 3 + 1 23.4 10 25 cm 3 = 64.45 10 25 cm 3

[ ]) (

[ ]) (

[ ])

[ ]

Method 2. Bond Polarizability For this method, we calculate the molecules polarizabilities by adding the polarizability of each bond, instead of the atoms. For the methane molecule
4 C H = 1 CH 4 C H =

26 10 25 cm 3 = 6.5 10 25 cm 3 4

[ ]

[ ]

To calculate the polarizability of a C-C bond, use ethane as follows:

6 C H + C C = 1 C 2 H 6

C C = 44.7 10 25 cm 3 6 6.5 10 25 cm 3 = 5.7 10 25 cm 3

[ ] (

[ ])

[ ]

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

= 3 5.7 10 25 cm 3 + 10 6.5 10 25 cm 3 = 82.1 10 25 cm 3

[ ]) (

[ ])

[ ]

1 C 2 H 5 Cl = 1 C C + 5 C H + 1 C Cl

H 5 Cl

= 1 5.7 10 25 cm 3 + 5 6.5 10 25 cm 3 + 1 26.25 10 25 cm 3 = 64.45 10 25 cm 3

[ ]) (

[ ]) (

[ ])

[ ]

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 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 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

n - butanol diethyl ether methyl ethyl ketone

Methyl ethyl ketone and n-butanol are much more polar than diethyl ether due to their greater asymmetry, so their values are greater than diethyl ethers. Now we must determine if there is greater attraction in n-butanol or methyl ethyl ketone. scales with the magnitude of van der Waals interactions. Since induction and dispersion forces are similar in these molecules, we must consider the strength of dipole-dipole forces. There is greater charge separation in the double bond of ketone, so

methyl ethyl ketone > n - butanol > diethyl ether

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 mol K (300 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

)1 / 3 = 1.18 109 [m]

15

r = 11.8 [A ]

(b) The potential energy due to gravity can be calculated as follows

G = G m2 Ar r

m2 where G is the gravitation constant G = 6.67 10 11 and mAr is the mass of an argon 2 kg s atom. The mass of an argon atom is calculated as follows

1 [kg ] 39.948 [g Ar] 1 [mol] - 26 kg m Ar = 1 [mol Ar ] 1000 [g ] = 6.633 10 23 atom 6.023 10 [atoms]
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 +I Ar Ar

From Table 4.1

I Ar = 15.76 [eV] = 2.52 10 -4 [erg]

Ar = 16.6 10 25 cm 3

[ ]

Using the distance calculated in Part (a) r = 1.18 10 7 [cm] , we get

Ar Ar = 1.93 10 10 [erg] = 1.93 10 17 [J ]

(d) The potential energy due to London interactions is around 10 35 times greater than the potential energy due to gravity. Clearly, London interactions are much more important, and gravitational effects can be neglected.

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:

* =
where
r* =

1 1 = 12 6 4 ( ) ( ) r * r *

We want to compare this to an exponential repulsive function

* exp

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 0.1 0 0.9 -0.1 -0.2 -0.3 1 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 2 2.1

Lennard-Jones exponential

Potential functions
20

15

Lennard-Jones exponential

10

0 0.7 -5 1 1.3 1.6 1.9

We draw the following conclusions: 1. The most stable configuration (the bottom of the well) occurs at a greater separation for the exp model. 2. The Lennard-Jones potential increases more steeply at small radii, i.e., it behaves more like the hard-sphere potential. 3. The two models are in reasonable qualitative agreement

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.
=6 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 ]

)(

(b)

=6

QNa QCl Q Q + 12 Na Na r r

= 5.01 10 11 [erg] + 12

(4.803 10

10

= 2.089 10 11 [erg] = 13.0 [eV]

(c)

esu )(4.803 10 10 esu ) 3.90 10 -8 cm

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

We start with Equation 4.19: to get 12 6 = 4 r r Differentiation with respect to r yields 12 12 6 6 d = 4 + = 0 dr rr r r where we set this derivative equal to zero to find the minimum. Solving gives 1 = 2 r
6

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 He CH4 NH3 H2O

Tc [K ] 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. 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] 0 0 1.47 1.85 [cm x 1025]
3

Species He CH4 NH3 H2O

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: CH 4 > NH 3 > H 2O > He bCH 4 > bNH 3 > bH 2O > bHe

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: Species CH4 C6H6 CH3OH Tc [K ] Pc 10 -5 [Pa ]
m3 b 10 5 mol 4.306 11.94 6.58

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 186 can be rewritten to calculate .

=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 CH4 C6H6 CH3OH

1010 [m]
3.24 4.56 3.74

Table 4.2 Value 1010 [m] 3.8 5.27 3.6

Percent Difference 14.7 13.5 3.8

23

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:

Species CH4 C6H6 CH3OH

Tc [K ]

Pc 10 -5 [Pa ]

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=
2 C6 2N a

J m3 a 2 mol 0.2303 1.883 0.9464

3 3 3a 3 C6 = 2 2N a
The values can be found in Table 4.2. The following table can now be created Species CH4 C6H6 CH3OH

1010 [m]
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

Therefore

C6 =

Ii I j 3 i j I +I 2 j i

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 van der Waals:

P=

RT a v b v2 RT a 1/2 v b T v( v + b) RT a(T ) v b v (v + b ) + b( v b)

Redlich-Kwong

P=

Peng-Robinson:

P=

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

=3 2 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 1 smaller and polar (smaller b, same a)

Species 2 larger and non-polar (larger 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]) 10 [L] 8.314 mol K (1000 [K ])ln W = 38.29 kJ

(b) Instead of substituting the ideal gas law into the definition of work, the Redlich-Kwong equation is used:
W = n
v2 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 m b = 2.1110 5 mol m3 v1 = 0.0005 mol 3 m v2 = 0.005 mol

28

and evaluating the resulting formula gives

W = 37.35 kJ

(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:
P 1 = 1.65 MPa P2 = 15.6 MPa

From the steam tables:

kJ 1 = 3522.6 u kg kJ 2 = 3462.2 u kg
Therefore,

kJ 1 = 8.101 s kg K kJ 2 = 7.00 s kg K

kJ kJ kJ kJ (1000 K ) 7.00 = w 3462 . 2 3522 . 6 8 . 101 kg K kg kg kg K kJ = 1040 w 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,

1 b b = 1 + + + ... b v v 1 v and a b 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 and C ' = 2ab(RT ) a 2

(RT )2

(RT )4

Therefore,

30

2 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

If we substitute the first expression into the second, we obtain

2 1 B C 1 B C RT 1 B C + + ... = + + C' RT + 1 + B ' RT + RT v + 2 + 3 v v v2 v3 v v 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 2 vc b Tc vc

(1)

RTc 2a P + =0= 2 3 v Tc (vc b ) Tc vc

(2)

2 2 RTc 6a P 2 =0= 3 4 Tc vc v ( vc b ) Tc

(3)

If we multiply Equation 2 by 2 and Equation 3 by (v-b) and add them together: 0= 4a

3 vc

6a(vc b )
4 vc

this can be solved to give: vc = 3b If we plug this back into Equation 2 and solve for a, we get: a= 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:
27 R 2Tc2 64 Pc

a=

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 27 R 2Tc3 a= 64 Pc RTc b= 8 Pc The Berthelot equation is P= RT a v b Tv 2

(1) (2) (3)

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:
27 R 2Tc3 64 Pc
Tv 2

P=

8 PcTr 3v r 1

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

Finally, substitute Equation 1: P=

2 8PcTr 3PcTc vc 3v r 1 Tv 2

This can be rewritten as Pr = 8Tr 3 2 3vr 1 Tr vr

35

4.24 (a) The virial equation is:

z= Pv D B C = 1 + + 2 + 3 +... RT v v v

(1)

We can rewrite this equation:

(z 1)v =

C Pv 1 v = B + +... RT 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

(z -1)v (cm3 / mol)

-125

(z -1)v -130

-135 0 1 0.5 1.5 2

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

(z -1)v (cm3 / mol)

y = 177.058x - 140.373
-125 (z -1)v -130 lin

-135 0 1 0.5 1.5 2

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

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

37

Second Virial Coefficient of Water by 4 Methods

0

-50

B (water) cm 3 /mol

-100 B (average) -150 B (lowest P) B (Level) -200 B (Linear) CRC -250 1000 1250 1500 250 500 750 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 v3 c c

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 Pc vc = 1 43 . 2 BH 2 O = v RT c mol c 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 v4 c c c

(1)

and
2P 6B 12C H 2O = 0 = RTc 2 + H 2O + 4 5 v 2 v3 vc vc Tc c

(2)

Multiply Equation 1 by (4/vc) and add to Equation 2 to get:

2 v3 c 2 BH 2 O v4 c =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
v mid

[P

sat

f (v ) dv

v low v high v mid

[ f (v ) P

sat

]dv

[ f (v ) represents the particular EOS implicit in molar volume being used.] 4. If the values of the expressions are not equal, repeat the process until they are.
(a)

1. Guess P sat : P sat = 6 [bar ]

2. Calculate molar volume solutions for: RT a P sat = 1 / 2 v b T v (v + b ) J K1/2 m 3 J 41 . 851 2 (363.15 [K ]) 8.314 mol K mol 6 105 [Pa ] = m3 m3 v 0.0001 (363.15 K )1 / 2 v v + 0.0001 mol mol m3 m3 m3 = 0 . 000551 = 0 . 00459 vlow = 0.000152 v v high mid mol mol mol 3.
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
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 = 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 ) v b v(v + b) + b(v b )

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:

Tc = 305.4 [K ]

Pc = 48.84 [Pa ]

w = 0.099

Now we can calculate the required parameters. J 0.45724 (305.4 [K ]) 8.314 mol K 48.84 105 [Pa ]
2

a=

J m3 = 0.6036 2 mol m3 mol

J 0.07780 (305.4 [K ]) 8.314 mol K = 4.045 10 5 b= 5 48.84 10 [Pa ] (T ) = 1 + 0.37464 + 1.54226(0.099) 0.26992(0.099)2 (T ) = 1.12

243.15 K 1 3 05.4 K

Now, we can find the three solutions to the Peng-Robinson EOS: P sat = RT a (T ) v b v(v + b) + b(v b )

Using the values calculated above and P sat = 10.6 105 [Pa ] J R = 8.314 mol K we get m3 4 v = 7.199 10 5 , v = 2.167 10 mol 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 1m = 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 1m = 0.0229 g = vap = 3 3 v vap (100)3 cm3 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 2 Pc mol

m3 mol (Note: Critical data for nitrogen obtained in Table A.1.1.) 0.08664 RTc = 2.69 10 5 b= Pc Now use the EOS to find the molar volume: P= 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

and the mass m = 6.55 10 6 mol (0.02801 kg/mol) = 1.83 105 kg Now, calculate the value of the gas: Value = ($6.1 / kg ) 1.83 105 kg = $1,116,300

44

If we use the ideal gas law, we find: J 8.314 (295 K ) RT mol K = 1.98 10 4 = v= P 12400000 Pa Following the steps above, Value = $1,113,200 The value calculated using the ideal gas law is $3100 less than the value calculated using the Redlich-Kwong EOS.
(b) First, calculate the a and b parameters:

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

or at the critical point

v3 RTc 2 RT a 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
2 3 v 3 3v 2 vc + 3vvc vc =0

Setting the coefficients equal we get the following expressions.

3vc =
2 3vc = 3 vc =

RTc Pc a PcTc0.5 ab RTc b b2 Pc

(1) (2) (3)

Pc Tc0.5

Using Equation 2, find an expression for a:

2 RTC 2 0.5 a= 3vc + P + b Pc Tc C

Substitute the above expression into Equation 3 to get

2 3 b 3 + 3vc b 2 + 3vc b vc =0

The one real root to this equation is b = 21 / 3 1 vc Substitute Equation 4 into Equation 1:

(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

RTc Pc 3P c zc = RTc

1 = 3

(Equation 4.50)

The Redlich-Kwong equation is P= RT a v b T 0.5v(v + b )

We can use Equation 4 to get

0.2599 RT a b P= vr 0.2599 T 0.5vvc (vr + 0.2599 )

Now, substitute Equation 4.48

P= 3Tr Pc a 0 . 5 v r 0.2599 T vvc (v r + 0.2599 )

Replacing a with Equation 4.47 yields P= 3Tr Pc 0.42748R 2Tc2.5 v r 0.2599 PC T 0.5 vvc (v r + 0.2599)

From Equation 4.48

R 2Tc2 = Pc2 b 2

(0.08664)2

48

which upon substitution yields P= 3Tr Pc Pc b 2 0.42748 v r 0.2599 (0.08664 )2 Tr0.5 vvc (v r + 0.2599)

Now, use Equation 4: P= 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) (Equation 4.49)

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 ) sat (T + 5 C ) v sat (T C ) 1 v = sat ( ) ( ) T T 5 C 5 C + 10 K sat (T ) ( ) v v T This approximation is valid even though the saturation pressure changes because molar volume is weakly dependent on pressure. From the steam tables

m3 sat (15 C ) = 0.001001 v kg 3 m sat (20 C ) = 0.001002 v kg m3 sat (25 C ) = 0.001003 v kg

m3 sat (95 C ) = 0.001040 v kg 3 m sat (100 C ) = 0.001044 v kg m3 sat (105 C ) = 0.001047 v kg

Using these values, we can calculate the thermal expansion coefficients

m3 m3 0 . 001003 0 . 001001 1 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

(20 C ) = 2.0 10 4 K -1
4

[ ] (100 C ) = 6.71 10 [K ]
-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

sat dv sat (T ) v dP

The derivatives are determined from the following graph.

Specific Volume of Liquid Water vs. Pressure
0.001050

Specific Volume [m /kg]

0.001040 0.001030 0.001020 0.001010 0.001000 0.000990 0 5

v = -5E-07*P + 0.001044 R2 = 0.9949

T = 20C T = 100 C
Linear (T = 100 C)

Linear (T = 20C)
v = -5E-07*P + 0.001002 R2 = 0.9979

10

15

20

25

Pressure [MPa]

It is clear that
sat dv 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

1

5 10 7

m3 kg MPa

(20 C ) = 4.99 10 4

1 1 = 4.99 10 10 Pa MPa
1

m3 (100 C ) = 0.001044 kg

m3 kg MPa 1 1 = 4.79 10 10 (100 C ) = 4.79 10 4 MPa Pa

5 10 7

51

4.30 (a) Substitute critical data into the Rackett equation:

vcalc =

46 10 cm 3 vcalc = 38 mol Now, calculate the error.

(8.314)(190.6) [0.29056 0.08775(0.008)][1+ (1111 / 190 ) ] 5

2/7

v calc vexp Error = vexp Error = 0.8%

100 %

(b)

cm 3 vcalc = 54.2 mol

(c)

Error = 1.1%

cm 3 vcalc = 161.2 mol

(d)

Error = 10.8%

cm 3 vcalc = 20.5 mol

(e)

Error = 13.5%

cm 3 vcalc = 68.5 mol

Error = 19.7%

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.

Tr =

343.15 [K ] T = = 1.12 305.4 [K ] Tc 30 [bar ] P = = 0.616 Pr = Pc 48.74 [bar ] w = 0.099

By double interpolation of the charts z (0 ) = 0.8376 z (1) = 0.0168 and

z = z (0 ) + wz (1) = 0.8376 + (0.099 )(0.0168) = 0.8393

Therefore,
(0.8393) 30 [kg ] J 8.314 (343.15 [K ]) mol K 0.03007 [kg/mol]

V=

znRT = P

V = 0.796 m 3

[ ]
( [ ])

[30 10

[Pa ]]

(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

kg (MW ) propane = 0.0441

n =

50 [kg ] = 1130 [mol] kg 0.0441 mol

mol

Now calculate the volume: (1130 [mol]) 8.314 J (50 + 273.15 K ) mol K

V =

nRT = P

V = 0.870 m 3

[ ]

35 105 [Pa ]

(b) The Redlich-Kwong EOS is

P= where a= b=

RT a v b T 1 / 2 v(v + b )

J m 3 K1 / 2 0.42748R 2Tc2.5 = 18.33 2 Pc mol 0.08664 RTc = 6.28 10 5 Pc

m3 mol (Note: Critical data for propane obtained in Table A.1.1.) 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= where

RT a (T ) v b v(v + b ) + b(v b )

= 1 + 1 Tr
Tr =

[ (

(50 + 273.15) K = 0.873 T = 370 K Tc

)]2

= 1.081
a=

= 0.37464 + 1.54226(0.152) 0.26992(0.1152)2 = 0.605

J m3 0.45724(RTc )2 = 1.02 Pc mol m3 mol

0.07780 RTc b= = 5.64 10 5 Pc

Now every variable in the Peng-Robinson EOS is known, except v. m3 v = 0.0000942 mol V = 0.107 m 3

[ ]

(d) We must calculate the reduce temperature and pressure to use the compressibility charts:

Tr =

323.15 K T = = 0.873 370 K Tc 35 bar P = = 0.825 Pr = Pc 42.44 bar

By double-interpolation on the compressibility charts (Appendix C), z (0 ) = 0.1349 z (1) = 0.052

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

[ ]

Using the generalized compressibility charts: m3 v = 0.0000971 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:
J 2 8.314 mol K (304.2 K ) 73.76 10 5 [Pa ]
2

a = 0.45724

J m3 = 0.40 mol 2

J 8.314 mol K (304.2 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

liquid - vapor

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
a= b=

[ (

)]2

J m3 0.45724(RTc )2 = 0.25 mol Pc 0.07780 RTc = 2.68 10 5 Pc m3 mol

T = Tr Tc = 209.66 [K ]

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 )
4

v = 1.83 10

m3 mol

Therefore,
3 4 m 55.2 10 [Pa ] 1.83 10 mol = 0.58 z= J 8.314 mol K (209.66 [K ])
5

From the compressibility charts, z (0 ) = 0.5984 z (1) = 0.0897

Therefore, z = z (0 ) + wz (1) = 0.5984 + (0.008)0.0897 z = 0.599

60

Methanol:

Following the procedure outlined above, the Peng-Robinson equation produces m3 v = 3.14 10 4 mol z = 0.651 Using the compressibility charts: z (0 ) = 0.5984 z (1) = 0.0897

From Table A.1.1,

w = 0.559

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 =

(92 + 273.15) K = 0.9 T = 405.6 K Tc 306.5 bar P = = 2.718 Pr = Pc 112.77 bar

z (0 ) = 0.4133

From interpolation of the compressibility charts:

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 = 30 [kg ] 26.038 10
-3

nbut =

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

Substituting critical data from Table A.1.1 gives J K1/2 m3 aace = 8.03 2 mol J K1/2 m 3 abut = 29.07 2 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.
2 2 amix = y1 a1 + 2 y1 y 2 a12 + y 2 a2

J K1/2 m3 a12 = 8.03 29.07 (1 0.092) = 13.87 2 mol 1/2 3 J K m amix = 14.72 2 mol

63

bmix = y1b1 + y 2b2 = 5.53 10

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 V = (nace + nbut )v = (1152.2 [mol] + 860.2 [mol]) 0.00111 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):

Tc = 304.2 [K ]

Pc = 73.76 [bar ] J m 3 K1/2 0.42748R 2Tc2.5 = 6.466 Pc mol 0.08664 RTc = 2.97 10 5 Pc m3 mol

a1 = b1 =

Toluene (2):

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

We can use the mixing rules to calculate bmix. bmix = y1b1 + y 2b2 2 mol 5 bmix = 2.97 10 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] mol ntot

[ ]

We can then solve for amix.

J m 3 K1/2 a mix = 31.0 mol

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From the mixing rules, we know J m3 K1/2 2 2 amix = 31.0 = y1 a1 + 2 y1 y2 a12 + y2 a2 mol Therefore, J m 3 K1/2 a12 = 16.55 mol Equation 4.79 states
a12 = a1a 2 (1 k12 )

Substitution of the values provides:

k12 = 0.17

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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 0.025 0.561

m3 b mol 6.38 10 5 2.66 10 5 3.05 10 5

Species C2H6 (3) H2 (1) 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
2 2 2 a mix = y1 a1 + y1 y 2 a12 + y1 y3 a13 + y 2 y1 a21 + y 2 a 2 + y 2 y3 a 23 + y3 y1 a31 + y3 y 2 a32 + y3 a3 2 2 2 a mix = y1 a1 + 2 y1 y 2 a12 + 2 y1 y3 a13 + y 2 a2 + 2 y 2 y3 a 23 + y3 a3 bmix = y1b1 + y 2b2 + y3b3

Calculate mole fractions: n1 5 mol = = 0.5 n1 + n2 + n3 10 mol y 2 = 0 .4 y3 = 0.1 y1 = 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 3 J m a13 = 0.119 mol

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 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

The molar volume is calculated as follows v= m3 0.0125 m 3 V = = 0.00125 10 mol mol n1 + n2 + n3

[ ]

Therefore,
J m3 J 0 . 206 (300 K ) 8.314 mol K mol P= 2 3 3 3 0.00125 m 3.19 10 5 m 0.00125 m mol mol mol P = 1.92 MPa

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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.
2 2 Bmix = y1 B1 + 2 y1 y 2 B12 + y 2 B2

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, v= RT Bmix RT P = + Bmix 1 + P RT P cm 3 m3 v = 2445.6 = 0.002446 mol mol

(b) We can estimate k12 using an EOS where the a parameter is the only unknown. b can be calculated as follows

bmix = y1b1 + y 2b2 Using the Redlich-Kwong EOS,

bmix = 0.25 5.83 10 5 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 Now we can calculate k12 as follows
2 2 a mix = y1 a1 + 2 y1 y 2 a12 + y 2 a2

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 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

(Calculated using Equation 4.47)

From Equation 4.79

a12 = a1a 2 (1 k12 ) 8.81 k12 = 1 = 0.35 6.466 28.03

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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.

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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= Therefore,
V = (172.1 [mol])1.07 10 4 m3 3 = 0.018 m mol

10 [kg ] = 172.1 [mol] 0.05812 [kg/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.

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4.42 Using ThermoSolver should be straightforward; thus, only the answers are provided. (a)
Tc = 305.4 [K ]

Pc = 48.84 [bar ]

kJ h o f , 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 (i). Quantity v z Lee Kessler EOS m3 3.68 10 4 mol 0.5859 Peng Robinson EOS m3 3.58 10 4 mol 0.5711 % Difference 2.7 2.5 Lee Kessler EOS m3 8.34 10 5 mol 0.1383 Peng Robinson EOS m3 8.70 10 5 mol 0.1444 % Difference 4.3 4.4

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