Chapter 7: The Properties of Real Gases

Problem numbers in italics indicate that the solution is included in the Students Solutions Manual. Questions on Concepts Q7.1) Explain why the oscillations in the two-phase coexistence region using the
Redlich-Kwong and van der Waals equations of state (see Figure 7.4) do not correspond to reality. The oscillations predict that as V increases, P will increase. No real gas exhibits this behavior.

Q7.2) Explain the significance of the Boyle temperature.

The Boyle temperature provides a way to classify the way in which z varies with P at low values of P for different gases. If T > TB, z increases with increasing P; if T < TB, z decreases with increasing P.

Q7.3) The value of the Boyle temperature increases with the strength of the attractive
interactions between molecules. Arrange the Boyle temperatures of the gases Ar, CH4, and C6H6 in increasing order. Ar < CH4 < C6H6

Q7.4) Will the fugacity coefficient of a gas above the Boyle temperature be less than
one at low pressures? No. The integral

z 1 dP is always greater than zero for this case. Therefore, P

> 1 for all P.

Q7.5) Using the concept of the intermolecular potential, explain why two gases in
corresponding states can be expected to have the same value for z. Two different gases will have different values for the depth of the intermolecular potential and for the distance at which the potential becomes positive. By normalizing P, T, and V to their critical values, the differences in the intermolecular potential are to a significant extent also normalized.

Q7.6) By looking at the a and b values for the van der Waals equation of state, decide whether 1 mole of O2 or H2O has the higher pressure at the same value of T and V.
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Chapter 7/The Properties of Real Gases

A is significantly larger for H2O. Therefore, the attractive forces between H2O molecules are greater than between O2 molecules. Consequently, O2 will have a higher pressure.

Q7.7) Consider the comparison made between accurate results and those based on calculations using the van der Waals and Redlich-Kwong equations of state in Figures 7.1 and 7.5. Is it clear that one of these equations of state is better than the other under all conditions?
The Redlich-Kwong gives more accurate results for almost all of the values of pressure shown in these figures. However, it is not better under all conditions.

Q7.8) Why is the standard state of fugacity, f , equal to the standard state of pressure, P?
If this were not the case the fugacity would not become equal to the pressure in the limit of low pressures.

Q7.9) For a given set of conditions, the fugacity of a gas is greater than the pressure. What does this tell you about the interaction between the molecules of the gas?
If the fugacity is greater than the pressure, the repulsive pat of the potential dominates the interaction between the molecules.

Q7.10) A system containing argon gas is at pressure P1 and temperature T1. How would
you go about estimating the fugacity coefficient of the gas? Use the critical constants of the gas to determine the reduced pressure and temperature. With these results, estimate the fugacity coefficient using Figure 7.11.

Problems P7.1) A sample containing 35.0 g of Ar is enclosed in a container of volume 0.165 L at 390 K. Calculate P using the ideal gas, van der Waals, and Redlich-Kwong equations of state. Based on your results, does the attractive or repulsive contribution to the interaction potential dominate under these conditions?

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Chapter 7/The Properties of Real Gases

0.165 L 39.95 g = 0.1883 L mol ? 35.0 g mol RT 8.314 10 ? L bar K ? mol ? 390 K = 172 bar = = 0.1883 L mol ? Vm RT a 8.314 10 ? L bar K ? mol ? 390 K 1.355L2 bar mol ? 2 = 2 0.1883 L mol ? 0.0320 L mol ? Vm b Vm 0.1883 L mol ?

Vm =

Pideal gas PvdW =

= 169 bar RT a 1 PRK = Vm b T Vm (Vm + b ) = 8.314 10 ? L bar K ? mol ? 390 K 0.1883 L mol ? 0.02219 L mol ? 16.86 L bar mol K 1 ? 0.1883 L mol 0.1883L mol ? + 0.02219 L mol ? 390 K
2 ? 1 2

PRK = 174 bar Because PvdW < Pideal gas, the attractive part of the interaction appears to dominate using the van der Waals equation of state. However, because PRK > Pideal gas, the repulsive part of the interaction appears to dominate using the Redlich-Kwong equation of state. This is a case where a more accurate equation of state is needed to answer the question.

P7.2) Calculate the density of O2(g) at 375 K and 385 bar using the ideal gas and the van
der Waals equations of state. Use a numerical equation solver to solve the van der Waals equation for Vm or use an iterative approach starting with Vm equal to the ideal gas result. Based on your result, does the attractive or repulsive contribution to the interaction potential dominate under these conditions?

Vm = PvdW

RT 8.314 10 ? L bar K ? mol ? 375 K = = 8.10 10 ? L P 385 bar RT a 8.314 10 ? L bar K ? mol ? 370 K 1.382 L2 bar mol ? = 2 = Vm b Vm Vm 0.0319 L mol ? (Vm ) 2

The three solutions to this equation are Vm = ( 0.0131 0.0339i ) L mol ? and Vm = 0.0867 L mol ? Only the real solution is of significance.

idealgas vdW

M 32.0 g mol ? = = = 395 g L? ? Vm 0.0810 L mol

M 32.0 g mol ? = = = 369 g L? ? Vm 0.0867 L mol

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Chapter 7/The Properties of Real Gases Because the van der Waals density is less than the ideal gas density, the repulsive part of the potential dominates. 7.90 mol L1. Compare this with values calculated from the ideal and Redlich-Kwong equations of state. Use a numerical equation solver to solve the Redlich-Kwong equation for Vm or use an iterative approach starting with Vm equal to the ideal gas result. Discuss your results. For the ideal gas, 1 P 400 bar = = = 9.62 mol L? ? ? ? Vm RT 8.314 10 L bar K mol 500 K
PRK = RT a 1 Vm b T Vm (Vm + b ) 8.314 10 ? L bar K ? mol ? 500 K Vm 0.02208 L mol ?
1

P7.3) At 500 K and 400 bar, the experimentally determined density of N2 is

400 bar =

17.40 L2 bar mol ? K 2 1 Vm Vm + 0.02208 L mol ? 500 K

The three solutions to this equation are Vm = ( 0.00529 0.0186i ) L mol ? and Vm = 0.1145 L mol ? Only the real solution is of significance. 1 1 = 8.73 mol L? = ? Vm 0.1145 L mol The ideal gas density is greater than that calculated with the Redlich-Kwong equation of state and the experimental result showing that the repulsive part of the potential dominates. The Redlich-Kwong result is in error by +10%.

P7.4) The observed Boyle temperatures of H2, N2, and CH4 are 110, 327, and 510 K, respectively. Compare these values with those calculated for a van der Waals gas with the appropriate parameters.

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Chapter 7/The Properties of Real Gases

TB = a for a van der Waals gas. Rb In solving this problem, keep in mind that 1 dm3 = 1 L = 103 m3 .

TB ( H 2 ) =

0.2452 dm 6 bar mol ? = 111 K 8.314 10 ? L bar mol ? K ? 0.0265 dm3 mol This value is slightly higher than the experimental value.

TB ( N 2 ) =

1.370 dm 6 bar mol ? = 426 K 8.314 10 ? L bar mol ? K ? 0.0387 dm3 mol ? This value is substantially larger than the experimental value. 2.303 dm 6 bar mol ? = 643 K 8.314 10 ? L bar mol ? K ? 0.0431 dm3 mol ? This value is substantially larger than the experimental value.

TB ( CH 4 ) =

P7.5) Calculate the van der Waals parameters of methane from the values of the critical constants.
b= RTc 8.314 10 ? dm3bar K ? mol ? 190.56 K = = 0.0431 dm3 mol ? 8Pc 8 45.99 bar

? 3 ? ? 27 R 2Tc2 27 8.314 10 dm bar K mol = a= 64 Pc 64 45.99 bar

) (190.56 K )
2

= 2.303 dm 6 bar mol ?

P7.6) Calculate the Redlich-Kwong parameters of methane from the values of the critical constants.
a= R 2Tc
5

9 Pc 2 3 1
1 3

( 2 1) RT = ( 2 1) 8.3145 10 dm bar K mol b=

1 3 ? 3 ? c

(8.314 10 =

dm3 bar K ? mol ?

9 45.99 bar 2 3 1

) (190.56)
2

= 32.20 dm bar K mol2

6

1 2

190.56 K

3Pc

3 45.99 bar

= 0.02985 dm3mol ?

P7.7) Use the law of corresponding states and Figure 7.8 to estimate the molar volume of methane at T = 285 K and P = 180 bar.
Tr = 285 K 180 bar = 1.5 Pr = = 3.91. Therefore, z 0.8. 190.56 K 45.99 bar
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Chapter 7/The Properties of Real Gases PVm RT 8.314 10 ? dm3 bar K ? mol ? 285 K = 0.8; Vm = 0.8 = 0.8 RT P 180 bar ? Vm = 0.105 L mol

P7.8) Calculate the P and T values for which H2(g) is in a corresponding state to Xe(g)
at 450 K and 85.0 bar. T
Xe R

T Xe 450 K = Xe = = 1.55; T H 2 = 1.55TCH 2 = 1.55 32.98 K = 51.2 K TC 289.74 K P Xe 85.0 bar = = 1.46; P H 2 = 1.46 PCH 2 = 1.46 12.93 bar = 18.8 bar Xe PC 58.40 bar

PRXe =

P7.9) Assume that the equation of state for a gas can be written in the form
P (Vm b (T ) ) = RT . Derive an expression for =
a gas in terms of b (T ) ,

db (T ) , P, and Vm . dT

1 V 1 V and = for such V T P V P T

V RT V P b (T ) = RT ; = + b (T ) n P n nRT V = nb (T ) + P 1 V 1 ndb ( T ) nR 1 db ( T ) R + + = = = V T P V dT P Vm dT P RT 1 V 1 nRT = = 2 = V P T V P Vm P 2

P7.10) 1 mol of Ar initially at 298 K undergoes an adiabatic expansion against a

pressure Pexternal = 0 from a volume of 20.0 L to a volume of 65.0 L. Calculate the final temperature using the ideal gas and van der Waals equations of state. w = q = 0. U = 0 for an ideal gas and T = 0 because U is a function of T only. Using the results of Example Problem 3.5 for a van der Waals gas,

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Chapter 7/The Properties of Real Gases

1 1 U T , m = a Vm,i Vm, f m 105Pa 10 ? m3 1 1 6 ? 3 ? ? 3 ? bar dm 20.0 10 m mol 65.0 10 m mol

= 1.355 dm 6bar mol ? = 4.69 J T =

U T , m 4.69 J mol ? = = 0.376 K CV ,m 12.5 J K ? mol ?

T f = 297.6 K

P7.11) 1 mol of Ar undergoes an isothermal reversible expansion from an initial volume

of 1.00 L to a final volume of 65.0 L at 298 K. Calculate the work done in this process using the ideal gas and van der Waals equations of state. What percentage of the work done by the van der Waals gas arises from the attractive potential? For the ideal gas, Vf 65.0 L w = nRT ln = 1 mol 8.314 J mol ? K ? 298 K ln = 10.34 103 J Vi 1.00 L

For the van der Waals gas,

nRT n2a an 2 w = 2 dV = nRT ln (V nb) + V nb V V V i Vi

Vf

Vf

0.1355 Pa m 6 = 1mol 8.314 J mol ? K ? 298 K ln V 3.20 10 ? m3 + V 0.001 m3

0.065 m3

= 10.42 103J + 133 J = 10.41 103 J 133 J 100 = 1.3% 10.41 103J

P7.12) For a van der Waals gas, z =

Vm a . Expand the first term of this Vm b RTVm

a 1 expression in a Taylor series in the limit Vm >> b to obtain z 1 + b . RT Vm df ( x ) b 1 f ( x ) = f (0) + and x = x + ... In this case, f ( x ) = b Vm dx x =0 1 Vm

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Chapter 7/The Properties of Real Gases

z=

Vm a a 1 = b Vm b RTVm 1 RTVm Vm

b d 1 1 b b b 1 Vm 1 1 + = 1+ b Vm b Vm Vm b =1 1 d Vm Vm b =1 Vm
Vm

z 1+

b a a 1 = 1+ b Vm RTVm Vm RT ln z ln z and that P = 1 P . T P P T

P7.13) Show that T = 1 + T

=

1 V 1 V ; = V T P V P T PV z VP P V VP PV + + ; z = = = 2 2 RT T P RT RT T P RT RT 1 z 1 RT VP PV ln z + = + = = 2 RT T T P z T P VP RT ln z 1 Therefore 1 + T = 1 + T + = T T P T
V P V V PV z + = = P T RT RT P T RT RT 1 z RT V PV 1 ln z = = = P T z P T PV RT RT P ln z 1 Therefore 1 P = 1 P = P P T P

P7.14) A van der Waals gas has a value of z = 1.00084 at 298 K and 1 bar and the Boyle
temperature of the gas is 125 K. Because the density is low, you can calculate Vm from the ideal gas law. Use this information and the result of Problem P7.12 to estimate a and b.

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Chapter 7/The Properties of Real Gases 1 a a b ; TB = Vm RT Rb b TB 1 Vm T

z 1 = z 1 =

z 1 RT 0.00084 8.314 10 ? dm3 bar mol ? K ? 298 K = b= T 125 K 1 bar 1 B P 1 T 298 K = 0.0359 dm3 mol ? = 3.59 105 m3 mol ? a = RbTB = 8.314 J mol ? K ? 3.59 105 m3 mol ? 125 K = 3.73 102 m 6 Pa mol ? and Vc = 55.95 103 L. Use the values of Pc and Tc to calculate Vc. Assume that H2O behaves as (a) an ideal gas, (b) a van der Waals gas, and (c) a Redlich-Kwong gas at the critical point. For parts (b) and (c), use the formulas for the critical compression factor. Compare your answers with the experimental value. Assuming an ideal gas, RT 8.314 102 L bar mol1K 1 647.14 K Vc = c = = 0.2438 L Pc 220.64 bar For a van der Waals gas, PV 3 3 RTc 3 = 0.2438 L = 91.4 103 L zc = c c = ; Vc = RTc 8 8 Pc 8 For a Redlich-Kwong gas, PV RT zc = c c = 0.333; Vc = 0.333 c = 0.333 0.2438 L = 81.2 103 L RTc Pc

P7.15) The experimental critical constants of H2O are Tc = 647.14 K, Pc = 220.64 bar,

Although the agreement with experiment is better for the van der Waals and RedlichKwong models than for the ideal gas model, all results differ significantly from the true value.

P7.16) Another equation of state is the Bertholet equation, Vm =

expressions for = of V, T, and P.

RT a . Derive +b P RT 2

1 V 1 V and = from the Bertholet equation in terms V T P V P T

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Chapter 7/The Properties of Real Gases

V = nRT na + nb P RT 2 1 V 1 nR 2na 1 R 2a = + = = + 3 V T P V P RT Vm P RT 3 1 V 1 nRT nRT RT = = 2 = 2 = 2 V P T V P P V P Vm

P7.17) For the Bertholet equation, Vm =

RT a , find an expression for the +b P RT 2 Boyle temperature in terms of a, b, and R.

PVm Pb Pa = 1+ 2 3 RT RT R T z a Z = b 2 3 and at T = TB , =0 RT P T P T a Therefore b 2 3 = 0 R TB z= TB = a Rb

P7.18) The experimentally determined density of H2O at 1200 bar and 800 K is 537 g L1. Calculate z and Vm from this information. Compare this result with what you would have estimated from Figure 7.8. What is the relative error in using Figure 7.8 for this case?
Vm = z= M

18.02 g mol ? = 3.34 10 ? L mol ? 537 g L?

PVm 1200 bar 3.34 10 ? L mol ? = = 0.602 RT 8.314 10 ? L bar mol ? K ? 800 K

Because Pr =

800 K 1200 bar = 5.44 and Tr = = 1.24, Figure 7.7 predicts z = 0.75. 647.14 K 220.64 bar The relative error in z is 25%.

P7.19) The volume of a spherical molecule can be estimated as V = b/4NA where b is the
van der Waals parameter and NA is Avogadros number. Justify this relationship by 4 considering a spherical molecule of radius r, with volume V = r 3 . What is the volume 3 centered at the molecule that is excluded for the center of mass of a second molecule in terms of V? Multiply this volume by NA and set it equal to b. Apportion this volume

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Chapter 7/The Properties of Real Gases equally among the molecules to arrive at V = b/4NA. Calculate the radius of a methane molecule from the value of its van der Waals parameter b. The excluded volume is
b = 4NA Vmolecule

4 3 ( 2r ) = 8Vmolecule , or 4 Vmolecule per molecule. Therefore, 3 and Vmolecule = b/4NA.

NA

16 3 r = b 3
1 1

3b 3 3 4.31105 m3 3 ? 0 r = = = 1.6310 m 16 N A 16 6.022 1023

P7.20) At what temperature does the slope of the z versus P curve as P 0 have its
maximum value for a van der Waals gas? What is the value of the maximum slope? 1 a Z = b for a van der Waals gas RT P T ,P0 RT Z 1 a 1 1 2a = b = b + 2 3 2 RT RT RT RT RT T P T P0 Setting this derivative equal to zero gives b 2a 2a = 0 Tmax = RTmax Rb
2 1 a b b b b a = b = RTmax RTmax 2a 2a 4a

The maximum slope is

P7.21) Show that the van der Waals and Redlich-Kwong equations of state reduce to the
ideal gas equation of state in the limit of low density.

RT a 2 : In the limit of low density, Vm is large and Vm >> b. The second term in Vm b Vm 1 the van der Waals equation can be neglected because it goes as 2 , and in the first term, Vm RT RT . Vm b Vm

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Chapter 7/The Properties of Real Gases RT a 1 : In the limit of low density, Vm is large and Vm >> b. As Vm b T Vm (Vm + b ) for the van der Waals equation, the second term in the Redlich-Kwong equation can be 1 RT RT neglected because it goes as 2 . In the limit, the first term becomes . Vm b Vm Vm P=

P7.22) Show that the second virial coefficient for a van der Waals gas is given by
1 z B (T ) = RT 1 V m a =b RT T

Let u =

1 . The virial expansion takes the form Vm

2 dP ( u ) 1 d P (u ) P = RT P ( u ) u =0 + u+ u 2 + ... 2 du 2 u =0 du u =0

Therefore, the second virial coefficient is B (T ) = P= RT a RT 2 = au 2 Vm b Vm 1 u b

2 1 d P (u ) 2 RT du 2 u =0

dP RT d1 u RT RT = 2au = 2 2au = 2au 2 2 2 du u (1 u b ) (1 u b ) du (1 ub ) d 2P 2bRT = 2a 3 2 du (1 ub ) lim

u 0

2bRT

(1 ub )

2a = 2bRT 2a and d 2 P (u ) a =b 2 RT du u =0

1 B (T ) = 2 RT

P7.23) For a gas at a given temperature, the compressibility is described by the

P P empirical equation z = 1 9.00 10 + 4.00 105 o , where P = 1 bar. o P P Calculate the activity coefficient for P = 100, 200, 300, 400, and 500 bar. For which of these values is the activity coefficient greater than one?
3 2

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Chapter 7/The Properties of Real Gases

3 5 P 1 9.00 10 P + 4.00 10 ( P ) 1 z 1 ln = dP = dP P P 0 0 P 2

ln = 9.00 103 P + 2.00 105 P 2

= 0.497, 0.368, 0.406, 0.670, and 1.65 at 100, 200, 300, 400, and 500 bar, respectively.
z P. P T If z =1.00054 at 0C and 1 bar, and the Boyle temperature of the gas is 220 K, estimate the values of Vm, a and b for the van der Waals gas.

P7.24) For values of z near one, it is a good approximation to write z ( P ) = 1 +

From Example Problem 7.2, a 1 z = b RT P T RT We can write three equations in three unknowns: a P z 1 = b RT RT a 1 bar 5.4 104 = b 2 1 1 2 8.314 10 L bar mol K 273.15 K 8.314 10 L bar mol1 K 1 273.15 K a a = = 220 K TB = 2 Rb 8.314 10 L bar mol1 K 1 b RT a 8.314 102 L bar mol1 K 1 273.15 K a = = 1 bar P= Vm b Vm Vm b Vm Using an equation solver, the results are a = 1.15 L2 bar mol2 , b = 0.0630 L mol1 , Vm = 22.72 L.

P7.25) Calculate the critical volume for ethane using the data for Tc and Pc in Table 7.2
(see Appendix B, Data Tables) assuming a) the ideal gas equation of state and b) the van der Waals equation of state. Use an iterative approach to obtain Vc from the van der Waals equation, starting with the ideal gas result. How well do the calculations agree with the tabulated values for Vc? Using the ideal gas law, RT 8.314 102 L bar mol ? K ? 305.32 K = 0.5211 L Vc = c = 48.72 bar Pc Using the van der Waals equation of state, RTc a 8.314 10 ? L bar K ? mol ? 305.32 K 5.580 L2 bar mol ? 2 = Pc = Vc b Vc Vc 0.0651 L mol ? Vc2

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Chapter 7/The Properties of Real Gases Setting Vc = 0.5211 L gives Pc = 35.13 bar, which is below the experimental value Pc = 48.72 bar. Setting Vc = 0.300 L gives Pc = 46.06 bar, and setting Vc = 0.1784 L gives Pc = 48.72 bar. The relative error of this value for Vc is 0.1874 L 0.1455 L 100 = +29%. 0.1455 L

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