PART 1

Equilibrium

TRAPP: CHAP01 2006/3/8 18:03 PAGE 1 #1

TRAPP: CHAP01 2006/3/8 18:03 PAGE 2 #2

The properties of gases

Answers to discussion questions

D1.1

An equation of state is an equation that relates the variables that define the state of a system to each other.
Boyle, Charles, and Avogadro established these relations for gases at low pressures (perfect gases) by
appropriate experiments. Boyle determined how volume varies with pressure (V 1/p), Charles how
volume varies with temperature (V T ), and Avogadro how volume varies with amount of gas (V n).
Combining all of these proportionalities into one we find
V

AQ: Please
check we have
change P to
p.

nT
.
p

Inserting the constant of proportionality, R, yields the perfect gas equation

V=
D1.3

RnT
p

or

pV = nRT .

Consider three temperature regions:

(1) T < TB . At very low pressures, all gases show a compression factor, Z 1. At high pressures, all
gases have Z > 1, signifying that they have a molar volume greater than a perfect gas, which implies
that repulsive forces are dominant. At intermediate pressures, most gases show Z < 1, indicating
that attractive forces reducing the molar volume below the perfect value are dominant.
(2) T TB . Z 1 at low pressures, slightly greater than 1 at intermediate pressures, and significantly
greater than 1 only at high pressures. There is a balance between the attractive and repulsive forces
at low to intermediate pressures, but the repulsive forces predominate at high pressures where the
molecules are very close to each other.
(3) T > TB . Z > 1 at all pressures because the frequency of collisions between molecules increases
with temperature.

D1.5

The van der Waals equation corrects the perfect gas equation for both attractive and repulsive
interactions between the molecules in a real gas. See Justification 1.1 for a fuller explanation.
The Bertholet equation accounts for the volume of the molecules in a manner similar to the van der
Waals equation but the term representing molecular attractions is modified to account for the effect of
temperature. Experimentally one finds that the van der Waals a decreases with increasing temperature.
Theory (see Chapter 18) also suggests that intermolecular attractions can decrease with temperature.

TRAPP: CHAP01 2006/3/8 18:03 PAGE 3 #3

SOLUTIONS MANUAL

This variation of the attractive interaction with temperature can be accounted for in the equation of state
by replacing the van der Waals a with a/T .

Solutions to exercises
E1.1(a)

(a) The perfect gas equation [1.8] is: pV = nRT .

nRT
.
Solving for the pressure gives p =
V
131 g
= 1.00 mol.
The amount of xenon is n =
131 g mol1
p=

(1.00 mol) (0.0821 dm3 atm K1 mol1 ) (298.15 K)

1.0 dm3

= 24 atm .

That is, the sample would exert a pressure of 24 atm if it were a perfect gas, not 20 atm.
nRT
an2
(b) The van der Waals equation [1.21a] for the pressure of a gas is p =
2.
V nb
V
For xenon, Table 1.6 gives a = 4.137 dm6 atm mol2 and b = 5.16 102 dm3 mol1 .
Inserting these constants, the terms in the equation for p become
nRT
(1.00 mol) (0.08206 dm3 atm K1 mol1 ) (298.15 K)
=
= 25.8 atm,
V nb
1.0 dm3 {(1.00 mol) (5.16 102 dm3 mol1 )}
an2
(4.137 dm6 atm mol2 ) (1.00 mol)2
=
= 4.137 atm.
2
V
(1.0 dm3 )2
Therefore, p = 25.8 atm 4.137 atm = 22 atm .
E1.2(a)

Boyles law [1.5] in the form pf Vf = pi Vi can be solved for either initial or final pressure, hence
pi =

Vf
pf ,
Vi

Vf = 4.65 dm3 ,
Therefore,


(a) pi =

4.65 dm3

Vi = 4.65 dm3 + 2.20 dm3 = 6.85 dm3 ,

pf = 5.04 bar.

(5.04 bar) = 3.42 bar .



1 atm
= 3.38 atm .
(b) Since 1 atm = 1.013 bar, pi = (3.42 bar)
1.013 bar
E1.3(a)

6.85 dm3

The perfect gas law, pV = nRT [1.8], can be rearranged to

Hence,

pi
Tf
pf
=
or, solving for pf , pf =
pi .
Tf
Ti
Ti

p
nR
=
= constant, if n and V are constant.
T
V

Internal pressure = pump pressure + atmospheric pressure.

pi = 24 lb in2 + 14.7 lb in2 = 38.7 lb in2 ,
pf =

Ti = 268 K(5 C),

Tf = 308 K(35 C).

308 K
38.7 lb in2 = 44.5 lb in2 .
268 K

Therefore, p(pump) = 44.5 lb in2 14.7 lb in2 = 30 lb in2 .

TRAPP: CHAP01 2006/3/8 18:03 PAGE 4 #4

THE PROPERTIES OF GASES

Complications are those factors that destroy the constancy of V or n, such as the change in volume of
the tire, the change in rigidity of the material from which it is made, and loss of pressure by leaks and
diffusion.
E1.4(a)

The perfect gas law in the form p =

n=

0.255 g
20.18 g mol1

nRT
[1.8] is appropriate. T and V are given; n needs to be calculated.
V

= 1.26 102 mol,

T = 122 K,

V = 3.00 dm3 .

Therefore, upon substitution,

p=
E1.5(a)

(1.26 102 mol) (0.08206 dm3 atm K1 mol1 ) (122 K)

3.00 dm3

Boyles law in the form pf Vf = pi Vi is solved for Vf : Vf =

= 4.20 102 atm .

pi
Vi .
pf

pi = 1.0 atm,
pf = pex + gh[1.3] = pi + gh = 1.0 atm + gh,
gh = (1.025 103 kg m3 ) (9.81 m s2 ) (50 m) = 5.03 105 Pa.
Hence, pf = (1.01 105 Pa) + (5.03 105 Pa) = 6.04 105 Pa.
Vf =
E1.6(a)

1.01 105 Pa
6.04 105 Pa

3.0 m3 = 0.50 m3 .

The pressure in the apparatus is given by

p = patm + gh [1.3].




1 atm
1.013 105 Pa
patm = 770 Torr

= 1.026 105 Pa
760 Torr
760 Torr

6 3

10 cm
1 kg
3

9.806 m s2 = 977 Pa
gh = 0.99707 g cm
3
10 g
m3
p = 1.026 105 Pa + 977 Pa = 1.036 105 Pa = 104 kPa .

E1.7(a)

The gas pressure is calculated as the force per unit area that a column of water of height 206.402 cm
exerts on the gas due to its weight. The manometer is assumed to have uniform cross-sectional area, A.
Then force, F = mg, where m is the mass of the column of water and g is the acceleration of free fall.
As in Example 1.1, m = V = h A where h = 206.402 cm and A is the cross-sectional area.
p=

hAg
F
=
= hg.
A
A

TRAPP: CHAP01 2006/3/8 18:03 PAGE 5 #5

SOLUTIONS MANUAL

p = (0.99707 g cm


)


(206.402 cm)

1 kg
103 g

1m
102 cm

106 cm3
1 m3

(9.8067 m s2 )

= 2.0182 104 Pa.



1 m3
= 2.0000 102 m3 .
V = (20.000 dm3 )
103 dm3
0.25132 g
m
= 0.062789 mol.
=
n=
M
4.00260 g mol1
The perfect gas equation [1.8] can be rearranged to give R =

R=

pV
.
nT

(2.0182 104 Pa) (2.0000 102 m3 )

= 8.3147 JK1 mol1 .
(0.062789 mol) (773.15 K)

The accepted value is R = 8.3145 J K1 mol1 .

Although gas volume data should be extrapolated to p = 0 for the best value of R, helium is close
to being a perfect gas under the conditions here, and thus a value of R close to the accepted value is
obtained.
E1.8(a)

Since p < 1 atm, the approximation that the vapor is a perfect gas is adequate. Then (as in
Exercise 1.7(b)),
pV = nRT =

m
RT .
M

Upon rearrangement,

M=

RT
p

= (3.71 kg m3 )

(8.314 Pa m3 K1 mol1 ) (773 K)

9.32 104 Pa

= 0.256 kg mol1 = 256 g mol1 .

This molar mass must be an integral multiple of the molar mass of atomic sulfur; hence
number of S atoms =

256 g mol1
32.0 g mol1

= 8.

The formula of the vapor is then S8 .

E1.9(a)

The partial pressure of the water vapor in the room is:

pH2 O = (0.60) (26.74 Torr) = 16 Torr.

TRAPP: CHAP01 2006/3/8 18:03 PAGE 6 #6

THE PROPERTIES OF GASES

m
m
, pV = RT or
M
M





3 dm3
1 atm
10
(18.02 g mol1 )
(16 Torr)
(400 m3 )
760 Torr
m3

Assuming that the perfect gas equation [1.8] applies, with n =

m=

pVM
=
RT

(0.0821 dm3 atm K1 mol1 ) (300 K)

= 6.2 103 g = 6.2 kg .

E1.10(a)

(a) For simplicity assume a container of volume 1 dm3 . Then the total mass is
mT = nN2 MN2 + nO2 MO2 = 1.146 .g

(1)

Assuming that air is a perfect gas, pT V = nT RT , where nT is the total amount of gas

1 atm
(1 dm3 )
PT V
1.013 bar
=
nT =
= 0.03955 mol,
RT
(0.08206 dm3 atm K1 mol1 ) (300 K)


(0.987 bar)

nT = nN2 + nO2 = 0.03955 mol.

(2)

Equations (1) and (2) are simultaneous equations for the amounts of gas and may be solved for them.
Inserting nO2 from (2) into (1) we get
(nN2 ) (28.0136 g mol1 ) + (0.03955 mol nN2 ) (31.9988 g mol1 ) = 1.146 g.
(1.2655 1.1460) g = (3.9852 g mol1 ) (nN2 ).
nN2 = 0.02999 mol.
nO2 = nT nN2 = (0.03955 0.02999) mol = 9.56 103 mol.
The mole fractions are
xN2 =

0.02999 mol
0.03955 mol

= 0.7583 ,

xO2 =

9.56 103 mol

0.03955 mol

= 0.2417 .

The partial pressures are pN2 = (0.7583) (0.987 bar) = 0.748 bar ,
pO2 = (0.2417) (0.987 bar) = 0.239 bar .
The sum checks, (0.748 + 0.239) bar = 0.987 bar.
(b) The simplest way to solve this part is to realize that nT , pT , and mT remain the same as in part (a)
as these are experimentally determined quantities. However, the simultaneous equations that need
to be solved are modified as follows:
mT = nN2 MN2 + nO2 MO2 + nAr MAr = 1.146 g,
nT = nN2 + nO2 + nAr = 0.03955 mol,
Since xAr = 0.0100, nAr = 0.0003955 mol.

TRAPP: CHAP01 2006/3/8 18:03 PAGE 7 #7

SOLUTIONS MANUAL

Solving the equations yields

nN2 = 0.03084,

xN2 = 0.7798 ,

nO2 = 0.008314,

xO2 = 0.2102 .

The partial pressures are:

pN2 = xN2 pT = 0.7798 0.987 bar = 0.770 bar ,
pO2 = xO2 pT = 0.2102 0.987 bar = 0.207 bar ,
pAr = xAr pT = 0.0100 0.987 bar = 0.00987 bar .
E1.11(a)

This exercise uses the formula, M =

RT
, which was developed and used in Exercises 1.7(b) and
p

1.8(a). Substituting the data,

M=

(1.23 kg m3 ) (8.314 dm3 kPa K1 mol1 ) (330 K)

20 kPa

103 g
kg

103 m3

dm3

= 169 g mol1 .
E1.12(a)

The easiest way to solve this exercise is to assume a sample of mass 1.000 g, then calculate the volume
at each temperature, plot the volume against the Celsius temperature, and extrapolate to V = 0.
Draw up the following table.
/ C

/(g dm3 )

V /(dm3 g1 )

85
0
100

1.877
1.294
0.946

0.5328
0.7728
1.057

V versus is plotted in Fig. 1.1. The extrapolation gives a value for absolute zero close to 273 C.
Alternatively, one could use an equation for V as a linear function of , which is Charless law, and solve
for the value of absolute zero. V = V0 (1 + ).
1
At absolute zero, V = 0, then (abs. zero) = . The value of can be obtained from any one of the

data points (except = 0) as follows.

From V = V0 (1 + ),

=

V
1
V0

1.057
0.7728

100 C

1
= 0.003678( C)1

1
1
=
= 272 C .

0.003678( C)1

which is close to the value obtained graphically.

TRAPP: CHAP01 2006/3/8 18:03 PAGE 8 #8

V/(dm3 g1)

THE PROPERTIES OF GASES

u/ C

E1.13(a)

(a) p =

Figure 1.1

nRT
[1.8].
V
n = 1.0 mol,

T = 273.15 K (i)

V = 22.414 dm3 (i) or

(i) p =
(ii) p =

or

1000 K (ii).

100 cm3 (ii).

(1.0 mol) (8.206 102 dm3 atm K1 mol1 ) (273.15 K)

22.414 dm3
(1.0 mol) (8.206 102 dm3 atm K1 mol1 ) (1000 K)
0.100 dm3

= 1.0 atm .

= 8.2 102 atm .

nRT
an2
2 [1.21a].
V nb
V
From Table 1.6, a = 5.507 dm6 atm mol2 and b = 6.51 102 dm3 mol1 . Therefore,
(i)
nRT
(1.0 mol) (8.206 102 dm3 atm K1 mol1 ) (273.15 K)
= 1.003 atm,
=
V nb
[22.414 (1.0) (6.51 102 )] dm3

(b) p =

an2
(5.507 dm6 atm mol2 ) (1.0 mol)2
=
= 1.11 102 atm,
2
V
(22.414 dm3 )2
and p = 1.003 atm 1.11 102 atm = 0.992 atm = 1.0 atm .
(ii)

(1.0 mol) (8.206 102 dm3 atm K1 mol1 ) (1000 K)

nRT
,
=
V nb
(0.100 0.0651) dm3
= 2.27 103 atm,
an2
(5.507 dm6 atm mol2 ) (1.0 mol)2
=
= 5.51 102 atm,
2
V
(0.100 dm3 )2
and p = 2.27 103 atm 5.51 102 atm = 1.7 103 atm .

TRAPP: CHAP01 2006/3/8 18:03 PAGE 9 #9

10

SOLUTIONS MANUAL

COMMENT. It is instructive to calculate the percentage deviation from perfect gas behaviour for (i) and (ii).

0.992 1.000
100% = 0.8%.
1.000
2
(17 10 ) (8.2 102 )
(ii)
100% = 107%.
8.2 102
(i)

Deviations from perfect gas behavior are not observed at p 1 atm except with very precise apparatus.
E1.14(a)

The conversions needed are as follows:

1 atm = 1.013 105 Pa

1 Pa = 1 kg m1 s2

1 dm6 = 106 m6

1 dm3 = 103 m3 .

Therefore,
a = 0.751 atm dm6 mol2 becomes, after substitution of the conversions,
a = 7.61 102 kg m5 s2 mol2 , and
b = 0.0226 dm3 mol1 becomes
b = 2.26 105 m3 mol1 .
E1.15(a)

The definition of Z is used Z =

pVm
Vm
[1.17] = .
RT
Vm

Vm is the actual molar volume, Vm is the perfect gas molar volume. Vm =

smaller than that of a perfect gas, Vm = 0.88Vm , and

RT
. Since Vm is 12 per cent
p

0.88Vm
= 0.88 .
Vm
ZRT
(0.88) (8.206 102 dm3 atm K1 mol1 ) (250 K)
=
= 1.2 dm3 mol1 .
(b) Vm =
p
15 atm
(a) Z =

Since Vm < Vm attractive forces dominate.

E1.16(a)

The amount of gas is first determined from its mass; then the van der Waals equation is used to determine
its pressure at the working temperature. The initial conditions of 300 K and 100 atm are in a sense
superfluous information.
n=

92.4 kg
28.02 103 kg mol1

= 3.30 103 mol

V = 1.000 m3 = 1.000 103 dm3

p=

nRT
(3.30 103 mol) (0.08206 dm3 atm K1 mol1 ) (500 K)
an2
2 [1.21a] =
V nb
V
(1.000 103 dm3 ) (3.30 103 mol) (0.0387 dm3 mol1 )

(1.352 dm6 atm mol2 ) (3.30 103 mol)2

(1.000 103 dm3 )2

= (155 14.8) atm = 140 atm .

E1.17(a)

(a) p =

nRT
(10.0 mol) (0.08206 dm3 atm K1 mol1 ) (300 K)
= 50.7 atm .
[1.8] =
V
4.860 dm3

TRAPP: CHAP01 2006/3/8 18:03 PAGE 10 #10

THE PROPERTIES OF GASES

p=

(b)

11

 n 2
nRT
[1.21a]
a
V nb
V
(10.0 mol) (0.08206 dm3 atm K1 mol1 ) (300 K)
(4.860 dm3 ) (10.0 mol) (0.0651 dm3 mol1 )


10.0 mol 2
(5.507 dm6 atm mol2 )
4.860 dm3

= 58.49 23.32 = 35.2 atm .

V
.
n
To complete the calculation of Z, a value for the pressure, p, is required. The implication in the definition
[1.17] is that p is the actual pressure as determined experimentally. This pressure is neither the perfect
gas pressure nor the van der Waals pressure. However, on the assumption that the van der Waals equation
provides a value for the pressure close to the experimental value, we can calculate the compression factor
as follows
The compression factor is calculated from its definition [1.17] after inserting Vm =

Z=

(35.2 atm) (4.860 dm3 )

pV
=
= 0.695 .
nRT
(10.0 mol) (0.08206 dm3 atm K1 mol1 ) (300 K)

COMMENT. If the perfect gas pressure had been used, Z would have been 1, the perfect gas value.

E1.18(a)

n = n(H2 ) + n(N2 ) = 2.0 mol + 1.0 mol = 3.0 mol,

xJ =

nJ
[1.14].
n

2.0 mol
1.0 mol
x(N2 ) =
= 0.67 ,
= 0.33 .
3.0 mol
3.0 mol
(b) The perfect gas law is assumed to hold for each component individually as well as for the mixture
RT
.
as a whole. Hence, pJ = nJ
V
(a) x(H2 ) =

(8.206 102 dm3 atm K1 mol1 ) (273.15 K)

RT
= 1.00 atm mol1 .
=
V
22.4 dm3
p(H2 ) = (2.0 mol) (1.00 atm mol1 ) = 2.0 atm .
p(N2 ) = (1.0 mol) (1.00 atm mol1 ) = 1.0 atm .
(c) p = p(H2 ) + p(N2 )[1.15] = 2.0 atm + 1.0 atm = 3.0 atm .
Question. Does Daltons law hold for a mixture of van der Waals gases?
E1.19(a)

Equations [1.22] are solved for b and a, respectively, and yield b =

Vc
and a = 27b2 pc = 3Vc2 pc .
3

Substituting the critical constants,

b=

1
(98.7 cm3 mol1 ) = 32.9 cm3 mol1 ,
3

a = 3 (98.7 103 dm3 mol1 )2 (45.6 atm) = 1.33 dm6 atm mol2 .
Note that knowledge of the critical temperature, Tc , is not required.

TRAPP: CHAP01 2006/3/8 18:03 PAGE 11 #11

12

SOLUTIONS MANUAL

As b is approximately the volume occupied per mole of particles

vmol

b
32.9 106 m3 mol1
=
= 5.46 1029 m3 .
NA
6.022 1023 mol1

Then, with vmol =

E1.20(a)

4 3
r , r
3

1/3

3
(5.46 1029 m3 )
4

= 0.24 nm .

The Boyle temperature, TB , is the temperature at which B = 0. In order to express TB in terms of a and
b, the van der Waals equation must be recast into the form of the virial equation.
a
RT
2 [1.21b].
Vm b Vm

p=

Factoring out

RT
RT
yields p =
Vm
Vm


1
a
.

1 b/Vm
RTVm

So long as b/Vm < 1, the first term inside the brackets can be expanded using (1x)1 = 1+x+x 2 + ,
which gives





RT
a 
1
p=
1+ b
+

Vm
RT
Vm
We can now identify the second virial coefficient as B = b
Since at the Boyle temperature B = 0, TB =

a
.
RT

a
27Tc
=
.
bR
8

(a) From Table 1.6, a = 6.260 dm6 atm mol2 , b = 5.42 102 dm3 mol1 . Therefore,
TB =

6.260 dm6 atm mol2

(5.42 102 dm mol1 ) (8.206 102 dm3 atm K1 mol1 )
3

(b) As in Exercise 1.19(a), vmol


r
E1.21(a)

= 1.41 103 K .

b
5.42 105 m3 mol1
=
= 9.00 1029 m3
NA
6.022 1023 mol1
1/3

3
(9.00 1029 m3 )
4

= 0.59 nm .

The reduced temperature and pressure of hydrogen are calculated from the relations
Tr =

T
Tc

and

pr =

p
[1.24].
pc

298 K
= 8.968 [Tc = 33.23 K, Table 1.5],
33.23 K
1.0 atm
= 0.0781 [pc = 12.8 atm, Table 1.5].
pr =
12.8 atm

Tr =

Hence, the gases named will be in corresponding states at T = 8.968 Tc and at p = 0.0781 pc .

TRAPP: CHAP01 2006/3/8 18:03 PAGE 12 #12

THE PROPERTIES OF GASES

13

(a) For ammonia, Tc = 405.5 K and pc = 111.3 atm (Table 1.5), so

T = (8.968) (405.5 K) = 3.64 103 K ,
p = (0.0781) (111.3 atm) = 8.7 atm .
(b) For xenon, Tc = 289.75 K and pc = 58.0 atm, so
T = (8.968) (289.75 K) = 2.60 103 K ,
p = 0.0781) (58.0 atm) = 4.5 atm .
(c) For helium, Tc = 5.21 K and pc = 2.26 atm, so
T = (8.968) (5.21 K) = 46.7 K ,
p = (0.0781) (2.26 atm) = 0.18 atm .
E1.22(a)

The van der Waals equation [1.21b] is solved for b, which yields
RT

b = Vm 

a
p+ 2
Vm

.

Substituting the data

(8.314 J K1 mol1 ) (273 K)




6 Pa mol2
0.50
m
(3.0 106 Pa) +
(5.00 104 m3 mol1 )2

b = 5.00 104 m3 mol1

= 0.46 104 m3 mol1 .

Z=

(3.0 106 Pa) (5.00 104 m3 )

pVm
[1.17] =
= 0.66.
RT
(8.314 J K1 mol1 ) (273 K)

COMMENT. The denition of Z involves the actual pressure, volume, and temperature and does not depend

upon the equation of state used to relate these variables.

Solutions to problems
Solutions to numerical problems
P1.1

Since the Neptunians know about perfect gas behavior, we may assume that they will write pV = nRT
at both temperatures. We may also assume that they will establish the size of their absolute unit to be
the same as the N, just as we write 1K = 1 C. Thus
pV (T1 ) = 28.0 dm3 atm = nRT1 = nR (T1 + 0 N),
pV (T2 ) = 40.0 dm3 atm = nRT2 = nR (T1 + 100 N),
or T1 =

28.0 dm3 atm

,
nR

T1 + 100 N =

40.0 dm3 atm

.
nR

TRAPP: CHAP01 2006/3/8 18:03 PAGE 13 #13

14

SOLUTIONS MANUAL

T1 + 100 N
40.0 dm3 atm
=
= 1.429 or T1 + 100 N = 1.429T1 , T1 = 233 absolute units.
T1
28.0 dm3 atm
As in the relationship between our Kelvin scale and Celsius scale T = absolute zero( N) so absolute
zero( N) = 233 N .

Dividing,

COMMENT. To facilitate communication with Earth students we have converted the Neptunians units of

the pV product to units familiar to humans, which are dm3 atm. However, we see from the solution that only
the ratio of pV products is required, and that will be the same in any civilization.

Question. If the Neptunians unit of volume is the lagoon (L), their unit of pressure is the poseidon (P),
their unit of amount is the nereid (n), and their unit of absolute temperature is the titan (T), what is the
value of the Neptunians gas constant (R) in units of L, P, n, and T?
P1.3

The value of absolute zero can be expressed in terms of by using the requirement that the volume of
a perfect gas becomes zero at the absolute zero of temperature. Hence
0 = V0 [1 + (abs. zero)].
1
Then (abs. zero) = .

All gases become perfect in the limit of zero pressure, so the best value of and, hence, (abs. zero)
is obtained by extrapolating to zero pressure. This is done in Fig. 1.2. Using the extrapolated value,
= 3.6637 103 C1 , or

(abs. zero) =

1
= 272.95 C ,
3.6637 103 C1

which is close to the accepted value of 273.15 C.

3.672
3.670
3.668
3.666

3.664
3.662
0

200

400
p / Torr

600

800

Figure 1.2

TRAPP: CHAP01 2006/3/8 18:03 PAGE 14 #14

THE PROPERTIES OF GASES

P1.5

15

nR
p
p3
p
=
= constant, if n and V are constant. Hence,
=
, where p is the measured pressure at
T
V
T
T3
temperature,
  T , and p3 and T3 are the triple point pressure and temperature, respectively. Rearranging,
p3
T.
p=
T3
6.69 kPa
p3
= 0.0245 kPa K 1 . Thus the change in p,
p, is proportional to
is a constant =
T3
273.16 K
the change in temperature,
T :
p = (0.0245 kPa K 1 ) (
T ).

The ratio

(a)
p = (0.0245 kPa K 1 ) (1.00 K) = 0.0245 kPa .


 
373.16 K
T
p3 =
(6.69 kPa) = 9.14 kPa .
(b) Rearranging, p =
T3
273.16 K
p
(c) Since is a constant at constant n and V , it always has the value 0.0245 kPa K 1 ; hence
T

p = p374.15 K p373.15 K = (0.0245 kPa K 1 ) (1.00 K) = 0.0245 kPa .

P1.7

RT
(8.206 102 dm3 atm K 1 mol1 ) (350 K)
=
= 12.5 dm3 mol1 .
p
2.30 atm
RT
a
RT
 + b[rearrange1.21b]
[1.21b], we obtain Vm = 

(b) From p =
a
Vm b Vm2
p+ 2
Vm
Then, with a and b from Table 1.16,
(a) Vm =


8.206 102 dm3 atm K1 mol1 (350 K)
2
3
1

Vm

2  + (5.42 100 dm mol )
(2.30 atm) + (6.260 dm6 atm mol2 )/ 12.5 dm3 mol1


28.72 dm3 mol1 
+ 5.42 102 dm3 mol1 12.3 dm3 mol1 .
2.34

Substitution of 12.3 dm3 mol1 into the denominator of the first expression again results in
Vm = 12.3 dm3 mol1 , so the cycle of approximation may be terminated.
P1.9

As indicated by eqns1.18and 1.19 the compression factor of a gas may be expressed as either a virial
1
. The virial form of the van der Waals equation is derived in Exercise 1.20(a)
expansion in p or in
V
m





a 
1
RT
1+ b
+

and is p =
Vm
RT
Vm



a 
1
pVm
=1+ b
+

Rearranging, Z =
RT
RT
Vm
On the assumption that the perfect gas expression for Vm is adequate for the second term in this expansion,
we can readily obtain Z as a function of p.

Z =1+

1
RT


a 
b
p +
RT

TRAPP: CHAP01 2006/3/8 18:03 PAGE 15 #15

16

(a)

SOLUTIONS MANUAL

Tc = 126.3 K.


RT
RT 
a 
Vm =
Z =
+ b
+
p
p
RT
=

(0.08206 dm3 atm K 1 mol1 ) (126.3 K)

10.0 atm




1.352 dm6 atm mol2
3
1
+ (0.0387 dm mol )
(0.08206 dm3 atm K 1 mol1 ) (126.3 K)

= (1.036 0.092) dm3 mol1 = 0.944 dm3 mol1 .

Z=

 p 
(10.0 atm) (0.944 dm3 mol1 )
(Vm ) =
= 0.911.
RT
(0.08206 dm3 atm K 1 mol1 ) (126.3 K)

(b) The Boyle temperature corresponds to the temperature at which the second virial coefficient is zero,
hence correct to the first power in p, Z = 1, and the gas is close to perfect. However, if we assume
that N2 is a van der Waals gas, when the second virial coefficient is zero,


a
b
RTB

TB =


= 0,

or

TB =

a
.
bR

1.352 dm6 atm mol2

(0.0387 dm mol1 ) (0.08206 dm3 atm K 1 mol1 )
3

= 426 K.

The experimental value (Table 1.5) is 327.2 K. The discrepancy may be explained by two
considerations.
1. Terms beyond the first power in p should not be dropped in the expansion for Z.
2. Nitrogen is only approximately a van der Waals gas.
RT
, and using TB = 327.2 K
When Z = 1, Vm =
p
=

(0.08206 dm3 atm K1 mol1 ) 327.2 K

10.0 atm

= 2.69 dm3 mol1

and this is the ideal value of Vm . Using the experimental value of TB and inserting this value into
the expansion for Vm above, we have
Vm =

0.08206 dm3 atm K1 mol1 327.2 K

10.0 atm




6
2
1.352
dm
atm
mol
+ 0.0387 dm3 mol1
0.08206 dm3 atm K 1 mol1 327.2 K

= (2.685 0.012) dm3 mol1 = 2.67 dm3 mol1

and Z =

Vm
2.67 dm3 mol1
=
= 0.992 1.

Vm
2.69 dm3 mol1

TRAPP: CHAP01 2006/3/8 18:03 PAGE 16 #16

THE PROPERTIES OF GASES

17

(c) TI = 621 K [Table 2.9].

Vm =

0.08206 dm3 atm K1 mol1 621 K

10.0 atm




1.352 dm6 atm mol2
3
1
+ 0.0387 dm mol
0.08206 dm3 atm K 1 mol1 621 K

= (5.096 + 0.012) dm3 mol1 = 5.11 dm3 mol1

and Z =

5.11 dm3 mol1

5.10 dm3 mol1

= 1.002 1.

Based on the values of TB and TI given in Tables 1.4 and 2.9 and assuming that N2 is a van der Waals
gas, the calculated value of Z is closest to 1 at TI , but the difference from the value at TB is less than
the accuracy of the method.
P1.11

(a) Vm =

molar mass
M
18.02 g mol1
= 0.1353 dm3 mol1 .
=
=
density

1.332 102 g dm3

pVm
(327.6 atm) (0.1353 dm3 mol1 )
[1.17b] =
= 0.6957 .
RT
(0.08206 dm3 atm K 1 mol1 ) (776.4 K)
(c) Two expansions for Z based on the van der Waals equation are given in Problem 1.9. They are



a 
1
Z =1+ b
+

RT
Vm





5.464 dm6 atm mol2

3
1
= 1 + (0.0305 dm mol )
(0.08206 dm3 atm K1 mol1 ) (776.4 K)

(b) Z =

= 1 0.4084 = 0.5916 0.59.

0.1353 dm3 mol1
 

a 
1
b
(p) +
Z =1+
RT
RT

=1+

1
(0.08206 dm

atm K 1 mol1 ) (776.4 K)

(0.0305 dm mol
3

5.464 dm6 atm mol2

(0.08206 dm3 atm K 1 mol1 ) (776.4 K)

327.6 atm

= 1 0.2842 0.72 .
1
Vm
is not as good. However, when terms beyond the second are included the results from the two
expansions for Z converge.

In this case the expansion in p gives a value close to the experimental value; the expansion in

P1.13

Vc = 2b,

Tc =

a
[Table 1.7]
4bR

TRAPP: CHAP01 2006/3/8 18:03 PAGE 17 #17

18

SOLUTIONS MANUAL

Hence, with Vc and Tc from Table 1.5, b =

1
1
Vc = (118.8 cm3 mol1 ) = 59.4 cm3 mol1 .
2
2

a = 4bRTc = 2RTc Vc
= (2) (8.206 102 dm3 atm K 1 mol1 ) (289.75 K) (118.8 103 dm3 mol1 )
= 5.649 dm6 atm mol2 .
Hence
p=
=

RT
nRT na/RTV
ea/RTVm =
e
Vm b
V nb
(1.0 mol) (8.206 102 dm3 atm K 1 mol1 ) (298 K)
(1.0 dm3 ) (1.0 mol) (59.4 103 dm3 mol1 )



(1.0 mol) (5.649 dm6 atm mol2 )
exp
(8.206 102 dm3 atm K 1 mol1 ) (298 K) (1.0 dm6 atm mol1 )

= 26.0 atm e0.231 = 21 atm .

Solutions to theoretical problems

P1.15

This expansion has already been given in the solutions to Exercise 1.20(a) and Problem 1.14; the
result is
p=

RT
Vm



b2
a  1
+ 2 + .
1+ b
RT Vm
Vm

Compare this expansion with p =

and hence find B = b

RT
Vm


1+


B
C
+
+ [1.19]
Vm
Vm 2

a
and C = b2 .
RT

Since C = 1200 cm6 mol2 ,

b = C 1/2 = 34.6 cm3 mol1

a = RT (b B) = (8.206 102 ) (273 dm3 atm mol1 ) (34.6 + 21.7) cm3 mol1
= (22.40 dm3 atm mol1 ) (56.3 103 dm3 mol1 ) = 1.26 dm6 atm mol2 .
P1.17

The critical point corresponds to a point of zero slope that is simultaneously a point of inflection in a
plot of pressure versus molar volume. A critical point exists if there are values of p, V , and T that result
in a point that satisfies these conditions.
p=

B
C
RT
2 + 3.
Vm
Vm
Vm

TRAPP: CHAP01 2006/3/8 18:03 PAGE 18 #18

THE PROPERTIES OF GASES


p
RT
2B
3C
= 2 + 3 4 =0
V
V
V
V
m
m
m
m
 2 T
2RT
6B
12C
p
=

+
=0
Vm2 T
Vm3
Vm4
Vm5
RTc Vc2 + 2BVc 3C
RTc Vc2 3BVc + 6C

That is,

which solve to Vc =

=0
=0

19

at the critical point.

3C
B2
, Tc =
.
B
3RC

Now use the equation of state to find pc

pc =

RTc
B
C
2 + 3 =
Vc
Vc
Vc

It follows that Zc =
P1.19

pc V c
=
RTc

RB2
3RC

B3
27C 2

B
3C

3C
B


B

B
3C

2
+C

B
3C

3
=

B3
.
27C 2


  
1
3RC
1
=
.

2
R
3
B

For a real gas we may use the virial expansion in terms of p [1.18]
RT
nRT
(1 + B p + )
(1 + B p + ) =
M
V

p=

which rearranges to

p
RT
RT B
=
+
p + .

M
M

Therefore, the limiting slope of a plot of

B RT
p
against p is
. From Fig. 1.3 the limiting slope is

B RT
(5.84 5.44) 104 m2 s2
= 4.4 102 kg1 m3 .
=
M
(10.132 1.223) 104 Pa
From Fig. 1.2,
B =

RT
= 5.40 104 m2 s2 ; hence
M

4.4 102 kg1 m3

= 0.81 106 Pa1 ,
5.40 104 m2 s2

B = (0.81 106 Pa1 ) (1.0133 105 Pa atm1 ) = 0.082 atm1 .

B = RTB [Problem 1.18]
= (8.206 102 dm3 atm K 1 mol1 ) (298 K) (0.082 atm1 )
= 2.0 dm3 mol1 .

P1.21

The critical temperature is that temperature above which the gas cannot be liquefied by the application
of pressure alone. Below the critical temperature two phases, liquid and gas, may coexist at equilibrium,
and in the two-phase region there is more than one molar volume corresponding to the same conditions

TRAPP: CHAP01 2006/3/8 18:03 PAGE 19 #19

20

SOLUTIONS MANUAL
y = 5.3963 + 0.046074x R = 0.99549

(p/r) / (104 m2 s1)

5.9
5.8
5.7
5.6
5.5
5.4
0

10

p/(104 Pa)

12

Figure 1.3

of temperature and pressure. Therefore, any equation of state that can even approximately describe this
situation must allow for more than one real root for the molar volume at some values of T and p, but
as the temperature is increased above Tc , allows only one real root. Thus, appropriate equations of state
must be equations of odd degree in Vm .
The equation of state for gas A may be rewritten Vm2 (RT /p)Vm (RTb/p) = 0, which is a quadratic
and never has just one real root. Thus, this equation can never model critical behavior. It could possibly
model in a very crude manner a two-phase situation, since there are some conditions under which a
quadratic has two real positive roots, but not the process of liquefaction.
The equation of state of gas B is a first-degree equation in Vm and therefore can never model critical
behavior, the process of liquefaction, or the existence of a two-phase region.
A cubic equation is the equation of lowest degree that can show a cross-over from more than one real
root to just one real root as the temperature increases. The van der Waals equation is a cubic equation
in Vm .
P1.23

The two masses represent the same volume of gas under identical conditions, and therefore, the same
number of molecules (Avogadros principle) and moles, n. Thus, the masses can be expressed as
nMN = 2.2990 g
for chemical nitrogen and
nAr MAr + nN MN = n[xAr MAr + (1 xAr )MN ] = 2.3102 g
for atmospheric nitrogen. Dividing the latter expression by the former yields
2.3102
xAr MAr
+ (1 xAr ) =
MN
2.2990
and xAr =


so

xAr


MAr
2.3102
1 =
1
MN
2.2990

(2.3102/2.2990) 1
(2.3102/2.2990) 1
=
= 0.011 .
(MAr /MN ) 1
(39.95 g mol1 )/(28.013 g mol1 1)

COMMENT.

This value for the mole fraction of argon in air is close to the modern value.

TRAPP: CHAP01 2006/3/8 18:03 PAGE 20 #20

THE PROPERTIES OF GASES

21

Solutions to applications
P1.25

1 t = 103 kg. Assume 300 t per day.

n(SO2 ) =
V=
P1.27

300 103 kg
64 103 kg mol1

= 4.7 106 mol.

nRT
(4.7 106 mol) (0.082 dm3 atm K 1 mol1 ) 1073 K
=
= 4.1 108 dm3 .
p
1.0 atm

The pressure at the base of a column of height H is p = gH (Example 1.1). But the pressure at any
altitude h within the atmospheric column of height H depends only on the air above it; therefore
p = g(H h) and dp = g dh.
Since =

pM
pMgdh
dp
Mg dh
[Problem 1.2], dp =
, implying that
=
RT
RT
p
RT

This relation integrates to p = p0 eMgh/RT

For air M 29 g mol1 and at 298 K
Mg
(29 103 kg mol1 ) (9.81 m s2 )
= 1.15 104 m1 [1 J = 1 kg m2 s2 ].

RT
2.48 103 J mol1

(a) h = 15 cm.

p = p0 e(0.15 m)(1.1510

m1 )

= 0.99998 p0 ;

(b) h = 11 km = 1.1 104 m.

p = p0 e(1.110
P1.29

4 )(1.15104 m 1 )

= 0.28 p0 ;

p p0
= 0.00 .
p0
p p0
= 0.72 .
p0

Refer to Fig. 1.3.

Air
(environment)

Ground

Figure 1.4

TRAPP: CHAP01 2006/3/8 18:03 PAGE 21 #21

22

SOLUTIONS MANUAL

The buoyant force on the cylinder is

Fbuoy = Fbottom Ftop
= A(pbottom ptop )
according to the barometric formula.
ptop = pbottom eMgh/RT
where M is the molar mass of the
 environment (air). Since h is small, the exponential can be expanded
1
in a Taylor series around h = 0 ex = 1 x + x 2 + . Keeping the first-order term only yields
2!

Mgh
.
1
RT


ptop = pbottom

The buoyant force becomes




pbottom M
Mgh
= Apbottom 1 1 +
= Ah
g
RT
RT




pbottom V
pbottom VM
g = nMg
n=
=
RT
RT


Fbuoy

n is the number of moles of the environment (air) displaced by the balloon, and nM = m, the mass of
the displaced environment. Thus Fbuoy = mg. The net force is the difference between the buoyant force
and the weight of the balloon. Thus
Fnet = mg mballoon

g = (m mballoon )g

This is Archimedes principle.

TRAPP: CHAP01 2006/3/8 18:03 PAGE 22 #22