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

PART 1 Equilibrium
TRAPP: CHAP01 2006/3/8 18:03 PAGE 2 #2
TRAPP: CHAP01 2006/3/8 18:03 PAGE 3 #3
1
The properties of gases
Answers to discussion questions
D1.1 An equation of state is an equation that relates the variables that dene the state of a systemto 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 howvolume varies with amount of gas (V n).
Combining all of these proportionalities into one we nd
AQ: Please
check we have
change P to
p.
V
nT
p
.
Inserting the constant of proportionality, R, yields the perfect gas equation
V =
RnT
p
or pV = nRT.
D1.3 Consider three temperature regions:
(1) T < T
B
. 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 T
B
. Z 1 at low pressures, slightly greater than 1 at intermediate pressures, and signicantly
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 > T
B
. 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 Justication 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 modied to account for the effect of
temperature. Experimentally one nds 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 4 #4
4 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.
Solving for the pressure gives p =
nRT
V
.
The amount of xenon is n =
131 g
131 g mol
1
= 1.00 mol.
p =
(1.00 mol) (0.0821 dm
3
atmK
1
mol
1
) (298.15 K)
1.0 dm
3
= 24 atm .
That is, the sample would exert a pressure of 24 atm if it were a perfect gas, not 20 atm.
(b) The van der Waals equation [1.21a] for the pressure of a gas is p =
nRT
V nb

an
2
V
2
.
For xenon, Table 1.6 gives a = 4.137 dm
6
atmmol
2
and b = 5.16 10
2
dm
3
mol
1
.
Inserting these constants, the terms in the equation for p become
nRT
V nb
=
(1.00 mol) (0.08206 dm
3
atmK
1
mol
1
) (298.15 K)
1.0 dm
3
{(1.00 mol) (5.16 10
2
dm
3
mol
1
)}
= 25.8 atm,
an
2
V
2
=
(4.137 dm
6
atmmol
2
) (1.00 mol)
2
(1.0 dm
3
)
2
= 4.137 atm.
Therefore, p = 25.8 atm 4.137 atm = 22 atm .
E1.2(a) Boyles law [1.5] in the form p
f
V
f
= p
i
V
i
can be solved for either initial or nal pressure, hence
p
i
=
V
f
V
i
p
f
,
V
f
= 4.65 dm
3
, V
i
= 4.65 dm
3
+ 2.20 dm
3
= 6.85 dm
3
, p
f
= 5.04 bar.
Therefore,
(a) p
i
=
_
4.65 dm
3
6.85 dm
3
_
(5.04 bar) = 3.42 bar .
(b) Since 1 atm = 1.013 bar, p
i
= (3.42 bar)
_
1 atm
1.013 bar
_
= 3.38 atm .
E1.3(a) The perfect gas law, pV = nRT [1.8], can be rearranged to
p
T
=
nR
V
= constant, if n and V are constant.
Hence,
p
f
T
f
=
p
i
T
i
or, solving for p
f
, p
f
=
T
f
T
i
p
i
.
Internal pressure = pump pressure + atmospheric pressure.
p
i
= 24 lb in
2
+ 14.7 lb in
2
= 38.7 lb in
2
, T
i
= 268 K(5

C), T
f
= 308 K(35

C).
p
f
=
308 K
268 K
38.7 lb in
2
= 44.5 lb in
2
.
Therefore, p(pump) = 44.5 lb in
2
14.7 lb in
2
= 30 lb in
2
.
TRAPP: CHAP01 2006/3/8 18:03 PAGE 5 #5
THE PROPERTIES OF GASES 5
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 lawin the formp =
nRT
V
[1.8] is appropriate. T and V are given; n needs to be calculated.
n =
0.255 g
20.18 g mol
1
= 1.26 10
2
mol, T = 122 K, V = 3.00 dm
3
.
Therefore, upon substitution,
p =
(1.26 10
2
mol) (0.08206 dm
3
atmK
1
mol
1
) (122 K)
3.00 dm
3
= 4.20 10
2
atm .
E1.5(a) Boyles law in the form p
f
V
f
= p
i
V
i
is solved for V
f
: V
f
=
p
i
p
f
V
i
.
p
i
= 1.0 atm,
p
f
= p
ex
+ gh[1.3] = p
i
+ gh = 1.0 atm + gh,
gh = (1.025 10
3
kg m
3
) (9.81 ms
2
) (50 m) = 5.03 10
5
Pa.
Hence, p
f
= (1.01 10
5
Pa) + (5.03 10
5
Pa) = 6.04 10
5
Pa.
V
f
=
1.01 10
5
Pa
6.04 10
5
Pa
3.0 m
3
= 0.50 m
3
.
E1.6(a) The pressure in the apparatus is given by
p = p
atm
+ gh [1.3].
p
atm
= 770 Torr
_
1 atm
760 Torr
_

_
1.013 10
5
Pa
760 Torr
_
= 1.026 10
5
Pa
gh = 0.99707 g cm
3

_
1 kg
10
3
g
_

_
10
6
cm
3
m
3
_
9.806 m s
2
= 977 Pa
p = 1.026 10
5
Pa + 977 Pa = 1.036 10
5
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 =
F
A
=
hAg
A
= hg.
TRAPP: CHAP01 2006/3/8 18:03 PAGE 6 #6
6 SOLUTIONS MANUAL
p = (0.99707 g cm
3
)
_
1 kg
10
3
g
_

_
10
6
cm
3
1 m
3
_
(206.402 cm)
_
1 m
10
2
cm
_
(9.8067 m s
2
)
= 2.0182 10
4
Pa.
V = (20.000 dm
3
)
_
1 m
3
10
3
dm
3
_
= 2.0000 10
2
m
3
.
n =
m
M
=
0.25132 g
4.00260 g mol
1
= 0.062789 mol.
The perfect gas equation [1.8] can be rearranged to give R =
pV
nT
.
R =
(2.0182 10
4
Pa) (2.0000 10
2
m
3
)
(0.062789 mol) (773.15 K)
= 8.3147 JK
1
mol
1
.
The accepted value is R = 8.3145 J K
1
mol
1
.
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
M
RT.
Upon rearrangement,
M =
_
RT
p
_
= (3.71 kg m
3
)
(8.314 Pa m
3
K
1
mol
1
) (773 K)
9.32 10
4
Pa
= 0.256 kg mol
1
= 256 g mol
1
.
This molar mass must be an integral multiple of the molar mass of atomic sulfur; hence
number of S atoms =
256 g mol
1
32.0 g mol
1
= 8.
The formula of the vapor is then S
8
.
E1.9(a) The partial pressure of the water vapor in the room is:
p
H
2
O
= (0.60) (26.74 Torr) = 16 Torr.
TRAPP: CHAP01 2006/3/8 18:03 PAGE 7 #7
THE PROPERTIES OF GASES 7
Assuming that the perfect gas equation [1.8] applies, with n =
m
M
, pV =
m
M
RT or
m =
pVM
RT
=
(16 Torr)
_
1 atm
760 Torr
_
(400 m
3
)
_
10
3
dm
3
m
3
_
(18.02 g mol
1
)
(0.0821 dm
3
atmK
1
mol
1
) (300 K)
= 6.2 10
3
g = 6.2 kg .
E1.10(a) (a) For simplicity assume a container of volume 1 dm
3
. Then the total mass is
m
T
= n
N
2
M
N
2
+ n
O
2
M
O
2
= 1.146 .g (1)
Assuming that air is a perfect gas, p
T
V = n
T
RT, where n
T
is the total amount of gas
n
T
=
P
T
V
RT
=
(0.987 bar)
_
1 atm
1.013 bar
_
(1 dm
3
)
(0.08206 dm
3
atmK
1
mol
1
) (300 K)
= 0.03955 mol,
n
T
= n
N
2
+ n
O
2
= 0.03955 mol. (2)
Equations (1) and (2) are simultaneous equations for the amounts of gas and may be solved for them.
Inserting n
O
2
from (2) into (1) we get
(n
N
2
) (28.0136 g mol
1
) + (0.03955 mol n
N
2
) (31.9988 g mol
1
) = 1.146 g.
(1.2655 1.1460) g = (3.9852 g mol
1
) (n
N
2
).
n
N
2
= 0.02999 mol.
n
O
2
= n
T
n
N
2
= (0.03955 0.02999) mol = 9.56 10
3
mol.
The mole fractions are
x
N
2
=
0.02999 mol
0.03955 mol
= 0.7583 , x
O
2
=
9.56 10
3
mol
0.03955 mol
= 0.2417 .
The partial pressures are p
N
2
= (0.7583) (0.987 bar) = 0.748 bar ,
p
O
2
= (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 n
T
, p
T
, and m
T
remain the same as in part (a)
as these are experimentally determined quantities. However, the simultaneous equations that need
to be solved are modied as follows:
m
T
= n
N
2
M
N
2
+ n
O
2
M
O
2
+ n
Ar
M
Ar
= 1.146 g,
n
T
= n
N
2
+ n
O
2
+ n
Ar
= 0.03955 mol,
Since x
Ar
= 0.0100, n
Ar
= 0.0003955 mol.
TRAPP: CHAP01 2006/3/8 18:03 PAGE 8 #8
8 SOLUTIONS MANUAL
Solving the equations yields
n
N
2
= 0.03084, x
N
2
= 0.7798 ,
n
O
2
= 0.008314, x
O
2
= 0.2102 .
The partial pressures are:
p
N
2
= x
N
2
p
T
= 0.7798 0.987 bar = 0.770 bar ,
p
O
2
= x
O
2
p
T
= 0.2102 0.987 bar = 0.207 bar ,
p
Ar
= x
Ar
p
T
= 0.0100 0.987 bar = 0.00987 bar .
E1.11(a) This exercise uses the formula, M =
RT
p
, which was developed and used in Exercises 1.7(b) and
1.8(a). Substituting the data,
M =
(1.23 kg m
3
) (8.314 dm
3
kPa K
1
mol
1
) (330 K)
20 kPa

_
10
3
g
kg
_

_
10
3
m
3
dm
3
_
= 169 g mol
1
.
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 dm
3
) V/(dm
3
g
1
)
85 1.877 0.5328
0 1.294 0.7728
100 0.946 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 = V
0
(1 + ).
At absolute zero, V = 0, then (abs. zero) =
1

. The value of can be obtained from any one of the

data points (except = 0) as follows.
From V = V
0
(1 + ),
=
_
V
V
0
1
_

=
_
1.057
0.7728
_
1
100

C
= 0.003678(

C)
1

=
1
0.003678(

C)
1
= 272

C .
which is close to the value obtained graphically.
TRAPP: CHAP01 2006/3/8 18:03 PAGE 9 #9
THE PROPERTIES OF GASES 9
V
/
(
d
m
3

g

1
)
u/ C
Figure 1.1
E1.13(a) (a) p =
nRT
V
[1.8].
n = 1.0 mol, T = 273.15 K (i) or 1000 K(ii).
V = 22.414 dm
3
(i) or 100 cm
3
(ii).
(i) p =
(1.0 mol) (8.206 10
2
dm
3
atmK
1
mol
1
) (273.15 K)
22.414 dm
3
= 1.0 atm .
(ii) p =
(1.0 mol) (8.206 10
2
dm
3
atmK
1
mol
1
) (1000 K)
0.100 dm
3
= 8.2 10
2
atm .
(b) p =
nRT
V nb

an
2
V
2
[1.21a].
From Table 1.6, a = 5.507 dm
6
atmmol
2
and b = 6.51 10
2
dm
3
mol
1
. Therefore,
(i)
nRT
V nb
=
(1.0 mol) (8.206 10
2
dm
3
atmK
1
mol
1
) (273.15 K)
[22.414 (1.0) (6.51 10
2
)] dm
3
= 1.003 atm,
an
2
V
2
=
(5.507 dm
6
atmmol
2
) (1.0 mol)
2
(22.414 dm
3
)
2
= 1.11 10
2
atm,
and p = 1.003 atm 1.11 10
2
atm = 0.992 atm = 1.0 atm .
(ii)
nRT
V nb
=
(1.0 mol) (8.206 10
2
dm
3
atmK
1
mol
1
) (1000 K)
(0.100 0.0651) dm
3
,
= 2.27 10
3
atm,
an
2
V
2
=
(5.507 dm
6
atmmol
2
) (1.0 mol)
2
(0.100 dm
3
)
2
= 5.51 10
2
atm,
and p = 2.27 10
3
atm 5.51 10
2
atm = 1.7 10
3
atm .
TRAPP: CHAP01 2006/3/8 18:03 PAGE 10 #10
10 SOLUTIONS MANUAL
COMMENT. It is instructive to calculate the percentage deviation from perfect gas behaviour for (i) and (ii).
(i)
0.992 1.000
1.000
100% = 0.8%.
(ii)
(17 10
2
) (8.2 10
2
)
8.2 10
2
100% = 107%.
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 10
5
Pa 1 Pa = 1 kg m
1
s
2
1 dm
6
= 10
6
m
6
1 dm
3
= 10
3
m
3
.
Therefore,
a = 0.751 atm dm
6
mol
2
becomes, after substitution of the conversions,
a = 7.61 10
2
kg m
5
s
2
mol
2
, and
b = 0.0226 dm
3
mol
1
becomes
b = 2.26 10
5
m
3
mol
1
.
E1.15(a) The denition of Z is used Z =
pV
m
RT
[1.17] =
V
m
V

m
.
V
m
is the actual molar volume, V

m
is the perfect gas molar volume. V

m
=
RT
p
. Since V
m
is 12 per cent
smaller than that of a perfect gas, V
m
= 0.88V

m
, and
(a) Z =
0.88V

m
V

m
= 0.88 .
(b) V
m
=
ZRT
p
=
(0.88) (8.206 10
2
dm
3
atmK
1
mol
1
) (250 K)
15 atm
= 1.2 dm
3
mol
1
.
Since V
m
< V

m
attractive forces dominate.
E1.16(a) The amount of gas is rst determined fromits 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
superuous information.
n =
92.4 kg
28.02 10
3
kg mol
1
= 3.30 10
3
mol
V = 1.000 m
3
= 1.000 10
3
dm
3
p =
nRT
V nb

an
2
V
2
[1.21a] =
(3.30 10
3
mol) (0.08206 dm
3
atm K
1
mol
1
) (500 K)
(1.000 10
3
dm
3
) (3.30 10
3
mol) (0.0387 dm
3
mol
1
)

(1.352 dm
6
atmmol
2
) (3.30 10
3
mol)
2
(1.000 10
3
dm
3
)
2
= (155 14.8) atm = 140 atm .
E1.17(a) (a) p =
nRT
V
[1.8] =
(10.0 mol) (0.08206 dm
3
atmK
1
mol
1
) (300 K)
4.860 dm
3
= 50.7 atm .
TRAPP: CHAP01 2006/3/8 18:03 PAGE 11 #11
THE PROPERTIES OF GASES 11
(b) p =
nRT
V nb
a
_
n
V
_
2
[1.21a]
=
(10.0 mol) (0.08206 dm
3
atmK
1
mol
1
) (300 K)
(4.860 dm
3
) (10.0 mol) (0.0651 dm
3
mol
1
)
(5.507 dm
6
atmmol
2
)
_
10.0 mol
4.860 dm
3
_
2
= 58.49 23.32 = 35.2 atm .
The compression factor is calculated from its denition [1.17] after inserting V
m
=
V
n
.
To complete the calculation of Z, a value for the pressure, p, is required. The implication in the denition
[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
Z =
pV
nRT
=
(35.2 atm) (4.860 dm
3
)
(10.0 mol) (0.08206 dm
3
atmK
1
mol
1
) (300 K)
= 0.695 .
COMMENT. If the perfect gas pressure had been used, Z would have been 1, the perfect gas value.
E1.18(a) n = n(H
2
) + n(N
2
) = 2.0 mol + 1.0 mol = 3.0 mol, x
J
=
n
J
n
[1.14].
(a) x(H
2
) =
2.0 mol
3.0 mol
= 0.67 , x(N
2
) =
1.0 mol
3.0 mol
= 0.33 .
(b) The perfect gas law is assumed to hold for each component individually as well as for the mixture
as a whole. Hence, p
J
= n
J
RT
V
.
RT
V
=
(8.206 10
2
dm
3
atmK
1
mol
1
) (273.15 K)
22.4 dm
3
= 1.00 atmmol
1
.
p(H
2
) = (2.0 mol) (1.00 atmmol
1
) = 2.0 atm .
p(N
2
) = (1.0 mol) (1.00 atmmol
1
) = 1.0 atm .
(c) p = p(H
2
) + p(N
2
)[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 =
V
c
3
and a = 27b
2
p
c
= 3V
2
c
p
c
.
Substituting the critical constants,
b =
1
3
(98.7 cm
3
mol
1
) = 32.9 cm
3
mol
1
,
a = 3 (98.7 10
3
dm
3
mol
1
)
2
(45.6 atm) = 1.33 dm
6
atm mol
2
.
Note that knowledge of the critical temperature, T
c
, is not required.
TRAPP: CHAP01 2006/3/8 18:03 PAGE 12 #12
12 SOLUTIONS MANUAL
As b is approximately the volume occupied per mole of particles
v
mol

b
N
A
=
32.9 10
6
m
3
mol
1
6.022 10
23
mol
1
= 5.46 10
29
m
3
.
Then, with v
mol
=
4
3
r
3
, r
_
3
4
(5.46 10
29
m
3
)
_
1/3
= 0.24 nm .
E1.20(a) The Boyle temperature, T
B
, is the temperature at which B = 0. In order to express T
B
in terms of a and
b, the van der Waals equation must be recast into the form of the virial equation.
p =
RT
V
m
b

a
V
2
m
[1.21b].
Factoring out
RT
V
m
yields p =
RT
V
m
_
1
1 b/V
m

a
RTV
m
_
.
So long as b/V
m
< 1, the rst terminside the brackets can be expanded using (1x)
1
= 1+x+x
2
+ ,
which gives
p =
RT
V
m
_
1 +
_
b
a
RT
_

_
1
V
m
_
+
_
We can now identify the second virial coefcient as B = b
a
RT
.
Since at the Boyle temperature B = 0, T
B
=
a
bR
=
27T
c
8
.
(a) From Table 1.6, a = 6.260 dm
6
atm mol
2
, b = 5.42 10
2
dm
3
mol
1
. Therefore,
T
B
=
6.260 dm
6
atmmol
2
(5.42 10
2
dm
3
mol
1
) (8.206 10
2
dm
3
atmK
1
mol
1
)
= 1.41 10
3
K .
(b) As in Exercise 1.19(a), v
mol

b
N
A
=
5.42 10
5
m
3
mol
1
6.022 10
23
mol
1
= 9.00 10
29
m
3
r
_
3
4
(9.00 10
29
m
3
)
_
1/3
= 0.59 nm .
E1.21(a) The reduced temperature and pressure of hydrogen are calculated from the relations
T
r
=
T
T
c
and p
r
=
p
p
c
[1.24].
T
r
=
298 K
33.23 K
= 8.968 [T
c
= 33.23 K, Table 1.5],
p
r
=
1.0 atm
12.8 atm
= 0.0781 [p
c
= 12.8 atm, Table 1.5].
Hence, the gases named will be in corresponding states at T = 8.968 T
c
and at p = 0.0781 p
c
.
TRAPP: CHAP01 2006/3/8 18:03 PAGE 13 #13
THE PROPERTIES OF GASES 13
(a) For ammonia, T
c
= 405.5 K and p
c
= 111.3 atm (Table 1.5), so
T = (8.968) (405.5 K) = 3.64 10
3
K ,
p = (0.0781) (111.3 atm) = 8.7 atm .
(b) For xenon, T
c
= 289.75 K and p
c
= 58.0 atm, so
T = (8.968) (289.75 K) = 2.60 10
3
K ,
p = 0.0781) (58.0 atm) = 4.5 atm .
(c) For helium, T
c
= 5.21 K and p
c
= 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
b = V
m

RT
_
p +
a
V
2
m
_.
Substituting the data
b = 5.00 10
4
m
3
mol
1

(8.314 J K
1
mol
1
) (273 K)
_
(3.0 10
6
Pa) +
_
0.50 m
6
Pa mol
2
(5.00 10
4
m
3
mol
1
)
2
__
= 0.46 10
4
m
3
mol
1
.
Z =
pV
m
RT
[1.17] =
(3.0 10
6
Pa) (5.00 10
4
m
3
)
(8.314 J K
1
mol
1
) (273 K)
= 0.66.
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(T
1
) = 28.0 dm
3
atm = nRT
1
= nR (T
1
+ 0

N),
pV(T
2
) = 40.0 dm
3
atm = nRT
2
= nR (T
1
+ 100

N),
or T
1
=
28.0 dm
3
atm
nR
, T
1
+ 100

N =
40.0 dm
3
atm
nR
.
TRAPP: CHAP01 2006/3/8 18:03 PAGE 14 #14
14 SOLUTIONS MANUAL
Dividing,
T
1
+ 100

N
T
1
=
40.0 dm
3
atm
28.0 dm
3
atm
= 1.429 or T
1
+ 100

N = 1.429T
1
, T
1
= 233 absolute units.
As in the relationship between our Kelvin scale and Celsius scale T = absolute zero(

N) so absolute
zero(

N) = 233

N .
COMMENT. To facilitate communication with Earth students we have converted the Neptunians units of
the pV product to units familiar to humans, which are dm
3
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 = V
0
[1 + (abs. zero)].
Then (abs. zero) =
1

.
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 10
3
C
1
, or
(abs. zero) =
1
3.6637 10
3
C
1
= 272.95

C ,
which is close to the accepted value of 273.15

C.
3.662
3.664
3.666
3.668
3.670
3.672
0 800 200 400 600
p / Torr
Figure 1.2
TRAPP: CHAP01 2006/3/8 18:03 PAGE 15 #15
THE PROPERTIES OF GASES 15
P1.5
p
T
=
nR
V
= constant, if n and V are constant. Hence,
p
T
=
p
3
T
3
, where p is the measured pressure at
temperature, T, and p
3
and T
3
are the triple point pressure and temperature, respectively. Rearranging,
p =
_
p
3
T
3
_
T.
The ratio
p
3
T
3
is a constant =
6.69 kPa
273.16 K
= 0.0245 kPa K
1
. Thus the change in p, p, is proportional to
the change in temperature, T : p = (0.0245 kPa K
1
) (T).
(a) p = (0.0245 kPa K
1
) (1.00 K) = 0.0245 kPa .
(b) Rearranging, p =
_
T
T
3
_
p
3
=
_
373.16 K
273.16 K
_
(6.69 kPa) = 9.14 kPa .
(c) Since
p
T
is a constant at constant n and V, it always has the value 0.0245 kPa K
1
; hence
p = p
374.15 K
p
373.15 K
= (0.0245 kPa K
1
) (1.00 K) = 0.0245 kPa .
P1.7 (a) V
m
=
RT
p
=
(8.206 10
2
dm
3
atmK
1
mol
1
) (350 K)
2.30 atm
= 12.5 dm
3
mol
1
.
(b) From p =
RT
V
m
b

a
V
2
m
[1.21b], we obtain V
m
=
RT
_
p +
a
V
2
m
_ +b[rearrange1.21b]
Then, with a and b from Table 1.16,
V
m

_
8.206 10
2
dm
3
atmK
1
mol
1
_
(350 K)
(2.30 atm) +
_
(6.260 dm
6
atmmol
2
)/
_
12.5 dm
3
mol
1
_
2
_ + (5.42 100
2
dm
3
mol
1
)

28.7

2 dm
3
mol
1
2.34
+
_
5.42 10
2
dm
3
mol
1
_
12.3 dm
3
mol
1
.
Substitution of 12.3 dm
3
mol
1
into the denominator of the rst expression again results in
V
m
= 12.3 dm
3
mol
1
, so the cycle of approximation may be terminated.
P1.9 As indicated by eqns 1.18 and 1.19 the compression factor of a gas may be expressed as either a virial
expansion in p or in
_
1
V
m
_
. The virial form of the van der Waals equation is derived in Exercise 1.20(a)
and is p =
RT
V
m
_
1 +
_
b
a
RT
_

_
1
V
m
_
+
_
Rearranging, Z =
pV
m
RT
= 1 +
_
b
a
RT
_

_
1
V
m
_
+
On the assumption that the perfect gas expression for V
m
is adequate for the second termin this expansion,
we can readily obtain Z as a function of p.
Z = 1 +
_
1
RT
_

_
b
a
RT
_
p +
TRAPP: CHAP01 2006/3/8 18:03 PAGE 16 #16
16 SOLUTIONS MANUAL
(a)
T
c
= 126.3 K.
V
m
=
_
RT
p
_
Z =
RT
p
+
_
b
a
RT
_
+
=
(0.08206 dm
3
atmK
1
mol
1
) (126.3 K)
10.0 atm
+
_
(0.0387 dm
3
mol
1
)
_
1.352 dm
6
atmmol
2
(0.08206 dm
3
atmK
1
mol
1
) (126.3 K)
__
= (1.036 0.092) dm
3
mol
1
= 0.944 dm
3
mol
1
.
Z =
_
p
RT
_
(V
m
) =
(10.0 atm) (0.944 dm
3
mol
1
)
(0.08206 dm
3
atmK
1
mol
1
) (126.3 K)
= 0.911.
(b) The Boyle temperature corresponds to the temperature at which the second virial coefcient is zero,
hence correct to the rst power in p, Z = 1, and the gas is close to perfect. However, if we assume
that N
2
is a van der Waals gas, when the second virial coefcient is zero,
_
b
a
RT
B
_
= 0, or T
B
=
a
bR
.
T
B
=
1.352 dm
6
atmmol
2
(0.0387 dm
3
mol
1
) (0.08206 dm
3
atmK
1
mol
1
)
= 426 K.
The experimental value (Table 1.5) is 327.2 K. The discrepancy may be explained by two
considerations.
1. Terms beyond the rst power in p should not be dropped in the expansion for Z.
2. Nitrogen is only approximately a van der Waals gas.
When Z = 1, V
m
=
RT
p
, and using T
B
= 327.2 K
=
(0.08206 dm
3
atm K
1
mol
1
) 327.2 K
10.0 atm
= 2.69 dm
3
mol
1
and this is the ideal value of V
m
. Using the experimental value of T
B
and inserting this value into
the expansion for V
m
above, we have
V
m
=
0.08206 dm
3
atm K
1
mol
1
327.2 K
10.0 atm
+
_
0.0387 dm
3
mol
1

_
1.352 dm
6
atm mol
2
0.08206 dm
3
atmK
1
mol
1
327.2 K
__
= (2.685 0.012) dm
3
mol
1
= 2.67 dm
3
mol
1
and Z =
V
m
V

m
=
2.67 dm
3
mol
1
2.69 dm
3
mol
1
= 0.992 1.
TRAPP: CHAP01 2006/3/8 18:03 PAGE 17 #17
THE PROPERTIES OF GASES 17
(c) T
I
= 621 K [Table 2.9].
V
m
=
0.08206 dm
3
atm K
1
mol
1
621 K
10.0 atm
+
_
0.0387 dm
3
mol
1

_
1.352 dm
6
atm mol
2
0.08206 dm
3
atmK
1
mol
1
621 K
__
= (5.096 + 0.012) dm
3
mol
1
= 5.11 dm
3
mol
1
and Z =
5.11 dm
3
mol
1
5.10 dm
3
mol
1
= 1.002 1.
Based on the values of T
B
and T
I
given in Tables 1.4 and 2.9 and assuming that N
2
is a van der Waals
gas, the calculated value of Z is closest to 1 at T
I
, but the difference from the value at T
B
is less than
the accuracy of the method.
P1.11 (a) V
m
=
molar mass
density
=
M

=
18.02 g mol
1
1.332 10
2
g dm
3
= 0.1353 dm
3
mol
1
.
(b) Z =
pV
m
RT
[1.17b] =
(327.6 atm) (0.1353 dm
3
mol
1
)
(0.08206 dm
3
atmK
1
mol
1
) (776.4 K)
= 0.6957 .
(c) Two expansions for Z based on the van der Waals equation are given in Problem 1.9. They are
Z = 1 +
_
b
a
RT
_

_
1
V
m
_
+
= 1 +
_
(0.0305 dm
3
mol
1
)
_
5.464 dm
6
atmmol
2
(0.08206 dm
3
atmK
1
mol
1
) (776.4 K)
__

1
0.1353 dm
3
mol
1
= 1 0.4084 = 0.5916 0.59.
Z = 1 +
_
1
RT
_

_
b
a
RT
_
(p) +
= 1 +
1
(0.08206 dm
3
atmK
1
mol
1
) (776.4 K)

_
(0.0305 dm
3
mol
1
)
_
5.464 dm
6
atmmol
2
(0.08206 dm
3
atmK
1
mol
1
) (776.4 K)
__
327.6 atm
= 1 0.2842 0.72 .
In this case the expansion in p gives a value close to the experimental value; the expansion in
1
V
m
is not as good. However, when terms beyond the second are included the results from the two
expansions for Z converge.
P1.13 V
c
= 2b, T
c
=
a
4bR
[Table 1.7]
TRAPP: CHAP01 2006/3/8 18:03 PAGE 18 #18
18 SOLUTIONS MANUAL
Hence, with V
c
and T
c
from Table 1.5, b =
1
2
V
c
=
1
2
(118.8 cm
3
mol
1
) = 59.4 cm
3
mol
1
.
a = 4bRT
c
= 2RT
c
V
c
= (2) (8.206 10
2
dm
3
atmK
1
mol
1
) (289.75 K) (118.8 10
3
dm
3
mol
1
)
= 5.649 dm
6
atmmol
2
.
Hence
p =
RT
V
m
b
e
a/RTV
m
=
nRT
V nb
e
na/RTV
=
(1.0 mol) (8.206 10
2
dm
3
atmK
1
mol
1
) (298 K)
(1.0 dm
3
) (1.0 mol) (59.4 10
3
dm
3
mol
1
)
exp
_
(1.0 mol) (5.649 dm
6
atmmol
2
)
(8.206 10
2
dm
3
atmK
1
mol
1
) (298 K) (1.0 dm
6
atmmol
1
)
_
= 26.0 atm e
0.231
= 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
V
m
_
1 +
_
b
a
RT
_
1
V
m
+
b
2
V
2
m
+
_
.
Compare this expansion with p =
RT
V
m
_
1 +
B
V
m
+
C
V
m
2
+
_
[1.19]
and hence nd B = b
a
RT
and C = b
2
.
Since C = 1200 cm
6
mol
2
, b = C
1/2
= 34.6 cm
3
mol
1
a = RT(b B) = (8.206 10
2
) (273 dm
3
atmmol
1
) (34.6 + 21.7) cm
3
mol
1
= (22.40 dm
3
atmmol
1
) (56.3 10
3
dm
3
mol
1
) = 1.26 dm
6
atmmol
2
.
P1.17 The critical point corresponds to a point of zero slope that is simultaneously a point of inection 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 satises these conditions.
p =
RT
V
m

B
V
2
m
+
C
V
3
m
.
TRAPP: CHAP01 2006/3/8 18:03 PAGE 19 #19
THE PROPERTIES OF GASES 19
_
p
V
m
_
T
=
RT
V
2
m
+
2B
V
3
m

3C
V
4
m
= 0
_

2
p
V
2
m
_
T
=
2RT
V
3
m

6B
V
4
m
+
12C
V
5
m
= 0
_

_
at the critical point.
That is,
RT
c
V
2
c
+ 2BV
c
3C = 0
RT
c
V
2
c
3BV
c
+ 6C = 0
_
which solve to V
c
=
3C
B
, T
c
=
B
2
3RC
.
Now use the equation of state to nd p
c
p
c
=
RT
c
V
c

B
V
2
c
+
C
V
3
c
=
_
RB
2
3RC
_

_
B
3C
_
B
_
B
3C
_
2
+C
_
B
3C
_
3
=
B
3
27C
2
.
It follows that Z
c
=
p
c
V
c
RT
c
=
_
B
3
27C
2
_

_
3C
B
_

_
1
R
_

_
3RC
B
2
_
=
1
3
.
P1.19 For a real gas we may use the virial expansion in terms of p [1.18]
p =
nRT
V
(1 +B

p + ) =
RT
M
(1 +B

p + )
which rearranges to
p

=
RT
M
+
RT B

M
p + .
Therefore, the limiting slope of a plot of
p

against p is
B

RT
M
. From Fig. 1.3 the limiting slope is
B

RT
M
=
(5.84 5.44) 10
4
m
2
s
2
(10.132 1.223) 10
4
Pa
= 4.4 10
2
kg
1
m
3
.
From Fig. 1.2,
RT
M
= 5.40 10
4
m
2
s
2
; hence
B

=
4.4 10
2
kg
1
m
3
5.40 10
4
m
2
s
2
= 0.81 10
6
Pa
1
,
B

= (0.81 10
6
Pa
1
) (1.0133 10
5
Pa atm
1
) = 0.082 atm
1
.
B = RTB

[Problem1.18]
= (8.206 10
2
dm
3
atmK
1
mol
1
) (298 K) (0.082 atm
1
)
= 2.0 dm
3
mol
1
.
P1.21 The critical temperature is that temperature above which the gas cannot be liqueed 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 20 #20
20 SOLUTIONS MANUAL
5.9
5.8
5.7
5.6
5.5
5.4
0 2 4 6
p/(10
4
Pa)
(
p
/
r
)
/
(
1
0
4

m
2

s

1
)
8 10 12
y = 5.3963 + 0.046074x R = 0.99549
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 T
c
, allows only one real root. Thus, appropriate equations of state
must be equations of odd degree in V
m
.
The equation of state for gas A may be rewritten V
2
m
(RT/p)V
m
(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 rst-degree equation in V
m
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 V
m
.
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
nM
N
= 2.2990 g
for chemical nitrogen and
n
Ar
M
Ar
+n
N
M
N
= n[x
Ar
M
Ar
+ (1 x
Ar
)M
N
] = 2.3102 g
for atmospheric nitrogen. Dividing the latter expression by the former yields
x
Ar
M
Ar
M
N
+ (1 x
Ar
) =
2.3102
2.2990
so x
Ar
_
M
Ar
M
N
1
_
=
2.3102
2.2990
1
and x
Ar
=
(2.3102/2.2990) 1
(M
Ar
/M
N
) 1
=
(2.3102/2.2990) 1
(39.95 g mol
1
)/(28.013 g mol
1
1)
= 0.011 .
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 21 #21
THE PROPERTIES OF GASES 21
Solutions to applications
P1.25 1 t = 10
3
kg. Assume 300 t per day.
n(SO
2
) =
300 10
3
kg
64 10
3
kg mol
1
= 4.7 10
6
mol.
V =
nRT
p
=
(4.7 10
6
mol) (0.082 dm
3
atmK
1
mol
1
) 1073 K
1.0 atm
= 4.1 10
8
dm
3
.
P1.27 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
RT
[Problem 1.2], dp =
pMgdh
RT
, implying that
dp
p
=
Mg dh
RT
This relation integrates to p = p
0
e
Mgh/RT
For air M 29 g mol
1
and at 298 K
Mg
RT

(29 10
3
kg mol
1
) (9.81 ms
2
)
2.48 10
3
J mol
1
= 1.1

5 10
4
m
1
[1 J = 1 kg m
2
s
2
].
(a) h = 15 cm.
p = p
0
e
(0.15 m)(1.1

510
4
m
1
)
= 0.99998 p
0
;
p p
0
p
0
= 0.00 .
(b) h = 11 km = 1.1 10
4
m.
p = p
0
e
(1.110
4
)(1.1510
4
m
1
)
= 0.28 p
0
;
p p
0
p
0
= 0.72 .
P1.29 Refer to Fig. 1.3.
h
Ground
Air
(environment)
Figure 1.4
TRAPP: CHAP01 2006/3/8 18:03 PAGE 22 #22
22 SOLUTIONS MANUAL
The buoyant force on the cylinder is
F
buoy
= F
bottom
F
top
= A(p
bottom
p
top
)
according to the barometric formula.
p
top
= p
bottom
e
Mgh/RT
where M is the molar mass of the environment (air). Since h is small, the exponential can be expanded
in a Taylor series around h = 0
_
e
x
= 1 x +
1
2!
x
2
+
_
. Keeping the rst-order term only yields
p
top
= p
bottom
_
1
Mgh
RT
_
.
The buoyant force becomes
F
buoy
= Ap
bottom
_
1 1 +
Mgh
RT
_
= Ah
_
p
bottom
M
RT
_
g
=
_
p
bottom
VM
RT
_
g = nMg
_
n =
p
bottom
V
RT
_
n is the number of moles of the environment (air) displaced by the balloon, and nM = m, the mass of
the displaced environment. Thus F
buoy
= mg. The net force is the difference between the buoyant force
and the weight of the balloon. Thus
F
net
= mg m
balloon
g = (m m
balloon
)g
This is Archimedes principle.