PART 1 Equilibrium

TRAPP-ISM: “TRAPPISM_CH01” — 2006/3/24 — 11:42 — PAGE 1 — #1

TRAPP-ISM: “TRAPPISM_CH01” — 2006/3/24 — 11:42 — PAGE 2 — #2
 1 The properties of gases

Answers to discussion questions

D1.2 The partial pressure of a gas in a mixture of gases is the pressure the gas would exert if it occupied alone
the same container as the mixture at the same temperature. It is a limiting law because it holds exactly
only under conditions where the gases have no effect upon each other. This can only be true in the limit
of zero pressure where the molecules of the gas are very far apart. Hence, Dalton’s law holds exactly
only for a mixture of perfect gases; for real gases, the law is only an approximation.

D1.4 The critical constants represent the state of a system at which the distinction between the liquid and
vapor phases disappears. We usually describe this situation by saying that above the critical temperature
the liquid phase cannot be produced by the application of pressure alone. The liquid and vapor phases
can no longer coexist, though fluids in the so-called supercritical region have both liquid and vapor
characteristics. (See Box 4.1 for a more thorough discussion of the supercritical state.)

D1.6 The van der Waals equation is a cubic equation in the volume, V . Any cubic equation has certain
properties, one of which is that there are some values of the coefficients of the variable where the
number of real roots passes from three to one. In fact, any equation of state of odd degree higher than
1 can in principle account for critical behavior because for equations of odd degree in V there are
necessarily some values of temperature and pressure for which the number of real roots of V passes
from n (odd) to 1. That is, the multiple values of V converge from n to 1 as T → Tc . This mathematical
result is consistent with passing from a two phase region (more than one volume for a given T and p) to
a one phase region (only one V for a given T and p and this corresponds to the observed experimental
result as the critical point is reached.

Solutions to exercises

E1.1(b) (a) The perfect gas law is

pV = nRT

implying that the pressure would be

nRT
p=
V

TRAPP-ISM: “TRAPPISM_CH01” — 2006/3/24 — 11:42 — PAGE 3 — #3

 4 INSTRUCTOR’S MANUAL

All quantities on the right are given to us except n, which can be computed from the given mass
of Ar.
25 g
n= = 0.626 mol
39.95 g mol−1
(0.626 mol) × (8.31 × 10−2 dm3 bar K−1 mol−1 ) × (30 + 273 K)
so p = = 10.5 bar
1.5 dm3
not 2.0 bar.

(b) The van der Waals equation is

RT a
p= −
Vm − b Vm2
(8.31 × 10−2 dm3 bar K−1 mol−1 ) × (30 + 273) K
so p =
(1.5L/0.626̄ mol) − 3.20 × 10−2 dm3 mol−1
(1.337 dm6 atm mol−2 ) × (1.013 bar atm−1 )
− = 10.4̄ bar
(1.5 dm3 /0.626̄ mol)2

E1.2(b) (a) Boyle’s law applies:

pV = constant so p f V f = pi Vi

and
pf Vf (1.97 bar) × (2.14 dm3 )
pi = = = 1.07 bar
Vi (2.14 + 1.80) dm3
(b) The original pressure in bar is



1 atm 760 Torr
pi = (1.07 bar) × × = 803 Torr
1.013 bar 1 atm

E1.3(b) The relation between pressure and temperature at constant volume can be derived from the perfect
gas law
pi pf
pV = nRT so p∝T and =
Ti Tf
The final pressure, then, ought to be
pi Tf (125 kPa) × (11 + 273) K
pf = = = 120 kPa
Ti (23 + 273) K

E1.4(b) According to the perfect gas law, one can compute the amount of gas from pressure, temperature,
and volume. Once this is done, the mass of the gas can be computed from the amount and the molar
mass using
pV = nRT
pV (1.00 atm) × (1.013 × 105 Pa atm−1 ) × (4.00 × 103 m3 )
so n = = = 1.66 × 105 mol
RT (8.3145 J K−1 mol−1 ) × (20 + 273) K

and m = (1.66 × 105 mol) × (16.04 g mol−1 ) = 2.67 × 106 g = 2.67 × 103 kg

TRAPP-ISM: “TRAPPISM_CH01” — 2006/3/24 — 11:42 — PAGE 4 — #4

 THE PROPERTIES OF GASES 5

E1.5(b) Identifying pex in the equation p = pex + ρgh [1.3] as the pressure at the top of the straw and p as the
atmospheric pressure on the liquid, the pressure difference is

p − pex = ρgh = (1.0 × 103 kg m−3 ) × (9.81 m s−2 ) × (0.15 m)

= 1.5 × 103 pa (= 1.5 × 10−2 atm)

E1.6(b) The pressure in the apparatus is given by

p = patm + ρgh [1.3]

patm = 760 Torr = 1 atm = 1.013 × 105 Pa

  6 
−3 1 kg 10 cm3
ρgh = 13.55 g cm × × × 0.100 m × 9.806 m s−2 = 1.33 × 104 Pa
103 g m3

p = 1.013 × 105 Pa + 1.33 × 104 Pa = 1.146 × 105 Pa = 115 kPa

E1.7(b) All gases are perfect in the limit of zero pressure. Therefore the extrapolated value of pVm /T will give
the best value of R.
m
The molar mass is obtained from pV = nRT = RT
M
m RT RT
which upon rearrangement gives M = =ρ
V p p
The best value of M is obtained from an extrapolation of ρ/p versus p to p = 0; the intercept is M/RT .
Draw up the following table

p/atm ( pVm /T )/(dm3 atm K−1 mol−1 ) (ρ/p)/(dm−3 atm−1 )

0.750 000 0.082 0014 1.428 59

0.500 000 0.082 0227 1.428 22
0.250 000 0.082 0414 1.427 90


pVm
From Figure 1.1(a), = 0.082 061 5 dm3 atm K−1 mol−1
T p=0

8.20615
8.206

8.204
dm3

8.202
m

8.200

0 0.25 0.50 0.75 1.0

Figure 1.1(a)

TRAPP-ISM: “TRAPPISM_CH01” — 2006/3/24 — 11:42 — PAGE 5 — #5

 6 INSTRUCTOR’S MANUAL


ρ
From Figure 1.1(b), = 1.427 55 g dm−3 atm−1
p p=0

1.4288

1.4286
1.4284
1.4282
dm–3

1.4280
1.4278

1.4276 1.42755
1.4274
0 0.25 0.50 0.75 1.0
Figure 1.1(b)


ρ
M = RT = (0.082 061 5 dm3 atm mol−1 K−1 ) × (273.15 K) × (1.42755 g dm−3 atm−1 )
p p=0

= 31.9987 g mol−1

The value obtained for R deviates from the accepted value by 0.005 percent. The error results from the
fact that only three data points are available and that a linear extrapolation was employed. The molar
mass, however, agrees exactly with the accepted value, probably because of compensating plotting
errors.

E1.8(b) The mass density ρ is related to the molar volume Vm by

M
Vm =
ρ

where M is the molar mass. Putting this relation into the perfect gas law yields

pM
pVm = RT so = RT
ρ

Rearranging this result gives an expression for M; once we know the molar mass, we can divide by the
molar mass of phosphorus atoms to determine the number of atoms per gas molecule

RT ρ (8.314 Pa m3 mol−1 ) × [(100 + 273) K] × (0.6388 kg m−3 )

M= =
p 1.60 × 104 Pa
= 0.124 kg mol−1 = 124 g mol−1

The number of atoms per molecule is

124 g mol−1
= 4.00
31.0 g mol−1

suggesting a formula of P4

TRAPP-ISM: “TRAPPISM_CH01” — 2006/3/24 — 11:42 — PAGE 6 — #6

 THE PROPERTIES OF GASES 7

E1.9(b) Use the perfect gas equation to compute the amount; then convert to mass.

pV
pV = nRT so n=
RT
We need the partial pressure of water, which is 53 percent of the equilibrium vapor pressure at the given
temperature and standard pressure.

p = (0.53) × (2.69 × 103 Pa) = 1.43̄ × 103 Pa

(1.43 × 103 Pa) × (250 m3 )
so n = = 1.45 × 102 mol
(8.3145 J K−1 mol−1 ) × (23 + 273) K

or m = (1.45 × 102 mol) × (18.0 g mol−1 ) = 2.61 × 103 g = 2.61̄ kg

E1.10(b) (a) The volume occupied by each gas is the same, since each completely fills the container. Thus solving
for V we have (assuming a perfect gas)

nJ RT 0.225 g
V= nNe =
pJ 20.18 g mol−1
= 1.115 × 10−2 mol, pNe = 8.87 kPa, T = 300 K
(1.115̄ × 10−2 mol) × (8.314 dm3 kPa K−1 mol−1 ) × 300 K)
V= = 3.137̄ dm3
8.87 kPa
= 3.14 dm3

(b) The total pressure is determined from the total amount of gas, n = nCH4 + nAr + nNe .

0.320 g 0.175 g
nCH4 = = 1.995̄ × 10−2 mol nAr = = 4.38 × 10−3 mol
16.04 g mol−1 39.95 g mol−1
n = (1.995̄ + 0.438 + 1.115̄) × 10−2 mol = 3.548̄ × 10−2 mol
nRT (3.548̄ × 10−2 mol) × (8.314 dm3 kPa K−1 mol−1 ) × (300 K)
p= [1.8] =
V 3.137̄ dm3
= 28.2 kPa

E1.11(b) This is similar to Exercise 1.11(a) with the exception that the density is first calculated.

RT
M=ρ [Exercise 1.8(a)]
p
33.5 mg
ρ= = 0.1340 g dm−3 , p = 152 Torr, T = 298 K
250 cm3
(0.1340 g dm−3 ) × (62.36 dm3 Torr K−1 mol−1 ) × (298 K)
M= = 16.14 g mol−1
152 Torr

E1.12(b) This exercise is similar to Exercise 1.12(a) in that it uses the definition of absolute zero as that temperature
at which the volume of a sample of gas would become zero if the substance remained a gas at low
temperatures. The solution uses the experimental fact that the volume is a linear function of the Celsius
temperature.

TRAPP-ISM: “TRAPPISM_CH01” — 2006/3/24 — 11:42 — PAGE 7 — #7

 8 INSTRUCTOR’S MANUAL

Thus V = V0 + αV0 θ = V0 + bθ , b = αV0

At absolute zero, V = 0, or 0 = 20.00 dm3 + 0.0741 dm3 ◦ C−1 × θ (abs. zero)

20.00 dm3
θ(abs. zero) = − = −270 ◦ C
0.0741 dm3 ◦ C−1

which is close to the accepted value of −273 ◦ C.

nRT
E1.13(b) (a) p=
V
n = 1.0 mol
T = (i) 273.15 K; (ii) 500 K
V = (i) 22.414 dm3 ; (ii) 150 cm3

(1.0 mol) × (8.206 × 10−2 dm3 atm K−1 mol−1 ) × (273.15 K)

(i) p=
22.414 dm3
= 10 atm
(1.0 mol) × (8.206 × 10−2 dm3 atm K−1 mol−1 ) × (500 K)
(ii) p=
0.150 dm3
= 270 atm (2 significant figures)

(b) From Table (1.5) for H2 S

a = 4.484 dm6 atm mol−1 b = 4.34 × 10−2 dm3 mol−1

nRT an2
p= − 2
V − nb V

(1.0 mol) × (8.206 × 10−2 dm3 atm K−1 mol−1 ) × (273.15 K)

(i) p=
22.414 dm3 − (1.0 mol) × (4.34 × 10−2 dm3 mol−1 )

(4.484 dm6 atm mol−1 ) × (1.0 mol)2

−
(22.414 dm3 )
2

= 0.99 atm
(1.0 mol) × (8.206 × 10−2 dm3 atm K−1 mol−1 ) × (500 K)
(ii) p=
0.150 dm3 − (1.0 mol) × (4.34 × 10−2 dm3 mol−1 )
−1
(4.484 dm6 atm mol ) × (1.0 mol)2
−
(0.150 dm3 )2

= 185.6 atm ≈ 190 atm (2 significant figures).

E1.14(b) The conversions needed are as follows:

1 atm = 1.013 × 105 Pa; 1 Pa = 1 kg m−1 s−2 ; 1 dm6 = 10−6 m6 ; 1 dm3 = 10−3 m3

TRAPP-ISM: “TRAPPISM_CH01” — 2006/3/24 — 11:42 — PAGE 8 — #8

 THE PROPERTIES OF GASES 9

Therefore,

a = 1.32 atm dm6 mol−2 becomes, after substitution of the conversions

a = 1.34 × 10−1 kg m5 s−2 mol−2 , and

b = 0.0436 dm3 mol−1 becomes

b = 4.36 × 10−5 m−3 mol−1

E1.15(b) The compression factor is

pVm Vm
Z= =
RT Vm,perfect

(a) Because Vm = Vmo + 0.12Vmo = (1.12)Vmo , we have Z = 1.12 Repulsive forces dominate.
(b) The molar volume is


RT
V = (1.12)Vmo = (1.12) ×
p
 
(0.08206 dm3 atm K−1 mol−1 ) × (350 K)
V = (1.12) × = 2.7 dm3 mol−1
12 atm

RT (8.314 J K−1 mol−1 ) × (298.15 K)

E1.16(b) (a) Vmo = =
p (200 bar) × (105 Pa bar−1 )

= 1.24 × 10−4 m3 mol−1 = 0.124 dm3 mol−1

(b) The van der Waals equation is a cubic equation in Vm . The most direct way of obtaining the molar
volume would be to solve the cubic analytically. However, this approach is cumbersome, so we
proceed as in Example 1.6. The van der Waals equation is rearranged to the cubic form





RT a ab RT a ab
Vm3 − b + Vm2 + Vm − = 0 or x 3 − b + x2 + x− =0
p p p p p p

with x = Vm /(dm3 mol−1 ).

The coefficients in the equation are evaluated as

RT (8.206 × 10−2 dm3 mol−1 ) × (298.15 K)

b+ = (3.183 × 10−2 dm3 mol−1 ) +
p (200 bar) × (1.013 atm bar−1 )

= (3.183 × 10−2 + 0.1208) dm3 mol−1 = 0.1526̄ dm3 mol−1

a 1.360 dm6 atm mol−2

= = 6.71 × 10−3 (dm3 mol−1 )2
p (200 bar) × (1.013 atm bar−1 )

ab (1.360 dm6 atm mol−2 ) × (3.183 × 10−2 dm3 mol−1 )

= = 2.137 × 10−4 (dm3 mol−1 )3
p (200 bar) × (1.013 atm bar−1 )

Thus, the equation to be solved is x 3 − 0.1526x 2 + (6.71 × 10−3 )x − (2.137 × 10−4 ) = 0.

TRAPP-ISM: “TRAPPISM_CH01” — 2006/3/24 — 11:42 — PAGE 9 — #9

 10 INSTRUCTOR’S MANUAL

Calculators and computer software for the solution of polynomials are readily available. In this case
we find

x = 0.112 or Vm = 0.112 dm3 mol−1

The difference is about 15 percent.

E1.17(b) The molar volume is obtained by solving Z = pVm /RT [1.17b], for Vm , which yields

ZRT (0.86) × (0.08206 dm3 atm K−1 mol−1 ) × (300 K)

Vm = = = 1.059 dm3 mol−1
p 20 atm

(a) Then, V = nVm = (8.2 × 10−3 mol) × (1.059 dm3 mol−1 ) = 8.7 × 10−3 dm3 = 8.7 cm3
(b) An approximate value of B can be obtained from eqn 1.22 by truncation of the series expansion after
the second term, B/Vm , in the series. Then,


pVm
B = Vm − 1 = Vm × (Z − 1)
RT

= (1.059 dm3 mol−1 ) × (0.86 − 1) = −0.15 dm3 mol−1

E1.18(b) (a) Mole fractions are

nN 2.5 mol
xN = = = 0.63
ntotal (2.5 + 1.5) mol

Similarly, xH = 0.37
(b) According to the perfect gas law

ptotal V = ntotal RT
ntotal RT
so ptotal =
V
(4.0 mol) × (0.08206 dm3 atm mol−1 K−1 ) × (273.15 K)
= = 4.0 atm
22.4 dm3
(c) The partial pressures are

pN = xN ptot = (0.63) × (4.0 atm) = 2.5 atm

and pH = (0.37) × (4.0 atm) = 1.5 atm

E1.19(b) The critical volume of a van der Waals gas is

Vc = 3b

so b = 13 Vc = 13 (148 cm3 mol−1 ) = 49.3 cm3 mol−1 = 0.0493 dm3 mol−1

By interpreting b as the excluded volume of a mole of spherical molecules, we can obtain an estimate
of molecular size. The centers of spherical particles are excluded from a sphere whose radius is the

TRAPP-ISM: “TRAPPISM_CH01” — 2006/3/24 — 11:42 — PAGE 10 — #10

 THE PROPERTIES OF GASES 11

diameter of those spherical particles (i.e. twice their radius); that volume times the Avogadro constant
is the molar excluded volume b


1/3
4π(2r)3 1 3b
b = NA so r =
3 2 4π NA
 1/3
1 3(49.3 cm3 mol−1 )
r= = 1.94 × 10−8 cm = 1.94 × 10−8 m
2 4π(6.022 × 1023 mol−1 )

The critical pressure is

a
pc =
27b2

so a = 27pc b2 = 27(48.20 atm) × (0.0493 dm3 mol−1 )2 = 3.16 dm6 atm mol−2
But this problem is overdetermined. We have another piece of information

8a
Tc =
27Rb
According to the constants we have already determined, Tc should be

8(3.16 dm6 atm mol−2 )

Tc = = 231 K
27(0.08206 dm3 atm K−1 mol−1 ) × (0.0493 dm3 mol−1 )

However, the reported Tc is 305.4 K, suggesting our computed a/b is about 25 percent lower than it
should be.

E1.20(b) (a) The Boyle temperature is the temperature at which limVm →∞ dZ/d(1/Vm ) vanishes. According to
the van der Waals equation


RT a
− Vm
pVm Vm − b Vm2 Vm a
Z= = = −
RT RT Vm − b Vm RT



dZ dZ dVm
so = ×
d(1/Vm ) dVm d(1/Vm )



dZ −Vm 1 a
= −Vm2 = −Vm2 + +
dVm (Vm − b)2 Vm − b Vm2 RT
Vm2 b a
= −
(Vm − b)2 RT

In the limit of large molar volume, we have

dZ a a
lim =b− = 0 so =b
Vm →∞d(1/Vm ) RT RT
 
a 4.484 dm6 atm mol−2
and T = =     = 1259 K
Rb 0.08206 dm3 atm K−1 mol−1 × 0.0434 dm3 mol−1

TRAPP-ISM: “TRAPPISM_CH01” — 2006/3/24 — 11:42 — PAGE 11 — #11

 12 INSTRUCTOR’S MANUAL

(b) By interpreting b as the excluded volume of a mole of spherical molecules, we can obtain an estimate
of molecular size. The centres of spherical particles are excluded from a sphere whose radius is the
diameter of those spherical particles (i.e. twice their radius); the Avogadro constant times the volume
is the molar excluded volume b


1/3
4π(2r)3 1 3b
b = NA so r =
3 2 4π NA
 1/3
1 3(0.0434 dm3 mol−1 )
r= = 1.286 × 10−9 dm = 1.29 × 10−10 m = 0.129 nm
2 4π(6.022 × 1023 mol−1 )

E1.21(b) States that have the same reduced pressure, temperature, and volume are said to correspond. The reduced
pressure and temperature for N2 at 1.0 atm and 25 ◦ C are

p 1.0 atm T (25 + 273) K

pr = = = 0.030 and Tr = = = 2.36
pc 33.54 atm Tc 126.3 K

The corresponding states are

(a) For H2 S

p = pr pc = (0.030) × (88.3 atm) = 2.6 atm

T = Tr Tc = (2.36) × (373.2 K) = 881 K

(Critical constants of H2 S obtained from Handbook of Chemistry and Physics.)

(b) For CO2

p = pr pc = (0.030) × (72.85 atm) = 2.2 atm

T = Tr Tc = (2.36) × (304.2 K) = 718 K

(c) For Ar

p = pr pc = (0.030) × (48.00 atm) = 1.4 atm

T = Tr Tc = (2.36) × (150.72 K) = 356 K

E1.22(b) The van der Waals equation is

RT a
p= − 2
V m − b Vm

which can be solved for b

RT −4 3 −1 (8.3145 JK−1 mol−1 ) × (288 K)

b = Vm − a = 4.00 × 10 m mol −  
p+ 2 0.76 m6 Pa mol−2
Vm 4.0 × 10 Pa +
6
(4.00 × 10−4 m3 mol−1 )2

= 1.3 × 10−4 m3 mol−1

TRAPP-ISM: “TRAPPISM_CH01” — 2006/3/24 — 11:42 — PAGE 12 — #12

 THE PROPERTIES OF GASES 13

The compression factor is

pVm (4.0 × 106 Pa) × (4.00 × 10−4 m3 mol−1 )
z= = = 0.67
RT (8.3145 J K−1 mol−1 ) × (288 K)

Solutions to problems

Solutions to numerical problems

P1.2 Solving for n from the perfect gas equation [1.8] yields n = pV /RT and n = m/M, hence ρ = m/V =
RT p RT RT
Mp/RT Rearrangement yields the desired relation, that is ρ = ρ , or = , and M =
M ρ M p/ρ
Draw up the following table and then plot p/ρ versus p to find the zero pressure limit of p/ρ where all
gases behave ideally.
ρ/(g dm−3 ) = ρ/(kg m−3 );

  
1 atm 1.013 × 105 Pa
1 Torr = (1 Torr) × × = 133.3 Pa
760 Torr 1 atm

p/Torr 91.74 188.98 277.3 452.8 639.3 760.0

p/(104 Pa) 1.223 2.519 3.696 6.036 8.522 10.132
ρ/(kgm−3 ) 0.225 0.456 0.664 1.062 1.468 1.734
(p/ρ) (104 m2 s−2 ) 5.44 5.52 5.56 5.68 5.81 5.84

p
is plotted in Figure 1.2. A straight line fits the data rather well. The extrapolation to p = 0 yields an
ρ
intercept of 5.40 × 104 m2 s−2 . Then

RT (8.314 J K−1 mol−1 ) × (298.15 K)

M= =
5.40 × 104 m2 s−2 5.40 × 104 m2 s−2
= 0.0459 kg mol−1 = 45.9 g mol−1

y = 5.3963 + 0.046074x R = 0.99549

5.9

5.8
(p/ρ) / (104 m2 s–1)

5.7

5.6

5.5

5.4
0 2 4 6 8 10 12
p/(104 Pa) Figure 1.2

TRAPP-ISM: “TRAPPISM_CH01” — 2006/3/24 — 11:42 — PAGE 13 — #13

 14 INSTRUCTOR’S MANUAL

COMMENT. This method of the determination of the molar masses of gaseous compounds is due to Can-
nizarro who presented it at the Karlsruhe conference of 1860 which had been called to resolve the problem of
the determination of the molar masses of atoms and molecules and the molecular formulas of compounds.

P1.4 The mass of displaced gas is ρV , where V is the volume of the bulb and ρ is the density of the gas. The
balance condition for the two gases is m(bulb) = ρV (bulb), m(bulb) = ρ V (bulb)
which implies that ρ = ρ . Because [Problem 1.2] ρ = pM/RT
the balance condition is pM = p M
p
which implies that M = × M
p
This relation is valid in the limit of zero pressure (for a gas behaving perfectly).
In experiment 1, p = 423.22 Torr, p = 327.10 Torr; hence

423.22 Torr
M = × 70.014 g mol−1 = 90.59 g mol−1
327.10 Torr

In experiment 2 p = 427.22 Torr, p = 293.10 Torr; hence

427.22 Torr
M = × 70.014 g mol−1 = 102.0 g mol−1
293.10 Torr

In a proper series of experiments one should reduce the pressure (e.g. by adjusting the balanced
weight). Experiment 2 is closer to zero pressure than experiment 1; it may be safe to conclude that
M ≈ 102 g mol−1 . The molecules CH2 FCF3 or CHF2 CHF2 have M ≈ 102 g mol−1 .

P1.6 We assume that no H2 remains after the reaction has gone to completion. The balanced equation is

N2 + 3H2 → 2NH3

We can draw up the following table

N2 H2 NH3 Total

Initial amount n n 0 n + n
1 2
Final amount n − 3n 0 3n n + 13 n
Specifically 0.33 mol 0 1.33 mol 1.66 mol
Mole fraction 0.20 0 0.80 1.00

 
nRT (8.206 × 10−2 dm3 atm K−1 mol−1 ) × (273.15 K)
p= = (1.66 mol) × = 1.66 atm
V 22.4 dm3

p(H2 ) = x(H2 )p = 0

p(N2 ) = x(N2 )p = (0.20 × (1.66 atm)) = 0.33 atm

p(NH3 ) = x(NH3 )p = (0.80) × (1.66 atm) = 1.33 atm

TRAPP-ISM: “TRAPPISM_CH01” — 2006/3/24 — 11:42 — PAGE 14 — #14

 THE PROPERTIES OF GASES 15

P1.8 From definition of Z [1.16] and the virial equation [1.19], Z may be expressed in virial form as


2
1 1
Z =1+B +C + ···
Vm Vm

Since Vm = RT /p [assumption of perfect gas], 1/Vm = p/RT ; hence upon substitution, and dropping
terms beyond the second power of (1/Vm )

 p   p 2
Z =1+B +C
RT RT


100 atm
Z = 1 + (−21.7 × 10−3 dm3 mol−1 ) ×
(0.0821 dm3 atm K−1 mol−1 ) × (273 K)

2
100 atm
+ (1.200 × 10−3 dm6 mol−2 ) ×
(0.0821 dm3 atm K−1 mol−1 ) × (273 K)
Z = 1 − (0.0968) + (0.0239) = 0.927

  
RT (0.0821 dm3 atm K−1 mol−1 ) × (273 K)
Vm = (0.927) × = (0.927) × = 0.208 dm3
p 100 atm

Question. What is the value of Z obtained from the next approximation using the value of Vm just
calculated? Which value of Z is likely to be more accurate?

Since B (TB ) = 0 at the Boyle temperature (Section 1.3b): B (TB ) = a + b e−c/TB = 0

2
P1.10

−c
−(1131 K2 )
Solving for TB : TB =

 =
 = 501.0 K
 −a
−(−0.1993 bar−1 )
ln 
ln
b (0.2002 bar−1 )





2 2a 1/2 1 2aR 1/2
P1.12 From Table 1.6 Tc = × , pc = ×
3 3bR 12 3b3

1/2

2a 12bpc
may be solved for from the expression for pc and yields . Thus
3bR R AQ: Please




 check the
2 12pc b 8 p c Vc equation
Tc = × = ×
3 R 3 R changed fro

    3 3
8 (40 atm) × 160 × 10 dm3 mol−1
−3
4p
to
4π
.
= × = 210 K
3 8.206 × 10−2 dm3 atm K−1 mol−1



b 1 Vc 160 × 10−6 m3 mol−1
vmol = = × = = 8.86 × 10−29 m3
NA 3 NA (3) × (6.022 × 1023 mol−1 )
4π 3
vmol = r
3

1/3
3
r= × (8.86 × 10−29 m3 ) = 0.28 nm
4π

TRAPP-ISM: “TRAPPISM_CH01” — 2006/3/24 — 11:42 — PAGE 15 — #15

 16 INSTRUCTOR’S MANUAL

Solutions to theoretical problems

pVm 1 a
P1.14 Z= =
− [see Exercise 1.20(a).]
RT b RTVm
1−
Vm



b −1 b b 2
which upon expansion of 1 − =1+ + + · · · yields
AQ: Pls check Vm Vm Vm
the changes that



a 
the letter ‘l’ to
1 1 2
‘c dots’ in the Z =1+ b− × + b2 + ···
inline and RT Vm Vm
displayed
equations. We note that all terms beyond the second are necessarily positive, so only if

2
a b b
> + + ···
RTVm Vm Vm

can Z be less than one. If we ignore terms beyond b/Vm , the conditions are simply stated as

a a
Z<1 when >b Z>1 when <b
RT RT

Thus Z < 1 when attractive forces predominate, and Z > 1 when size effects (short-range repulsions)
predominate.

P1.16 The Dieterici equation of state is listed in Table 1.6. At the critical point the derivatives of p with respect
to (wrt) Vm equal zero along the isotherm for which T = Tc . This means that (∂p/∂Vm )T = 0 and
(∂ 2 p/∂Vm2 )T = 0 at the critical point.

  
RT e−a/RT Vm ∂p aVm − ab − RT Vm2
p= =p
Vm − b ∂Vm T Vm2 (Vm − b)(RT )


  
∂ 2p ∂p aVm − ab − RT Vm2 (−2aVm2 + 4Vm ab + RT Vm3 − 2ab2 )
= +p
∂Vm2 T ∂Vm T Vm2 (Vm − b)(RT ) [Vm
3 [(V − b)2 (RT )]]
m

Each of these equations is evaluated at the critical point giving the three equations:

RTc e−a/RTc Vc
pc = aVc − ab − RTc Vc2 = 0
Vc − b

− 2aVc2 + 4Vc ab + RTc Vc3 − 2ab2 = 0

Solving the middle equation for Tc , substitution of the result into the last equation, and solving for Vc
yields the result: Vc = 2b or b = Vc /2 (The solution Vc = b is rejected because there is a singularity
in the Dieterici equation at the point Vm = b.) Substitution of Vc = 2b into the middle equation and

TRAPP-ISM: “TRAPPISM_CH01” — 2006/3/24 — 11:42 — PAGE 16 — #16

 THE PROPERTIES OF GASES 17

solving for Tc gives the result: Tc = a/4bR or a = 2RTc Vc . Substitution of Vc = 2b and Tc = a/4bR
into the first equation gives:

1  a  −2
pc = e
4 b2
The equations for Vc , Tc , pc are substituted into the equation for the critical compression factor (eqn 1.17)
to give: Zc = pc Vc /RTc = 2e−2 = 0.2707. This is significantly lower than the critical compression factor
that is predicted by the van der Waals equation (eqn 1.23): Zc (vdW) = pc Vc /RTc = 3/8 = 0.3750.
Experimental values for Zc are summarized in Table 1.4 where it is seen that the Dieterici equation
prediction if often better.
pVm
P1.18 RT = 1 + B p + C p2 + · · · [1.18]
RT
pVm B C
=1+ + 2 + · · · [1.19]
RT Vm Vm

B C
whence B p + C p2 + · · · = + 2 + ···
Vm Vm
Now multiply through by Vm , replace pVm by RT {1 + (B/Vm ) + · · · }, and equate coefficients of
1 BB RT + C R2 T 2 C
powers of : B RT + + ··· = B + + ···
Vm Vm Vm
B
Hence, B RT = B, implying that B =
RT

C − B2
Also, BB RT + C R2 T 2 = C, or B2 + CR2 T 2 = C, implying that C =
R2 T 2



∂Vm ∂Vm
P1.20 Write Vm = f (T , p); then dVm = dT + dp
∂T p ∂p T

Restricting the variations of T and p to those which leave Vm constant, that is dVm = 0, we obtain


∂p





 −
∂Vm ∂Vm ∂p ∂p −1 ∂p ∂T Vm
=− × =− × =

∂T p ∂p T ∂T Vm ∂Vm T ∂T Vm ∂p
∂Vm T

From the equation of state



∂p RT ∂p R b
= − 2 − 2(a + bT )Vm−3 = + 2
∂Vm T Vm ∂T Vm Vm Vm

Substituting




R b b

 + R+
∂Vm Vm Vm 2 Vm
= −
 = +

∂T P RT 2(a + bT ) RT 2(a + bT )
− 2 − +
Vm Vm3 Vm Vm2

TRAPP-ISM: “TRAPPISM_CH01” — 2006/3/24 — 11:42 — PAGE 17 — #17

 18 INSTRUCTOR’S MANUAL

(a + bT ) RT
From the equation of state =p−
Vm2 Vm



b b

 R+ R+
∂Vm V Vm RVm + b
Then =
m  = =
∂T RT RT RT 2pVm − RT
p +2 p− 2p −
Vm Vm Vm

P1.22 z = Vm /Vmo , where Vmo = the molar volume of a perfect gas

From the given equation of state

RT b + Vmo b
Vm = b + = b + Vmo then Z = =1+ o
p Vmo Vm

For Vm = 10b, 10b = b + Vmo or Vmo = 9b

10b 10
then Z = = = 1.11
9b 9

P1.24 The virial equation is


B C
pVm = RT 1 + + 2 + ··· or
Vm Vm

pVm B C
=1+ + 2 + ···
RT Vm Vm

(a) If we assume that the series may be truncated after the B term, then a plot of (pVm /RT ) vs (1/Vm )
will have B as its slope and 1 as its y-intercept. Transforming the data gives

p/MPa (Vm /dm3 )/(mol−1 ) pVm /RT (1/Vm )/(mol dm−3 )

0.4000 6.2208 0.9976 0.1608

0.5000 4.9736 0.9970 0.2011
0.6000 4.1423 0.9964 0.2414
0.8000 3.1031 0.9952 0.3223
1.000 2.4795 0.9941 0.4033
1.500 1.6483 0.9912 0.6067
2.000 1.2328 0.9885 0.8112
2.500 0.98357 0.9858 1.017
3.000 0.81746 0.9832 1.223
4.000 0.60998 0.9782 1.639

A plot of the data in the third column against that of the fourth column is shown in Figure 1.3. The
data fit a straight line reasonably well, and the y-intercept is very close to 1. The regression yields
B = −1.32 × 10−2 dm3 mol−1 .

TRAPP-ISM: “TRAPPISM_CH01” — 2006/3/24 — 11:42 — PAGE 18 — #18

 THE PROPERTIES OF GASES 19

=
=

(1/Vm )/(dm3mol–1)
Figure 1.3

(b) A quadratic function fits the data somewhat better (Figure 1.4) with a slightly better correlation
coefficient and a y-intercept closer to 1. This fit implies that truncation of the virial series after the
term with C is more accurate than after just the B term. The regression then yields

B = −1.51 × 10−2 dm3 mol−1 and C = 1.07 × 10−3 dm6 mol−2

(1/Vm )/(dm3mol–1)
Figure 1.4

Solutions to applications

P1.26 The perfect gas law is

pV
pV = nRT so n=
RT
At mid-latitudes
(1.00 atm) × [(1.00 dm2 ) × (250 × 10−3 cm)/10cm dm−1 ]
n= = 1.12 × 10−3 mol
(0.08206 dm3 atm K−1 mol−1 ) × (273 K)
In the ozone hole
(1.00 atm) × [(1.00 dm2 ) × (100 × 10−3 cm)/10 cm dm−1 ]
n= = 4.46 × 10−4 mol
(0.08206 dm3 atm K−1 mol−1 ) × (273 K)

TRAPP-ISM: “TRAPPISM_CH01” — 2006/3/24 — 11:42 — PAGE 19 — #19

 20 INSTRUCTOR’S MANUAL

The corresponding concentrations are

n 1.12 × 10−3 mol

= = 2.8 × 10−9 mol dm−3
V (1.00 dm ) × (40 × 103 m) × (10 dm m−1 )
2

n 4.46 × 10−4 mol

and = = 1.1 × 10−9 mol dm−3
V (1.00 dm2 ) × (40 × 103 m) × (10 dm m−1 )

respectively.

pV 4π 3 4π
P1.28 n= [1.2], V = r = × (3.0 m)3 = 113 m3 = volume of balloon
RT 3 3
p = 1.0 atm, T = 298 K
(1.0 atm) × (113 × 103 dm3 )
(a) n = = 4.62 × 103 mol
(8.206 × 10−2 dm3 atm K−1 mol−1 ) × (298 K)
(b) The mass that the balloon can lift is the difference between the mass of displaced air and the mass
of the balloon. We assume that the mass of the balloon is essentially that of the gas it encloses.
Then m(H2 ) = nM(H2 ) = (4.62 × 103 mol) × (2.02 g mol−1 ) = 9.33 × 103 g
Mass of displaced air = (113 m3 ) × (1.22 kg m−3 ) = 1.38 × 102 kg
Therefore, the payload is (138 kg) − (9.33 kg) = 1.3 × 102 kg
(c) For helium, m = nM(He) = (4.62 × 103 mol) × (4.00 g mol−1 ) = 18 kg
The payload is now 138 kg − 18 kg = 1.2 × 102 kg

P1.30 Avogadro’s principle states that equal volumes of gases represent equal amounts (moles) of the gases,
so the volume mixing ratio is equal to the mole fraction. The definition of partial pressures is

p J = xJ p

The perfect gas law is

nJ pJ xJ p
pV = nRT so = =
V RT RT

(a) n(CCl3 F) (261 × 10−12 ) × (1.0 atm)

= = 1.1 × 10−11 mol dm−3
V (0.08206 dm3 atm K−1 mol−1 ) × (10 + 273) K
n(CCl2 F2 ) (509 × 10−12 ) × (1.0 atm)
and = = 2.2 × 10−11 mol dm−3
V (0.08206 dm3 atm K−1 mol−1 ) × (10 + 273) K

(b) n(CCl3 F) (261 × 10−12 ) × (0.050 atm)

= = 8.0 × 10−13 mol dm−3
V (0.08206 dm3 atm K−1 mol−1 ) × (200 K)
n(CCl2 F2 ) (509 × 10−12 ) × (0.050 atm)
and = = 1.6 × 10−12 mol dm−3
V (0.08206 dm3 atm K−1 mol−1 ) × (200 K)

TRAPP-ISM: “TRAPPISM_CH01” — 2006/3/24 — 11:42 — PAGE 20 — #20