1

The properties of gases

Equations of state 18 Although gases are simple, both to describe and in

terms of their internal structure, they are of immense
1.1 The perfect gas equation of state 19
importance. We spend our whole lives surrounded
1.2 Using the perfect gas law 22 by gas in the form of air and the local variation in its
1.3 Mixtures of gases: partial pressures 23
properties is what we call the ‘weather’. To under-
stand the atmospheres of this and other planets we
The molecular model of gases 26 need to understand gases. As we breathe, we pump
gas in and out of our lungs, where it changes com-
1.4 The pressure of a gas according to the kinetic position and temperature. Many industrial processes
model 27 involve gases, and both the outcome of the reaction
1.5 The average speed of gas molecules 27 and the design of the reaction vessels depend on
knowledge of their properties.
1.6 The Maxwell distribution of speeds 28
1.7 Diffusion and effusion 30
1.8 Molecular collisions 32 Equations of state
Real gases 33
We can specify the state of any sample of substance
1.9 Molecular interactions 33 by giving the values of the following properties (all of
which are defined in the Foundations section):
1.10 The critical temperature 34
1.11 The compression factor 36 V, the volume of the sample
p, the pressure of the sample
1.12 The virial equation of state 36
T, the temperature of the sample
1.13 The van der Waals equation of state 37 n, the amount of substance in the sample
1.14 The liquefaction of gases 40 However, an astonishing experimental fact is that
these four quantities are not independent of one
FURTHER INFORMATION 1.1 41 another. For instance, we cannot arbitrarily choose
CHECKLIST OF KEY CONCEPTS 42 to have a sample of 0.555 mol H2O in a volume of
ROAD MAP OF KEY EQUATIONS 43 10 dm3 at 100 kPa and 500 K: it is found experimen-
QUESTIONS AND EXERCISES 43 tally that that state simply does not exist. If we select
the amount, the volume, and the temperature, then
we find that we have to accept a particular pressure
(in this case, close to 230 kPa). This experimental
generalization is summarized by saying the substance
obeys an equation of state, an equation of the form

p = f(n,V,T) Equation of state (1.1)

This expression tells us that the pressure depends

on (‘is a function of’) the amount, volume, and

9780199608119_C01.indd 18 9/21/12 4:37 PM


temperature and that if we know those three variables,
then the pressure can have only one value.
The equations of state of most substances are
not known, so in general we cannot write down an
explicit expression for the pressure in terms of the
other variables. However, certain equations of state
are known. In particular, the equation of state of a
low-pressure gas is known, and proves to be very
simple and very useful. This equation is used to
describe the behaviour of gases taking part in reac-
tions, the behaviour of the atmosphere, as a starting
point for problems in chemical engineering, and even
in the description of the structures of stars.
1.1 The perfect gas equation of state
The equation of state of a low-pressure gas was
among the first results to be established in physical
chemistry. The original experiments were carried
out by Robert Boyle in the seventeenth century and
there was a revival of interest later in the century
when people began to fly in balloons. This techno-
logical progress demanded more knowledge about
the response of gases to changes of pressure and
temperature and, like technological advances in
other fields today, that interest stimulated a lot of
experiments.
The experiments of Boyle and his successors led to
the formulation of the following perfect gas equation
of state:
Perfect gas
pV = nRT equation of state (1.2a)
This equation has the form of eqn 1.1 when re-
arranged into
nRT
p= (1.2b)
V Boyle’s law:
The gas constant R is currently an experimentally
determined quantity obtained by evaluating R = pV/
nRT as the pressure is allowed to approach zero. For
calculations, we shall normally use the approximate
value 8.3145 J K−1 mol−1. Values of R in a variety of
units are given in Table 1.1.
The perfect gas equation of state—more briefly,
the ‘perfect gas law’—is so called because it is an
idealization of the equations of state that gases actu-
ally obey. Specifically, it is found that all gases obey
the equation ever more closely as the pressure is
reduced towards zero. That is, eqn 1.2 is an example
of a limiting law, a law that becomes increasingly
valid in a certain limit, in this case as the pressure
is reduced to zero. The law is obeyed exactly in the
limit of zero pressure.
9780199608119_C01.indd 19
EQUATIONS OF STATE 19
Table 1.1
The gas constant in various units
R = 8.314 47 J K−1 mol−1
8.314 47 dm3 kPa K−1 mol−1
8.205 74 × 10−2 dm3 atm K−1 mol−1
62.364 dm3 Torr K−1 mol−1
1.987 21 cal K−1 mol−1
1 dm3 = 10−3 m3
A hypothetical substance that obeys eqn 1.2 at all
pressures, not just at very low pressures, is called a
perfect gas. From what has just been said, an actual
gas, which is termed a real gas, behaves more and
more like a perfect gas as its pressure is reduced
towards zero. In practice, normal atmospheric pres-
sure at sea level (p ≈ 100 kPa) is already low enough
for most real gases to behave almost perfectly, and
unless stated otherwise we shall always assume in
this text that the gases we encounter behave like
a perfect gas. The reason why a real gas behaves
differently from a perfect gas can be traced to the
attractions and repulsions that exist between actual
molecules and which are absent in a perfect gas
(Chapter 15).
A note on good practice A perfect gas is widely called an
‘ideal gas’ and the perfect gas equation of state is commonly
called ‘the ideal gas equation’. We use ‘perfect gas’ to imply
the absence of molecular interactions; we use ‘ideal’; in
Chapter 6 to denote mixtures in which all the molecular
interactions are the same but not necessarily zero.
The perfect gas law is based on and summarizes
three sets of experimental observations. One is
At constant temperature, the pressure of a fixed
amount of gas is inversely proportional to its
volume.
Mathematically:
1
p∝ At constant temperature Boyle’s law (1.3)
V
We can easily verify that eqn 1.2 is consistent with
Boyle’s law: by treating n and T as constants, the
perfect gas law becomes pV = constant, and hence
p ∝ 1/V. Boyle’s law implies that if we compress
(reduce the volume of) a fixed amount of gas at con-
stant temperature into half its original volume, then
its pressure will double. Figure 1.1 shows the graph
obtained by plotting experimental values of p against
9/21/12 4:37 PM
 20 CHAPTER 1 THE PROPERTIES OF GASES

Observed
Pressure, p

Pressure, p
Perfect gas
Increasing
temperature

Volume, V 1/Volume, 1/V

Fig. 1.1 The volume of a gas decreases as the pressure
on it is increased. For a sample that obeys Boyle’s law
and that is kept at constant temperature, the graph show-
ing the dependence is a hyperbola, as shown here. Each
curve corresponds to a single temperature, and hence is
an isotherm. The isotherms are hyperbolas (The chemist’s
toolkit 1.1).
Fig. 1.2 A good test of Boyle’s law is to plot the pressure
against 1/V (at constant temperature), when a straight line
should be obtained. This diagram shows that the observed
pressures approach a straight line (the blue line) as the vol-
ume is increased and the pressure reduced. A perfect gas
would follow the straight line at all pressures; real gases obey
Boyle’s law in the limit of low pressures.

V for a fixed amount of gas at different temperatures
and the curves predicted by Boyle’s law. Each curve
is a hyperbola (see The chemist’s toolkit 1.1 for a
discussion of graphs) and called an isotherm because
it depicts the variation of a property (in this case, the
pressure) at a single constant temperature. It is hard,
from this graph, to judge how well Boyle’s law is
obeyed. However, when we plot p against 1/V, we
get straight lines, just as we would expect from
Boyle’s law (Fig. 1.2).

The chemist’s toolkit 1.1 Graphs

The graphs of xy = a, with a a constant, or y = a/x are hyper- The horizontal and vertical axes of graphs are labelled
bolas. Examples are the isotherms in Fig. 1.1. The graph with pure numbers. Thus, if the units of x and y are denoted
of y = ax 2 is a parabola; it plays a role in the discussion ‘units of x’ and ‘units of y’, the plot should be of y/(units of
of molecular vibrations. These two ‘conic sections’ are y) against x/(units of x). It follows that the slope of a graph
illustrated in Sketch 1.1. is dimensionless. For a graph of the form y/(units of y) =
The graph of y = mx + b is a straight line of slope m and b + mx/(units of x), both m and b are pure numbers. To
passing through y = b at x = 0, the ‘intercept with the y-axis’ interpret them in terms of physical quantities we multiply
(Sketch 1.2). In the special case b = 0, y = mx and the both sides of this expression by ‘units of y’, and obtain
straight line passes through the origin y = 0 when x = 0. In
Interpretation
n
that case we say that ‘y is proportional to x’ (y ∝ x) the Interpretation of the slope
of the intercept
e
  
constant of proportionality being m. The intercept with the
 
units of y
x-axis occurs when x = −b/m (because then y = m(−b/m) + b y b i f y) + × ×x
units of x
= 0).

y
y = mx + b
(a) (b)
y

a Slope, m
y
Intercept, b

a1/2
a
0 x
1 a1/2 x –1 0 1 x x = –b/m

Sketch 1.1 The characteristics of (a) hyperbolas and (b) Sketch 1.2 The characteristics of a straight-line graph of y
parabolas. against x with y = mx + b.

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 EQUATIONS OF STATE 21

A note on good practice In general, it is best to plot data
as straight lines to test the validity of a theory because it is
difficult to distinguish between subtly different shapes of a
curve by eye. Instead, the mathematical function that repre-
sents the theory is rearranged so that the resulting graph has
the form of a straight line, y = mx + b.
The second experimental observation summarized
by eqn 1.2 is Charles’s law:
At constant pressure, the volume of a fixed amount
of gas varies linearly with the temperature.
The equation for this linear dependence is
V = A + Bθ Constant pressure Charles’s law (1.4a)
where θ (theta) is the temperature on the Celsius
scale and A and B are constants that depend on the
amount of gas and the pressure. Figure 1.3 shows
typical plots of volume against temperature for a
series of samples of gases at different pressures and
confirms that (at low pressures, and for temperatures
that are not too low) the volume varies linearly with
the Celsius temperature. We also see that all the
volumes extrapolate to zero as θ approaches the
same very low temperature (−273.15 °C, in fact),
regardless of the identity of the gas. Because a vol-
ume cannot be negative, this common temperature
must represent the absolute zero of temperature, a
temperature below which it is impossible to cool an
object. Indeed, as explained in Foundations 0.10, the
‘thermodynamic’ scale ascribes the value T = 0 to this
absolute zero of temperature. In terms of the thermo-
dynamic temperature, therefore, Charles’s law takes
the simpler form
Increasing
pressure
Volume, V
V∝T Constant pressure Charles’s law (1.4b)
It follows that doubling the temperature (such as
from 300 K to 600 K, corresponding to an increase
from 27 °C to 327 °C) doubles the volume, provided
the pressure remains the same. Now we can see that
eqn 1.2 is consistent with Charles’s law. First, we
rearrange it into V = nRT/p, and then note that when
the amount n and the pressure p are both constant,
we can write V ∝ T, as required.
The third feature of gases summarized by eqn 1.2
is Avogadro’s principle:
At a given temperature and pressure, equal volumes
of gas contain the same numbers of molecules.
That is, 1.00 dm3 of oxygen at 100 kPa and 300 K
contains the same number of molecules as 1.00 dm3
of carbon dioxide, or any other gas, at the same tem-
perature and pressure. The principle implies that if
we double the number of molecules, but keep the
temperature and pressure constant, then the volume
of the sample will double. We can therefore write
Constant temperature Avogadro’s
V∝n and pressure principle (1.5)
This result follows easily from eqn 1.2 if we treat p
and T as constants. Avogadro’s suggestion is a prin-
ciple rather than a law (a direct summary of experi-
ence), because it is based on a model of a gas, in
this case as a collection of molecules. Even though
there is no longer any doubt that molecules exist, this
relation remains a principle rather than a law.
The molar volume, Vm, the volume a substance
occupies per mole of molecules, was introduced in
Foundations 0.4:
V
Vm = Definition Molar volume (1.6a)
n
For a perfect gas, n = pV/RT, so in this case

n = pV / RT 1/(a / x )= x / a
 V 
Cancel V
1  RT
Vm = = =
pV /RT p/RT p

Observed Perfect gas Molar volume (1.6b)

To interpret this expression, note that
Perfect gas

Temperature, θ/°C
–273.15
Fig. 1.3 This diagram illustrates the content and implications
of Charles’s law, which asserts that the volume occupied by
a gas (at constant pressure) varies linearly with the tempera-
ture. When plotted against Celsius temperatures (as here), all
gases give straight lines that extrapolate to V = 0 at −273.15 °C.
This extrapolation suggests that −273.15 °C is the lowest
attainable temperature.
• Because eqn 1.6b makes no reference to the identity
of the gas, provided the gas is behaving perfectly,
its molar volume is the same whatever its chemical
identity at the same temperature and pressure.
The data in Table 1.2 show that this conclusion is
approximately true for most gases under normal
conditions (normal atmospheric pressure of about
100 kPa and room temperature).

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 22 CHAPTER 1 THE PROPERTIES OF GASES

understand the changes in the atmosphere that we

Table 1.2
call the weather (see Impact 1.1 following Section 1.3).
The molar volumes of gases at standard
ambient temperature and pressure
(SATP: 298.15 K and 1 bar)
Example 1.1
Gas Vm /(dm3 mol−1)
Predicting the pressure of a sample of gas
Perfect gas 24.7896* A chemist is investigating the conversion of atmospheric
Ammonia 24.8 nitrogen to usable form by the bacteria that inhabit the root
Argon 24.4 systems of certain legumes, and needs to know the pressure
Carbon dioxide 24.6 in kilopascals exerted by 1.25 g of nitrogen gas in a flask of
Nitrogen 24.8 volume 250 cm3 at 20 °C.
Oxygen 24.8
Strategy For this calculation, arrange eqn 1.2a (pV = nRT )
Hydrogen 24.8 into a form that gives the unknown (the pressure, p) in terms
Helium 24.8 of the information supplied, which in this case is eqn 1.2b
(p = nRT/V ). To use this expression, we need to know the
*At STP (0 °C, 1 atm), Vm = 24.4140 dm3 mol−1.
amount of molecules (in moles) in the sample, which we can
obtain from the mass and the molar mass (by using n = m/M )
and to convert the temperature to the Kelvin scale (by adding
273.15 to the Celsius temperature.
Chemists have found it convenient to report much
Solution The amount of N2 molecules (of molar mass
of their data on gases at a particular set of ‘standard’
28.02 g mol−1) present is
conditions.1 By standard ambient temperature and
pressure (SATP) they mean a temperature of 25 °C n(N2) =
m
=
1.25 g
=
1.25
mol
(more precisely, 298.15 K) and a pressure of exactly M (N2) 28.02 g mol−1 28.02
1 bar (100 kPa). The standard pressure is denoted The temperature of the sample is
pa, so pa = 1 bar exactly. The molar volume of a
perfect gas at SATP is 24.79 dm3 mol−1, as can be T/K = 20 + 273.15, so T = (20 + 273.15) K
verified by substituting the values of the temperature Therefore, from p = nRT/V,
and pressure into eqn 1.6b. This value implies that at R
SATP, 1 mol of perfect gas molecules occupies about
n



T

−1 −1
(1.25/ 28.02) mol × (8.3145 J K mol ) × (20 + 273.15) K
25 dm3 (a cube of about 30 cm on a side). An earlier p=
(2.50 × 10−4 ) m3
set of standard conditions, which is still encountered, 
is standard temperature and pressure (STP), namely V

0 °C and 1 atm. The molar volume of a perfect gas at (1.25/ 28.02) × (8.3145) × (20 + 273.15) J
STP is 22.41 dm3 mol−1. =
2.50 × 10−4 m3
1 J m−3 =1 Pa 1 kPa =103 Pa
 
1.2 Using the perfect gas law = 4.35 × 10 Pa
5
= 435 kPa

Here we review two elementary applications of the
perfect gas equation of state:
• The prediction of the pressure of a gas given its
temperature, its chemical amount, and the vol-
ume it occupies.
• The prediction of the change in pressure arising
from changes in the conditions.
Calculations like these underlie more advanced
considerations, including the way that meteorologists
1 at 37 °C.
Be very careful not to confuse these ‘standard conditions’ for
gases with the ‘standard states’ of substances, which are introduced
in Chapter 3.
Note how the units cancel like ordinary numbers. Had we
required the pressure in different units we could, instead,
have used Table 1.1 to select the appropriate value of R to
match the information required.
A note on good practice It is best to postpone a numer-
ical calculation to the last possible stage, and carry it out in a
single step. This procedure avoids rounding errors.
Self-test 1.1
Calculate the pressure exerted by 1.22 g of carbon dioxide
confined to a flask of volume 500 dm3 (ie, 5.00 × 102 dm3)
Answer: 143 Pa

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 EQUATIONS OF STATE 23

In some cases, we are given the pressure under one 1.3 Mixtures of gases: partial pressures
set of conditions and are asked to predict the pres-
Scientists are often concerned with mixtures of gases,
sure of the same sample under a different set of con-
such as when they are considering the properties of
ditions. In that case, we use the perfect gas law as
the atmosphere in meteorology, the composition of
follows. Suppose the initial pressure is p1, the initial
exhaled air in medicine, or the mixtures of hydro-
temperature is T1, and the initial volume is V1. Then
gen and nitrogen used in the industrial synthesis of
by dividing both sides of eqn 1.2a by the tempera-
ammonia. They need to be able to assess the contri-
ture, which gives pV/T = nR in general, we can write
bution that each component of a gaseous mixture
in this instance
makes to the total pressure.
p1V1 In the early nineteenth century, John Dalton
= nR
T1 carried out a series of experiments that led him to
formulate what has become known as Dalton’s law:
Suppose now that the conditions are changed to T2
and V2, and the pressure changes to p2 as a result. The pressure exerted by a mixture of perfect gases
Then under the new conditions eqn 1.2a tells us that is the sum of the pressures that each gas would
exert if it were alone in the container at the same
p2V2
= nR temperature:
T2
p = pA + pB + ... Perfect gases Dalton’s law (1.8)
The nR on the right of these two equations is the
same in each case, because R is a constant and the In this expression, pJ is the pressure that the gas J
amount of gas molecules has not changed. It follows would exert if it were alone in the container at the
that we can combine the two equations into a single same temperature. Dalton’s law is strictly valid only
equation: for mixtures of perfect gases (or for real gases at such
low pressures that they are behaving perfectly), but it
p1V1 p2V2 Combined can be treated as valid under most conditions we
= Constant
gas equation (1.7)
T1 T2 amount of gas
encounter.
This equation can be rearranged to calculate any one
Brief illustration 1.2 Dalton’s law
unknown (such as p2 for instance) in terms of the
other variables. Suppose we were interested in the composition of
inhaled and exhaled air, and we knew that a certain
mass of carbon dioxide exerts a pressure of 5 kPa
Brief Illustration 1.1 The combined gas
when present alone in a container, and that a certain
equation
mass of oxygen exerts 20 kPa when present alone in
Consider a sample of gas with an initial volume of the same container at the same temperature. Then,
15 cm3 that has been heated from 25 °C to 1000 °C when both gases are present in the container, the
and had its pressure increased from 10.0 kPa to 150.0 carbon dioxide in the mixture contributes 5 kPa to the
kPa. We may rearrange eqn 1.7 and use it to calculate total pressure and oxygen contributes 20 kPa; accord-
the final volume ing to Dalton’s law, the total pressure of the mixture is
pV
1 1 T2 p T the sum of these two pressures, or 25 kPa (Fig. 1.4).
V2 = × = 1 × 2 ×V
T1 p1 p2 T1 1

p1/ p2

 T2 /T1



V1
Self-test 1.3
10.0 kPa (1000 + 273.15) K Suppose some nitrogen, enough to generate a pres-
= × × 15 cm3 = 4.3 cm3
150.0 kPa (25 + 273.15) K sure of 10 kPa when there alone, is introduced into the
mixture. What is the new total pressure?
Answer: 35 kPa

Self-test 1.2
Calculate the final pressure of a gas that is com-
pressed from a volume of 20.0 dm3 to 10.0 dm3 and
cooled from 100 °C to 25 °C if the initial pressure is
1.00 bar.
Answer: 1.60 bar
For any type of gas (real or perfect) in a mixture,
the partial pressure, pJ, of the gas J is defined as
pJ = x J p Definition Partial pressure (1.9)
where xJ is the mole fraction of the gas J in the
mixture. The mole fraction of J is the amount of J

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 24 CHAPTER 1 THE PROPERTIES OF GASES

20
5 25 A
kPa kPa kPa B
pA pB pA + pB
xA = 0.708

xB = 0.292
A B A+B

xA = 0.375

Fig. 1.4 The partial pressure pA of a perfect gas A is the pres- xB = 0.625
sure that the gas would exert if it occupied a container alone;
similarly, the partial pressure pB of a perfect gas B is the
pressure that the gas would exert if it occupied the same
container alone. The total pressure p when both perfect
gases simultaneously occupy the container is the sum of
their partial pressures. xA = 0.229

xB = 0.771

molecules expressed as a fraction of the total amount

of molecules in the mixture. In a mixture that con- Fig. 1.5 A representation of the meaning of mole fraction.
In each case, a small square represents one molecule of A
sists of nA A molecules, nB B molecules, and so on
(yellow squares) or B (green squares). There are 48 squares
(where the nJ are amounts in moles), the mole frac- in each sample.
tion of J (where J = A, B, . . .) is
nJ Solution From eqn 0.2, the amounts of N2, O2, and Ar are
Mole
xJ = n = nA + nB + . . . Definition fraction (1.10a) m N2
n n N2 = =
75.5 g
= 2.70 mol
MN2 28.0 g mol−1
Mole fractions are unitless because the unit mole
mO2 23.2 g
in numerator and denominator cancel. For a binary nO2 = = = 0.725 mol
mixture, one that consists of two species, this general MO2 32.0 g mol−1
expression becomes mAr 1.3 g
nAr = = = 0.033 mol
M Ar 39.9 g mol−1
nA nB
xA = xB = xA + xB = 1
nA + nB nA + nB The mole fraction of N2 molecules is, from eqn 1.10b,
(1.10b) n N2 2.70 mol
x N2 = =
When only A is present, xA = 1 and xB = 0. When only nN2 + nO2 + nAr 2.70 mol + 0.725 mol + 0.033 mol

B is present, xB = 1 and xA = 0. When both are present n
in the same amounts, xA = 1/2 and xB = 1/2 (Fig. 1.5). = 0.780
When it is typographically more convenient, we
By repeating the calculation for the other constituents, we
write amounts as n(J), mole fractions as x(J), and
find that the mole factions of O2 and Ar in dry air are 0.210
partial pressures as p(J).
and 0.009, respectively.

Example 1.2 Self-test 1.4

Calculating mole fractions The mole fraction of NH3 in a sample of 10.0 mol of gas is
0.285. What mass of NH3 is present in the sample?
A mass of 100.0 g of dry air consists of 75.5 g of N2, 23.2 g of
Answer: 79.8 g
O2, and 1.3 g of Ar. Express the composition of dry air in
terms of mole fractions.

Strategy Begin by converting each mass to an amount in For a mixture of perfect gases, we can identify the
moles. Determine the mole fractions using eqn 1.10b as a partial pressure of J with the contribution that J
ratio of the amount of each constituent to the total amount of makes to the total pressure. Thus, if we introduce
substance. p = nRT/V into eqn 1.9, we get

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 EQUATIONS OF STATE 25

p
Table 1.3
nJ nRT n JRT
pJ = × = The composition of the Earth’s atmosphere
n V V
Substance Percentage
The quantity nJRT/V is the pressure that an amount
nJ of perfect gas J would exert in the otherwise By volume By mass
empty container. That is, for a perfect gas, the partial
pressure of a gas in a mixture is the pressure it Nitrogen, N2 78.08 75.53
would exert if it were alone in the container (at the Oxygen, O2 20.95 23.14
same temperature). If the gases are real, then their Argon, Ar 0.93 1.28
partial pressures are still given by eqn 1.9, for that Carbon dioxide, CO2 0.031 0.047
definition applies to all gases, and the sum of these Hydrogen, H2 5.0 × 10−3 2.0 × 10−4
partial pressures is the total pressure (because the Neon, Ne 1.8 × 10−3 1.3 × 10−3
sum of all the mole fractions is 1); however, we can Helium, He 5.2 × 10−4 7.2 × 10−5
no longer say that each partial pressure is the pres- Methane, CH4 2.0 × 10−4 1.1 × 10−4
sure that the gas would exert when it is alone in the Krypton, Kr 1.1 × 10−4 3.2 × 10−4
container. Nitric oxide, NO 5.0 × 10−5 1.7 × 10−6
Xenon, Xe 8.7 × 10−6 3.9 × 10−5
Ozone, O3 Summer: 7.0 × 10−6 1.2 × 10−5
Brief illustration 1.3 Partial pressures
Winter: 2.0 × 10−6 3.3 × 10−6
From Example 1.2, we have x(N2) = 0.780, x(O2) =
0.210, and x(Ar) = 0.009 for dry air at sea level. It then
follows from eqn 1.9 that when the total atmospheric
pressure is 100 kPa, the partial pressure of nitrogen is
One of the most variable constituents of air is water
p(N2) = x(N2)p = 0.780 × (100 kPa) = 78.0 kPa
vapour, and the humidity it causes. The presence of water
Similarly, for the other two components we find p(O2) vapour results in a lower density of air at a given temperature
= 21.0 kPa and p(Ar) = 0.9 kPa. Provided the gases are and pressure, as we may conclude from Avogadro’s prin-
perfect, these partial pressures are the pressures that ciple. The numbers of molecules in 1 m3 of moist air and
each gas would exert if it were separated from the dry air are the same (at the same temperature and pressure),
mixture and put in the same container on its own. but the mass of an H2O molecule is less than that of all the
other major constituents of air (the molar mass of H2O is
18 g mol−1, the average molar mass of air molecules is
Self-test 1.5 29 g mol−1), so the density of the moist sample is less than
that of the dry sample.
The partial pressure of oxygen in air plays an important The pressure and temperature vary with altitude. In the
role in the aeration of water, to enable aquatic life to troposphere the average temperature is 15 °C at sea level,
thrive, and in the absorption of oxygen by blood in our falling to −57 °C at the bottom of the tropopause at 11 km.
lungs (see Section 6.4). Calculate the partial pressures This variation is much less pronounced when expressed on
of a sample of gas consisting of 2.50 g of oxygen the Kelvin scale, ranging from 288 K to 216 K, an average of
and 6.43 g of carbon dioxide with a total pressure of 268 K. If we suppose that the temperature has its average
88 kPa. value all the way up to the edge of the troposphere, then the
Answer: 31 kPa, 57 kPa pressure varies with altitude, h, according to the barometric
formula:

p = p0e−h/H

Impact on environmental science 1.1
The gas laws and the weather
The biggest sample of gas readily accessible to us is the
atmosphere, a mixture of gases with the composition sum-
marized in Table 1.3. The composition is maintained moder-
ately constant by diffusion and convection (winds, particularly
the local turbulence called eddies) but the pressure and
temperature vary with altitude and with the local conditions,
particularly in the troposphere (the ‘sphere of change’), the
layer extending up to about 11 km.
where p0 is the pressure at sea level and H is a constant
approximately equal to 8 km. More specifically, H = RT/Mg,
where M is the average molar mass of air, T is the tempera-
ture, and g is the acceleration of free fall. The barometric
formula fits the observed pressure distribution quite well
even for regions well above the troposphere (Fig. 1.6). It
implies that the pressure of the air and its density fall to half
their sea-level value at h = H ln 2, or 6 km.
Local variations of pressure, temperature, and composition
in the troposphere are manifest as ‘weather’. A small region
of air is termed a parcel. First, we note that a parcel of warm

9780199608119_C01.indd 25 9/21/12 4:37 PM

 26 CHAPTER 1 THE PROPERTIES OF GASES
24
18
Altitude, h/km
12
0 Fig. 1.8 The model used for discussing the molecular basis
0 0.5 1
Pressure, p/p0
Fig. 1.6 The variation of atmospheric pressure with altitude
as predicted by the barometric formula.
Fig. 1.7 A typical weather map; this one for the North Atlantic
in Feburary 2012. Regions of high pressure are denoted
H and those of low pressure L. Pressures are in millibars
(1 mbar = 100 Pa).
air is less dense than the same parcel of cool air. As a
parcel rises, it expands without transfer of heat from its
surroundings: it uses energy to push back the surrounding
atmosphere and as a result it cools. Cool air can absorb
lower concentrations of water vapour than warm air, so the
moisture forms clouds. Cloudy skies can therefore be asso-
ciated with rising air and clear skies are often associated
with descending air.
The motion of air in the upper altitudes may lead to an accu-
mulation in some regions and a loss of molecules from other
regions. The former result in the formation of regions of high
pressure (‘highs’ or anticyclones) and the latter result regions
of low pressure (‘lows’, depressions, or cyclones). These
regions are shown as H and L on the weather map in Fig. 1.7.
The lines of constant pressure—differing by 4 mbar (400 Pa,
about 3 Torr)—marked on it are called isobars. The elon-
gated regions of high and low pressure are known, respec-
tively, as ridges and troughs.
9780199608119_C01.indd 26
of the physical properties of a perfect gas. The pointlike
molecules move randomly with a wide range of speeds
and in random directions, both of which change when they
collide with the walls or with other molecules.
The molecular model of gases
We remarked in Foundations (in the section on mat-
ter) that a gas may be pictured as a collection of par-
ticles in ceaseless, random motion (Fig. 1.8). Now we
develop this model of the gaseous state of matter to
see how it accounts for the perfect gas law. One of
the most important functions of physical chemistry is
to convert qualitative notions into quantitative state-
ments that can be tested experimentally by making
measurements and comparing the results with pre-
dictions. Indeed, an important component of science
as a whole is its technique of proposing a qualitative
model and then expressing that model mathemati-
cally. The ‘kinetic model’ (or the ‘kinetic molecular
theory’, KMT) of gases is an excellent example of
this procedure: the model is very simple, and the
quantitative prediction (the perfect gas law) is experi-
mentally verifiable.
The kinetic model of gases is based on three
assumptions:
1. A gas consists of molecules in ceaseless random
motion.
2. The size of the molecules is negligible in the sense
that their diameters are much smaller than the
average distance travelled between collisions.
3. The molecules do not interact, except during
collisions.
The assumption that the molecules do not interact
unless they are in contact implies that the potential
energy of the molecules (their energy due to their
position) is independent of their separation and may
be set equal to zero. The total energy of a sample of
gas is therefore the sum of the kinetic energies (the
9/21/12 4:37 PM
 THE MOLECULAR MODEL OF GASES 27

energy due to motion) of all the molecules present in v1 + v2 + ... + vN

;= Definition Mean speed (1.14)
it. It follows that the faster the molecules travel (and N
hence the greater their kinetic energy), the greater the
For samples consisting of large numbers of molecules,
total energy of the gas.
the mean speed is slightly smaller than the r.m.s.
speed. The precise relation is
1.4 The pressure of a gas according to the 1/ 2
kinetic model ⎛ 8⎞
;= ⎜ ⎟ vrms = 0.921vrms (1.15)
⎝ 3π ⎠
The kinetic model accounts for the steady pressure
exerted by a gas in terms of the collisions the mole- For elementary purposes, and for qualitative argu-
cules make with the walls of the container. Each ments, we don’t need to distinguish between the two
impact gives rise to a brief force on the wall, but as measures of average speed, but for precise work the
billions of collisions take place every second, the distinction is important.
walls experience a virtually constant force, and hence
the gas exerts a steady pressure. On the basis of this Brief illustration 1.4 Root-mean-square values
model, the pressure exerted by a gas of molar mass M Cars pass a point travelling at 45.0 (5), 47.0 (7), 50.0
in a volume V is (9), 53.0 (4), 57.0 (5) km h−1, where the number of cars
is given in parentheses. The r.m.s. speed of the cars is
2
nMvrms Pressure, given by eqn 1.12 in the form
p= according to KMT (1.11)
3V 1/ 2
⎧ 5 × (45.0 km h−1)2 + 7 × (47.0 km h−1)2 ⎫
⎪ ⎪
See Further information 1.1 for a derivation of this ⎨ + 5 × (57.0 km h−1)2 ⎬
#rms =⎪ ⎪
equation. Here vrms is the root-mean-square speed ⎪⎩ 5 + 7 + 5 ⎪⎭
(r.m.s. speed) of the molecules. This quantity is
= 50.2 km h−1
defined as the square root of the mean value of the
squares of the speeds, v, of the molecules. That is, for
a sample consisting of N molecules with speeds v1, Self-test 1.6
v2, . . . , vN, we square each speed, add the squares Calculate the mean speed of the cars (from eqn 1.14).
together, divide by the total number of molecules (to Answer: 50.0 km h−1
get the mean, denoted by 〈. . .〉), and finally take the
square root of the result:
Eqn 1.11 can be rearranged into
Root-mean-
vrms = 〈v2〉1/2 Definition (1.12)
square speed
pV = 13 nMvrms
2
(1.16)
1/ 2
⎛ v2 + v22 + ... + vN
2 ⎞
= ⎜⎜ 1 ⎟⎟ which is starting to resemble the equation pV = nRT.
⎝ N ⎠ This conclusion is a major success of the kinetic
The r.m.s. speed might at first sight seem to be a model, for the model implies an experimentally
rather peculiar measure of the mean speeds of the verified result.
molecules, but its significance becomes clear when
we make use of the fact that the kinetic energy of a 1.5 The average speed of gas molecules
molecule of mass m travelling at a speed v is Ek =
1
mv 2, which implies that the mean kinetic energy We now suppose that the expression for pV derived
2
of a collection of molecules, 〈Ek 〉, is the average of from the kinetic model, eqn 1.16, is indeed the equa-
this quantity, or 12 mvrms
2
. It follows from the relation tion of state of a perfect gas, pV = nRT. That being
1
mv 2
= 〈E 〉, that so, we can equate the expression on the right to nRT,
2 rms k
which gives
1/ 2
⎛ 2〈Ek 〉 ⎞
vrms = ⎜ ⎟ (1.13) 1
3
2
nMvrms = nRT
⎝ m ⎠
The n on each side now cancel to give
Therefore, wherever vrms appears, we can think of it as
a measure of the mean kinetic energy of the molecules
1
3
2
Mvrms = RT
of the gas. The r.m.s. speed is quite close in value The great usefulness of this expression is that we can
to another and more readily visualized measure of rearrange it into a formula for the r.m.s. speed of the
molecular speed, the mean speed, ;, of the molecules: gas molecules at any temperature, first by writing

9780199608119_C01.indd 27 9/21/12 4:37 PM

 28 CHAPTER 1 THE PROPERTIES OF GASES

2
vrms = 3RT/M and then by taking the square root of 1.6 The Maxwell distribution of speeds
both sides:
So far, we have dealt only with the average speed of
1/ 2
⎛ 3RT ⎞ r.m.s. speed molecules in a gas. Not all molecules, however, travel
vrms =⎜ ⎟ of molecules (1.17)
⎝ M ⎠ at the same speed: some move more slowly than the
average (until they collide, and get accelerated to a
Brief illustration 1.5 The r.m.s. speed of high speed, like the impact of a bat on a ball), and
molecules others may briefly move at much higher speeds than
Substitution of the molar mass of O2 (32.0 g mol−1, the average, but be brought to a sudden stop when
corresponding to 3.20 × 10−2 kg mol−1) and a tem- they collide. There is a ceaseless redistribution of
perature corresponding to 25 °C (that is, 298 K) into speeds among molecules as they undergo collisions.
eqn 1.17 gives an r.m.s. speed for these molecules of Each molecule collides about once every nanosecond
⎧
1/ 2 (1 ns = 10−9 s) or so in a gas under normal conditions.
 ⎫⎪
R T
⎪


⎪⎪ 3 × (8.3145 J K −1 mol−1) × (298 K) ⎪⎪ The mathematical expression that tells us the
#rms =⎨ ⎬ = 482 m s−1 probability, P, that the molecules in a sample of gas
⎪ 3.20 × 10−2 kg mol−1 ⎪
⎪  ⎪ have a speed that lies in a particular range at any
⎪⎩ M ⎪⎭
instant is called the distribution of molecular speeds.
(We used 1 J = 1 kg m2 s−2 to cancel units.) The same Thus, the distribution might tell us that at 20 °C
calculation for nitrogen molecules gives 515 m s−1. Both 19 out of 1000 O2 molecules, corresponding to P =
these values are not far off the speed of sound in air 0.019, have a speed in the range between 300 and
(346 m s−1 at 25 °C). That similarity is reasonable, because 310 m s−1, that 21 out of 1000 have a speed in the
sound is a wave of pressure variation transmitted by range 400 to 410 m s−1, corresponding to P = 0.021,
the movement of molecules, so the speed of propaga-
and so on. The precise form of the distribution was
tion of a wave should be approximately the same as the
worked out by James Clerk Maxwell towards the
speed at which molecules can adjust their locations.
end of the nineteenth century, and his expression
is known as the Maxwell distribution of speeds.
Self-test 1.7
According to Maxwell, the probability P(v,v + ∆v)
Calculate the rms speed of H2 molecules at 25 °C. that the molecules have a speed in a narrow range
Answer: 1920 m s−1 between v and v + ∆v (for example, between 300 m
s−1 and 310 m s−1, corresponding to v = 300 m s−1
and ∆v = 10 m s−1) is
The important conclusion to draw from eqn 1.17
is that P(v,v + ∆v) = ρ(v)∆v with
The r.m.s. speed of molecules in a gas is propor- 1/ 2
⎛ M ⎞ 2 − Mv2 / 2RT
tional to the square root of the temperature: vrms ρ(v) = 4π ⎜ ⎟ v e
∝ T 1/2. ⎝ 2πRT ⎠
Because the mean speed is proportional to the r.m.s. Maxwell distribution
(1.18)
of speeds
speed, the same is true of the mean speed too.
Therefore, doubling the thermodynamic tempera- (ρ is the Greek letter rho; for a review of exponential
ture (that is, doubling the temperature on the Kelvin functions, see The chemist’s toolkit 1.2.) This for-
scale) increases the mean and the r.m.s. speed of mula was used to calculate the numbers quoted
molecules by a factor of 21/2 = 1.414. . . . above. Its origin can be traced to the Boltzmann
distribution (Foundations 0.11), because the fraction
Brief illustration 1.6 Molecular speeds
of molecules that have a particular speed v have a
Cooling a sample of air from 25 °C (298 K) to 0 °C
kinetic energy Ek = 1/2mv2 (there is no contribution
(273 K) reduces the original r.m.s. speed of the mole-
from potential energy) and according to Boltzmann,
cules by a factor of
that fraction is proportional to e−Ek /kT, which becomes
∝T 1/ 2
first e−mv /2kT and then e−Mv /2RT when m and k are
2 2
#
#rms(273 K)  ⎛ 273 K ⎞
rms 1/ 2
= ⎜⎜ ⎟⎟ = 0.957 both multiplied by Avogadro’s constant, NA:
#rms(298 K) ⎝ 298 K ⎠

So, on a cold day, the average speed of air molecules mN A =M

A =R
E / kT
(which is changed by the same factor) is about 4 per
k kN
− mv2 / 2kT − Mv2 / 2RT
cent less than on a warm day. ρ(v) ∝ e = e

9780199608119_C01.indd 28 9/21/12 4:37 PM


The chemist’s toolkit 1.2 Exponential and
Gaussian functions
In preparation for their occurrence throughout the text
(and throughout physical chemistry), it will be useful to know
the shapes of the functions e−ax and e−ax (Sketch 1.3).
2
An exponential function, a function of the form e−ax,
starts off at 1 when x = 0 and decays toward zero,
which it reaches as x approaches infinity. This function
approaches zero more rapidly when a is large than when
it is small.
A Gaussian function, a function of the form e−ax , also
2
starts off at 1 when x = 0 and decays to zero as x increases,
however, its decay is initially slower but then plunges
down to zero more rapidly than an exponential function.
The illustration also shows the behaviour of the two
functions for negative values of x. The exponential func-
tion e−ax rises rapidly to infinity as x → −∞, but the
Gaussian function is symmetrical about x = 0 and traces
out a bell-shaped curve that falls to zero as x → ±∞.
1
10
9
8
7
6 • The opposite is true when the temperature, T, is
5 0
0 1 x 2
4 small, so the exponential factor falls towards zero
3 e–x
2 e–x 2
1 of the molecules having high speeds than at low
0 temperatures.
–5 –4 –3 –2 –1 0 x 1 2 3
Sketch 1.3 The exponential function, e−x, and the bell-
shaped Gaussian function, e−x . Note that both are equal
2
to 1 at x = 0 but the exponential function rises to infinity
as x → −∞. The enlargement in the right shows the
behaviour for x > 0 in more detail.
Note that the function ρ(v) is a ‘probability density’,
not the probability itself, in the sense that the actual
probability of molecules having a speed in the range
v to v + ∆v is given by the product of ρ(v) and the
width of the range. (This relation is like the mass of a
volume of material being given by the product of its
mass density and the size of the region, the volume.)
We shall encounter several other examples of prob-
ability densities elsewhere in the text.
Although eqn 1.18 looks complicated, its features
can be picked out quite readily. One of the skills to
develop in physical chemistry is the ability to inter-
pret the message carried by equations. Equations
9780199608119_C01.indd 29
THE MOLECULAR MODEL OF GASES 29
convey information, and it is far more important
to be able to read that information than simply to
remember the equation. Let’s read the information in
eqn 1.18 piece by piece.
• Because P(v,v + ∆v) is proportional to the range of
speeds ∆v, we see that the probability of the speed
lying in the range ∆v increases in proportion to the
width of the range. If at a given speed we double
the range of interest (but still keep it narrow), then
the probability of molecules having speeds lying
in that range doubles too.
• Equation 1.18 includes a decaying exponential func-
tion, the term 4π ( 2πMRT )1/ 2 v2e−Mv /2RT. Its presence
2
implies that the probability that molecules will be
found with very high speeds is very small because
e−ax becomes very small when ax2 is large.
2
• The factor M/2RT multiplying v2 in the exponent,
4π ( 2πMRT )1/ 2 v2e−Mv /2RT, is large when the molar
2
mass, M, is large, so the exponential factor goes
most rapidly towards zero when M is large. That
tells us that heavy molecules are unlikely to be
found with very high speeds.
high: then the factor M/2RT in the exponent is
3
relatively slowly as v increases. This tells us that at
high temperatures, there is a greater probability
4 5
• A factor v 2 in 4π ( 2πMRT )1/ 2 v2e−Mv /2RT multiplies
2
the exponential. This factor, which comes from
taking into account that high velocities can be
achieved in more ways than low velocities, goes to
zero as v goes to zero, so the probability of finding
molecules with very low speeds will also be very
small.
• The remaining factors (the term 4π(M/2πRT)1/2v 2
e−Mv /2RT) simply ensure that when we add together
2
the probabilities over the entire range of speeds
from zero to infinity, then we get 1.
Figure 1.9 is a graph of the Maxwell distribution,
and shows these features pictorially for the same gas
(the same value of M) but different temperatures.
As we deduced from the equation, we see that there
is only a small probability that molecules in the
sample have very low or very high speeds. However,
the probability of molecules having very high speeds
increases sharply as the temperature is raised, as the
tail of the distribution reaches up to higher speeds.
9/21/12 4:37 PM
 30 CHAPTER 1 THE PROPERTIES OF GASES
Low
temperature
Number of molecules
High
temperature
Speed
Fig. 1.9 The Maxwell distribution of speeds and its variation
with the temperature. Note the broadening of the distribution
and the shift of the r.m.s. speed to higher values as the tem-
perature is increased.
Heavy
molecules
Number of molecules
Light
molecules
Speed
Fig. 1.10 The Maxwell distribution of speeds also depends
on the molar mass of the molecules. Molecules of low molar
mass have a broad spread of speeds, and a significant frac-
tion may be found travelling much faster than the r.m.s.
speed. The distribution is much narrower for heavy mole-
cules, and most of them travel with speeds close to the
r.m.s. value.
This feature plays an important role in the rates of
gas-phase chemical reactions, for (as we shall see in
Section 10.10), the rate of a reaction in the gas phase
depends on the energy with which two molecules
crash together, which in turn depends on their
speeds.
Figure 1.10 is a plot of the Maxwell distribution
for molecules with different molar masses at the
same temperature. As can be seen, not only do heavy
molecules have lower average speeds than light mole-
cules at a given temperature, but they also have a
significantly narrower spread of speeds. That narrow
9780199608119_C01.indd 30
spread means that most molecules will be found
with speeds close to the average. In contrast, light
molecules (such as H2) have high average speeds and
a wide spread of speeds: many molecules will be
found travelling either much more slowly or much
more quickly than the average. This feature plays
an important role in determining the composition
of planetary atmospheres, because it means that a
significant fraction of light molecules travel at suffi-
ciently high speeds to escape from the planet’s
gravitational attraction. The ability of light mole-
cules to escape is one reason why hydrogen (molar
mass 2.02 g mol−1) and helium (4.00 g mol−1) are
very rare in the Earth’s atmosphere.
The Maxwell distribution has been verified experi-
mentally by passing a beam of molecules from an
oven at a given temperature through a series of coax-
ial slotted disks. The speed of rotation of the disks
brings the slots into line for molecules travelling at a
particular speed, so only molecules with that speed
pass through and are detected. By varying the rota-
tion speed, the shape of the speed distribution can
be explored and is found to match that predicted by
eqn 1.18. Although the selector measures the distri-
bution of speeds in one dimension, collisions within
the beam ensure that that distribution matches the
distribution in three dimensions and that the experi-
ment monitors the Maxwell distribution.
1.7 Diffusion and effusion
Diffusion is the process by which the molecules of
different substances mingle with each other. The
atoms of two solids diffuse into each other when the
two solids are in contact, but the process is very slow.
The diffusion of a solute through a liquid solvent is
much faster but mixing needs to be encouraged by
stirring or shaking (the process is then no longer pure
diffusion). The diffusion of one gas into another is
much faster. It accounts for the largely uniform com-
position of the atmosphere, for if a gas is produced
by a localized source (such as carbon dioxide from
the respiration of animals, oxygen from photosyn-
thesis by green plants, and pollutants from vehicles
and industrial sources), then the molecules of gas
will diffuse from the source and in due course be dis-
tributed throughout the atmosphere. In practice, the
process of mixing is accelerated by the bulk motion
we experience as winds. The process of effusion is the
escape of a gas through a small hole, as in a puncture
in an inflated balloon or tyre (Fig. 1.11).
The rates of diffusion and effusion of gases increase
with increasing temperature, for both processes
9/21/12 4:37 PM

(a)
(b)
Fig. 1.11 (a) Diffusion is the spreading of the molecules of
one substance into the region initially occupied by another
species. Note that molecules of both substances move, and
each substance diffuses into the other. (b) Effusion is the
escape of molecules through a small hole in a confining wall.
depend on the motion of molecules, and molecular
speeds increase with temperature. The rates also
decrease with increasing molar mass, for molecular
speeds decrease with increasing molar mass. The
dependence on molar mass, however, is simple only
in the case of effusion. In effusion, only a single
substance is in motion, not the two or more inter-
mingling gases involved in diffusion.
The experimental observations on the dependence
of the rate of effusion of a gas on its molar mass are
summarized by Graham’s law of effusion, proposed
by Thomas Graham in 1833:
At a given pressure and temperature, the rate of
effusion of a gas is inversely proportional to the
square root of its molar mass:
1 comparison of the rate of effusion of a gas or vapour
Rate of effusion ∝ Graham’s law (1.19)
M1/ 2
Rate in this context means the number (or amount
of molecules, in moles) of molecules that escape per
second.
Brief illustration 1.7 Graham’s law
The rates (in terms of amounts of molecules) at which
hydrogen (molar mass 2.02 g mol−1) and carbon diox-
ide (44.01 g mol−1) effuse under the same conditions
of pressure and temperature are in the ratio
9780199608119_C01.indd 31
THE MOLECULAR MODEL OF GASES 31
Rate ∝1/M 1/ 2
Rate of effusion of H2  ⎛ M (CO ) ⎞
1/ 2
= ⎜⎜ 2
⎟⎟
Rate of effusion of C O2 ⎝ M (H2) ⎠
1/ 2
⎛ 44
4.01 g mol−1 ⎞
=⎜ ⎟
⎜ 2.016 g mol−1 ⎟
⎝ ⎠
1/2
⎛ 44.01⎞
=⎜ = 4.672
⎝ 2.016 ⎟⎠
The mass of carbon dioxide that escapes in a given
interval is greater than the mass of hydrogen, because
although nearly 5 times as many hydrogen molecules
escape, each carbon dioxide molecule has over 20
times the mass of a molecule of hydrogen.
Self-test 1.8
Suppose 5.0 g of argon escapes by effusion; what
mass of nitrogen would escape under the same
conditions?
Answer: 4.2 g
Note on good practice Always make it clear what
terms mean: in this instance ‘rate’ alone is ambiguous;
you need to specify that it is the rate in terms of amount of
molecules.
The high rate of effusion of hydrogen and helium
is one reason why these two gases leak from contain-
ers and through rubber diaphragms so readily. The
different rates of effusion through a porous barrier
are employed in the separation of uranium-235 from
the more abundant and less useful uranium-238 in
the processing of nuclear fuel. The process depends
on the formation of uranium hexafluoride, a volatile
solid. However, because the ratio of the molar masses
of 238UF6 and 235UF6 is only 1.008, the ratio of the
rates of effusion is only (1.008)1/2 = 1.004. Thousands
of successive effusion stages are therefore required to
achieve a significant separation. The rate of effusion
of gases was once used to determine molar mass by
with that of a gas of known molar mass. However,
there are now much more precise methods available,
such as mass spectrometry.
Graham’s law is explained by noting that the
r.m.s. speed of molecules in a gas is inversely propor-
tional to the square root of their molar mass (eqn
1.17). Because the rate of effusion through a hole in
a container is proportional to the rate at which mole-
cules pass through the hole, it follows that the rate
should be inversely proportional to M1/2, which is in
accord with Graham’s law.
9/21/12 4:37 PM
 32 CHAPTER 1 THE PROPERTIES OF GASES

1.8 Molecular collisions Diameter, d

The average distance that a molecule travels between

collisions is called its mean free path, λ (lambda).
The mean free path in a liquid is less than the diam-
eter of the molecules, because a molecule in a liquid Radius, d
meets a neighbour even if it moves only a fraction of
a diameter. However, in gases, the mean free paths of
molecules can be several hundred molecular diam-
eters. If we think of a molecule as the size of a tennis Fig. 1.12 To calculate features of a perfect gas that are
ball, then the mean free path in a typical gas would related to collisions, a point is regarded as being surrounded
be about the length of a tennis court. by a sphere of diameter d. A molecule will hit another mole-
The collision frequency, z, is the average rate of cule if the centre of the former lies within a circle of radius d.
The collision cross-section is the target area, pd 2.
collisions made by one molecule. Specifically, z is the
average number of collisions one molecule makes in
a given time interval divided by the length of the
interval. It follows that the inverse of the collision
Table 1.4
frequency, 1/z, is the time of flight, the average time
Collision cross-sections of atoms and molecules
that a molecule spends in flight between two colli-
sions (for instance, if there are 10 collisions per sec- Species s/nm2
ond, so the collision frequency is 10 s−1, then the
average time between collisions is 1/10 of a second Argon, Ar 0.36
and the time of flight is 1/10 s). As we shall see, the Benzene, C6H6 0.88
collision frequency in a typical gas is about 109 s−1 Carbon dioxide, CO2 0.52
at 1 atm and room temperature, so the time of flight Chlorine, Cl2 0.93
in a gas is typically 1 ns. Ethene, C2H4 0.64
Because speed is distance travelled divided by the Helium, He 0.21
time taken for the journey, the r.m.s. speed vrms, Hydrogen, H2 0.27
which we can loosely think of as the average speed, is Methane, CH4 0.46
Nitrogen, N2 0.43
the average length of the flight of a molecule between
Oxygen, O2 0.40
collisions (that is, the mean free path, λ) divided by
Sulfur dioxide, SO2 0.58
the time of flight (1/z). It follows that the mean free
path and the collision frequency are related by 1 nm2 = 10−18 m2.


l

distance between collisions mean free path
vrms = =
time between collisions time of flight
 another, is therefore the area of a circle of radius d,
1/ z so σ = πd2. When this quantity is built into the kinetic
λ model, it is possible to show2 that
= = λz (1.20)
1/z kT
λ= Mean free path (1.21)
σp
Therefore, if we can calculate either λ or z, then we
can find the other from this equation and the value of where k is Boltzmann’s constant. Table 1.4 lists the
vrms given in eqn 1.17. collision cross-sections of some common atoms and
To find expressions for λ and z we need a slightly molecules. Similarly, by combining this expression
more elaborate version of the kinetic model. The with that in eqn 1.20,
basic kinetic model supposes that the molecules are
z = #rms / l
effectively point-like; however, to obtain collisions,  σ vrmsp
we need to assume that two ‘points’ score a hit when- z = Collision frequency (1.22)
kT
ever they come within a certain range d of each other,
where d can be thought of as the diameter of the
molecules (Fig. 1.12). The collision cross-section, σ
(sigma), the target area presented by one molecule to 2
See, for instance, our Physical Chemistry (2010).

9780199608119_C01.indd 32 9/21/12 4:37 PM

 REAL GASES 33

Brief illustration 1.8 Mean free path time to travel to its neighbour in a denser, higher-
From the information in Table 1.4 we can calculate pressure gas. For example, although the collision fre-
that the mean free path of O2 molecules in a sample of quency for an O2 molecule in oxygen gas at SATP is
oxygen at SATP (25 °C, 1 bar) is 6.2 × 109 s−1, at 2.0 bar and the same temperature the
k
collision frequency is doubled, to 1.2 × 1010 s−1.

 
T

(1.381× 10−23 J K −1) × (298 K) • Because eqn 1.22 shows that z ∝ vrms, and we
l=
.40 × 10
(0 − 18
m2) × (1 × 10

5
Pa)
 know that vrms ∝ 1/M1/2, heavy molecules have
s p lower collision frequencies than light molecules,
providing their collision cross-sections are the
(1.381× 10−233) × (298) J
= same.
(0.40 × 10−18) × (1× 105) Pa m2
Heavy molecules travel more slowly on average than
1 J = 1 Pa m−3 1 nm = 10−9 m
  light molecules do (at the same temperature), so they
= 1.0 × 10−7 m = 100 nm collide with other molecules less frequently.
Under the same conditions, the collision frequency is
6.2 × 109 s−1, so each molecule makes 6.2 billion colli-
sions each second. Real gases
So far, everything we have said applies to perfect
Self-test 1.9 gases, in which the average separation of the mole-
Use eqns 1.17 and 1.22, together with the information cules is so great that they move independently of one
in Table 1.4, to determine the collision frequency for another. In terms of the quantities introduced in the
Cl2 molecules in a sample of chlorine gas under the previous section, a perfect gas is a gas for which the
same conditions. mean free path, λ, of the molecules in the sample is
Answer: 7.3 × 109 s−1 much greater than d, the separation at which they are
regarded as being in contact:
Condition for perfect-gas behaviour: λ >> d
Once again, we should interpret the essence of
eqns 1.21 and 1.22 rather than trying to remember As a result of this large average separation, a perfect
them. gas is a gas in which the only contribution to the
energy comes from the kinetic energy of the motion
• Because λ ∝ 1/p, the mean free path decreases as
of the molecules and there is no contribution to the
the pressure increases.
total energy from the potential energy arising from
This decrease is a result of the increase in the number the interaction of the molecules with one another.
of molecules present in a given volume as the pres- However, in fact all molecules do interact with one
sure is increased, so each molecule travels a shorter another provided they are close enough together, so
distance before it collides with a neighbour. For the ‘kinetic energy only’ model is only an approxima-
example, the mean free path of an O2 molecule tion. Nevertheless, under most conditions the criter-
decreases from 73 nm to 36 nm when the pressure is ion λ >> d (the separation of the molecules is much
increased from 1.0 bar to 2.0 bar at 25 °C. greater than their diameters; think tennis court com-
pared with tennis ball) is satisfied and the gas can be
• Because λ ∝ 1/σ, the mean free path is shorter for
treated as though it is perfect.
molecules with large collision cross-sections.
For instance, the collision cross-section of a benzene
1.9 Molecular interactions
molecule (0.88 nm2) is about four times greater than
that of a helium atom (0.21 nm2), and at the same There are two types of contribution to the potential
pressure and temperature its mean free path is four energy of interaction between molecules. At rela-
times shorter. tively large separations (a few molecular diameters),
molecules attract each other. This attraction is
• Because z ∝ p, the collision frequency increases
responsible for the condensation of gases into liquids
with the pressure of the gas.
at low temperatures. At low enough temperatures
This dependence follows from the fact that, provided the molecules of a gas have insufficient kinetic energy
the temperature is the same, each molecule takes less to escape from each other’s attraction and they stick

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 34 CHAPTER 1 THE PROPERTIES OF GASES

140
50 °C
120
40 °C
0 100
Potential energy

Pressure, p/atm
Critical point
80 F 31.04 °C (Tc)
*

60 20 °C
E D C
40 B
A
Repulsions dominant 20
0 °C
Attractions dominant
0
Separation 0 0.2 0.4 0.6
Molar volume, Vm/(dm3 mol–1)
Fig. 1.13 The variation of the potential energy of two mole-
cules with their separation. High positive potential energy Fig. 1.14 The experimental isotherms of carbon dioxide at
(at very small separations) indicates that the interactions several temperatures. The critical isotherm is at 31.04 °C.
between them are strongly repulsive at these distances.
At intermediate separations, where the potential energy is
negative, the attractive interactions dominate. At large separ-
ations (on the right) the potential energy is zero and there is striking differences between the two at temperatures
no interaction between the molecules.
below about 50 °C and at pressures above about 1 bar.

together. Second, although molecules attract each
other when they are a few diameters apart, as soon as
they come into contact they repel each other. This
repulsion is responsible for the fact that liquids and
solids have a definite bulk and do not collapse to an
infinitesimal point.
Molecular interactions—the attractions and re-
pulsions between molecules—give rise to a potential
energy that contributes to the total energy of a gas.
Because attractions correspond to a lowering of total
energy as molecules get closer together, they make a
negative contribution to the potential energy. On the
other hand, repulsions make a positive contribution
to the total energy as the molecules squash together.
Figure 1.13 illustrates the general form of the vari-
ation of the intermolecular potential energy. At large
separations, the energy-lowering interactions are
dominant, but at short distances the energy-raising
repulsions dominate.
Molecular interactions affect the bulk properties
of a gas and, in particular, their equations of state.
For example, the isotherms of real gases have shapes
that differ from those implied by Boyle’s law, particu-
larly at high pressures and low temperatures when
the interactions are most important. Figure 1.14
shows a set of experimental isotherms for carbon
dioxide. They should be compared with the perfect-
gas isotherms shown in Fig. 1.1. Although the experi-
mental isotherms resemble the perfect-gas isotherms
at high temperatures (and at low pressures, off the
scale on the right of the graph), there are very
1.10 The critical temperature
To understand the significance of the isotherms in
Fig. 1.14, let’s begin with the isotherm at 20 °C and
follow the changes from A to F:
• At point A the sample of carbon dioxide is a gas.
• As the sample is compressed to B by pressing in
a piston, the pressure increases broadly in agree-
ment with Boyle’s law.
• The increase continues until the sample reaches
point C.
• Beyond this point, we find that the piston can be
pushed in without any further increase in pres-
sure, through D to E.
• The reduction in volume from E to F requires a
very large increase in pressure.
This variation of pressure with volume is exactly
what we expect if the gas at C condenses to a com-
pact liquid at E. Indeed, if we could observe the
sample we would see that:
• At C the liquid begins to condense to a liquid.
• The condensation is complete when the piston is
pushed in to E.
• At E, the piston is resting on the surface of the
liquid.
• The subsequent reduction in volume, from E to F,
corresponds to the very high pressure needed to
compress a liquid into a smaller volume.

9780199608119_C01.indd 34 9/21/12 4:37 PM

 REAL GASES 35

In terms of intermolecular interactions:

Table 1.5
• The step from C to E corresponds to the molecules The critical temperatures of gases
being so close on average that they attract each
other and cohere into a liquid. Critical temperature/°C

• The step from E to F represents the effect of trying Noble gases

to force the molecules even closer together when
Helium, He −268 (5.2 K)
they are already in contact, and hence trying
Neon, Ne −229
to overcome the strong repulsive interactions Argon, Ar −123
between them. Krypton, Kr −64
If we could look inside the container at point D, Xenon, Xe 17
we would see a liquid separated from the remaining
Halogens
gas by a sharp surface (Fig. 1.15). At a slightly higher
temperature (at 30 °C, for instance), a liquid forms, Chlorine, Cl2 144
but a higher pressure is needed to produce it. It might Bromine, Br2 311
be difficult to make out the surface because the
Small inorganic molecules
remaining gas is at such a high pressure that its
density is similar to that of the liquid. At the special Ammonia, NH3 132
Carbon dioxide, CO2 31
temperature of 31.04 °C (304.19 K) the gaseous state
Hydrogen, H2 −240
of carbon dioxide appears to transform continuously
Nitrogen, N2 −147
into the condensed state and at no stage is there a
Oxygen, O2 −118
visible surface between the two states of matter.
Water, H2O 374
At this temperature (which is 304.19 K for carbon
dioxide but varies from substance to substance), Organic compounds
called the critical temperature, Tc, and at all higher
Benzene, C6H6 289
temperatures, a single form of matter fills the con-
Methane, CH4 −83
tainer at all stages of the compression and there is Tetrachloromethane, CCl4 283
no separation of a liquid from the gas. We have to
conclude that a gas cannot be condensed to a liquid
by the application of pressure unless the temperature
is below the critical temperature.
at each end of the horizontal part of the isotherm
Figure 1.14 also shows that in the critical isotherm,
have merged to a single point, the critical point of the
the isotherm at the critical temperature, the volumes
gas. The pressure and molar volume at the critical
point are called the critical pressure, pc, and critical
molar volume, Vc, of the substance. Collectively, pc,
Vc, and Tc are the critical constants of a substance.
Table 1.5 lists the critical temperatures of some com-
T < Tc T ≈ Tc T > Tc mon gases. The data there imply, for example, that
liquid nitrogen cannot be formed by the application
of pressure unless the temperature is below 126 K
(−147 °C). The critical temperature is sometimes used
to distinguish the terms ‘vapour’ and ‘gas’:
a vapour is the gaseous phase of a substance below
Increasing temperature its critical temperature (and which can therefore
be liquefied by compression alone)
Fig. 1.15 When a liquid is heated in a sealed container, the a gas is the gaseous phase of a substance above its
density of the vapour phase increases and that of the liquid
phase decreases, as depicted here by the changing density
critical temperature (and which cannot therefore
of shading. There comes a stage at which the two densities be liquefied by compression alone)
are equal and the interface between the two fluids disap-
pears. This disappearance occurs at the critical temperature.
Oxygen at room temperature is therefore a true gas;
The container needs to be strong: the critical temperature of the gaseous phase of water at room temperature is a
water is at 373 °C and the vapour pressure is then 218 atm. vapour.

9780199608119_C01.indd 35 9/21/12 4:37 PM

 36 CHAPTER 1 THE PROPERTIES OF GASES
The dense fluid obtained by compressing a gas
when its temperature is higher than its critical tem-
perature is not a true liquid, but it behaves like a
liquid in many respects: it has a density similar to
that of a liquid, for instance, and can act as a solvent.
However, despite its density, the fluid is not strictly a
liquid because it never possesses a surface that separ-
ates it from a vapour phase. Nor is it much like a
gas, because it is so dense. It is an example of a super-
critical fluid. Supercritical fluids are currently being
used as solvents. For example, supercritical carbon
dioxide is used to extract caffeine in the manufacture
of decaffeinated coffee where, unlike organic solvents,
it does not result in the formation of an unpleasant
and possibly toxic residue. Supercritical fluids are
also currently of great interest in industrial processes,
for they can be used instead of chlorofluorocarbons
(CFCs) and hence avoid the environmental damage
that CFCs are known to cause. Because supercritical
carbon dioxide is obtained either from the atmos-
phere or from renewable organic sources (by fermen-
tation) its use does not increase the net load of
atmospheric carbon dioxide.
1.11 The compression factor
A useful quantity for discussing the properties of real
gases is the compression factor, Z, which is the ratio
of the actual experimentally determined molar vol-
ume of a gas, Vm, to the molar volume of a perfect
perfect
gas, V m , under the same conditions:
Vm
Z= perfect
Definition Compression factor
Vm
For a perfect gas, Vm = V m perfect
, so Z = 1 and devi-
ations of Z from 1 are a measure of how far a real gas
departs from behaving perfectly. The molar volume
of a perfect gas is RT/p (recall eqn 1.6b), so we can
rewrite the definition of Z as
V perfect =RT / p
m  Vm pVm
Z = = (1.23b)
RT /p RT
When Z is measured for real gases, it is found to
vary with pressure, as shown in Fig. 1.16. At low
pressures, some gases (methane, ethane, and ammo-
nia, for instance) have Z < 1. That is, their molar
volumes are smaller than that of a perfect gas, sug-
gesting that the molecules are pulled together slightly.
We can conclude that for these molecules and these
conditions, the attractive interactions are dominant.
The compression factor rises above 1 at high pres-
sures, whatever the identity of the gas, and for some
9780199608119_C01.indd 36
2
Compression factor, Z
H2
1
Perfect gas
CH4
C2H4
NH3
0
0 200 400 600 800
Pressure, p/atm
Fig. 1.16 The variation of the compression factor, Z, with
pressure for several gases at 0 °C. A perfect gas has Z = 1 at
all pressures. Of the gases shown, hydrogen shows positive
deviations at all pressures (at this temperature); all the other
gases show negative deviations initially but positive devi-
ations at high pressures. The negative deviations are a result
of the attractive interactions between molecules and the
positive deviations are a result of the repulsive interactions.
gases (hydrogen in the illustration) Z > 1 at all pres-
sures. The type of behaviour exhibited depends on
the temperature. The observation that Z > 1 tells us
that the molar volume of the gas is now greater than
that expected for a perfect gas of the same tempera-
ture and pressure, so the molecules are pushed apart
slightly. This behaviour indicates that the repulsive
forces are dominant. For hydrogen, the attractive
interactions are so weak that the repulsive interac-
tions dominate even at low pressures.
(1.23a)
1.12 The virial equation of state
We can use the deviation of Z from its ‘perfect’ value
of 1 to construct an empirical (observation based)
equation of state. To do so we suppose that, for real
gases, the relation Z = 1 is only the first term of a
lengthier expression and write instead
B C
Z = 1+ + 2 + (1.24a)
Vm V m
The coefficients B, C, . . . are called virial coefficients;
B is the second virial coefficient, C, the third, and
so on; the unwritten A = 1 is the first. The word
‘virial’ comes from the Latin word for force, and it
reflects the fact that intermolecular forces are now
significant. The virial coefficients, which are also
denoted B2, B3, etc. in place of B, C, etc., vary from
gas to gas and depend on the temperature. This tech-
nique, of taking a limiting expression (in this case,
Z = 1, which applies to gases at very large molar
9/21/12 4:37 PM
 REAL GASES 37

volumes) and supposing that it is the first term of a ⎛ pV ⎞

B = ⎜ m − 1⎟Vm
more complicated expression, is quite common in ⎝ RT ⎠
physical chemistry. The limiting expression is the The value of the second virial coefficient at this tem-
first approximation to the true expression, whatever perature is therefore
that may be, and the additional terms progressively
⎛ 36.2 bar 1.00 dm3 mol−1 ⎞
take into account the secondary effects that the limit- ⎜

 ⎟
⎜ (36.2 × 10 Pa) × (1.00 × 10−3 m3 mol−1) ⎟
5
ing expression ignores. B=⎜ − 1⎟
⎝ (8.3145 J K −1 mol−1) × (473 K) ⎠
The most important additional term on the right
in eqn 1.24a is the one proportional to B (because × 1.00 × 10−3 m3 mol−1
under most conditions C/V m 2
<< B/Vm and C/V m 2
can = −79.5 × 10−6 m3 mol−1 = −79.5 cm3 mol−1
be neglected). In that case
Self-test 1.10
B
Z ≈ 1+ (1.24b) The second virial coefficient for NH3 is −45.6 cm3
Vm
mol−1 at a temperature of 573 K. Determine the pres-
From the graphs in Fig. 1.16, it follows that, for the sure at which the molar volume is 1.00 dm3 mol−1 at
temperature to which the data apply, B must be this temperature.
positive for hydrogen (so that Z > 1) but negative Answer: 45.6 bar
for methane, ethane, and ammonia (so that for them
Z < 1). However, in all cases Z rises again as the gas
is compressed further (corresponding to small values 1.13 The van der Waals equation of state
of Vm and high pressures in Fig. 1.16), indicating that Although it is the most reliable equation of state,
2
C/V m is positive. The values of the virial coefficients the virial equation does not give us much immediate
for many gases are known from measurements of Z insight into the behaviour of gases and their con-
over a range of molar volumes and using mathemat- densation to liquids. The van der Waals equation,
ical software to fit the data to eqn 1.24a by varying which was proposed in 1873 by the Dutch physicist
the coefficients until a good match is obtained. Johannes van der Waals, is only an approximate
To convert eqn 1.24a into an equation of state, we equation of state but it has the advantage of showing
combine it with eqn 1.23b (Z = pVm /RT), which gives how the intermolecular interactions contribute to
pVm B C the deviations of a gas from the perfect gas law. We
= 1+ + 2 + ... can view the van der Waals equation as another
RT Vm V m
example of taking a soundly based qualitative idea
Now multiply both sides by RT/Vm and obtain and building up a mathematical expression that can
be tested quantitatively.
RT ⎛ B C ⎞
p= ⎜⎜1 + + 2 + ...⎟⎟ The repulsive interaction between two molecules
Vm ⎝ Vm V m ⎠ implies that they cannot come closer than a certain
Next, replace Vm by V/n throughout to get p as a distance. Therefore, instead of being free to travel
function of n, V, and T: anywhere in a volume V, the actual volume in which
the molecules can travel is reduced to an extent pro-
nRT ⎛ nB n2C ...⎞ Virial equation
p= ⎜⎜1 + + 2 + ⎟⎟ (1.25) portional to the number of molecules present and
of state
V ⎝ V V ⎠ the volume they each exclude (Fig. 1.17). We can
Equation 1.25 is the virial equation of state. When
the molar volume is very large, the terms B/Vm and
2
C/V m are both very small, and only the 1 inside the
parentheses survives. In this limit, the virial equation r
2r
of state approaches that of a perfect gas.

Brief illustration 1.9 The virial equation of

Excluded volume
state
3 −1
The molar volume of NH3 is 1.00 dm mol at 36.2 bar Fig. 1.17 When two molecules, each of radius r and volume
and 473 K. Assuming that under these conditions the Vmol = 43 pr 3 approach each other, the centre of one of them
virial equation of state may be written as p = (RT/Vm ) × cannot penetrate into a sphere of radius 2r and therefore
(1 − B/Vm), so volume 8Vmol surrounding the other molecule.

9780199608119_C01.indd 37 9/21/12 4:37 PM

 38 CHAPTER 1 THE PROPERTIES OF GASES

therefore model the effect of the repulsive, volume- 2

⎛ n⎞
excluding forces by changing V in the perfect gas Reduction in pressure = a × ⎜ ⎟
⎝V ⎠
equation to V − nb, where b is the proportionality
constant between the reduction in volume and the It follows that the equation of state allowing for both
amount of molecules present in the container (see the repulsions and attractions is
following Derivation). nRT ⎛ n⎞
2
van der Waals
p= −a⎜ ⎟ equation of state (1.26a)
V − nb ⎝V ⎠

Derivation 1.1 This expression is the van der Waals equation of

state. To show its resemblance to the perfect gas
The molar volume of a gas described by the van der
equation pV = nRT, eqn 1.26a is sometimes rear-
Waals equation
ranged by bringing the term in a to the left, to give
The volume of a sphere of radius R is 43 pR 3. Figure 1.17 p + an2/V 2, and then multiplying both sides by V − nb:
shows that the closest distance of two hard-sphere mole-
cules of radius r, and volume Vmolecule = 43 pr 3, is 2r. Therefore, ⎛ an2 ⎞
⎜⎜ p + 2 ⎟⎟ (V − nb) = nRT (1.26b)
the excluded volume is 43 p(2r)3 = 8( 43 pr 3), or 8Vmolecule. The
⎝ V ⎠
volume excluded per molecule is one-half this volume, or
4Vmolecule, so b ≈ 4VmoleculeNA. We have built the van der Waals equation by using
physical arguments about the volumes of molecules
and the effects of forces between them. It can be
derived in other ways, but the present method has the
So far, the perfect gas equation of state changes advantage of showing how to derive the form of an
from p = nRT/V to equation out of general ideas. The derivation also
nRT has the advantage of keeping imprecise the signifi-
p= cance of the van der Waals parameters, the constants
V − nb
a and b: they are much better regarded as empirical
This equation of state—it is not yet the full van der parameters than as precisely defined molecular prop-
Waals equation—should describe a gas in which erties. The van der Waals parameters depend on the
repulsions are important. Note that when the pres- gas, but are taken as independent of temperature
sure is low, the volume is large compared with the (Table 1.6). It follows from the way we have con-
volume excluded by the molecules (which we write structed the equation that a (the parameter repre-
V >> nb). The nb can then be ignored in the denom- senting the role of attractions) can be expected to be
inator and the equation reduces to the perfect gas large when the molecules attract each other strongly,
equation of state. It is always a good plan to verify whereas b (the parameter representing the role of
that an equation reduces to a known form when a
plausible physical approximation is made.
The effect of the attractive interactions between
molecules is to reduce the pressure that the gas exerts. Table 1.6
We can model the effect by supposing that the attrac- van der Waals parameters of gases
tion experienced by a given molecule is proportional
Substance a/(102 kPa b/(10−2
to the concentration, n/V, of molecules in the con-
dm6 mol−2) dm3 mol−1)
tainer. Because the attractions slow the molecules
down, the molecules strike the walls less frequently Air 1.4 0.039
and strike it with a weaker impact. (This slowing Ammonia, NH3 4.114 3.71
does not mean that the gas is cooler close to the walls: Argon, Ar 1.320 3.20
the simple relation between T and r.m.s. speed in eqn Carbon dioxide, CO2 3.119 4.29
1.17 is valid only in the absence of intermolecular Ethane, C2H6 5.435 6.51
forces.) We can therefore expect the reduction in Ethene, C2H4 4.545 5.82
pressure to be proportional to the square of the Helium, He 0.0337 2.38
molar concentration, one factor of n/V reflecting the Hydrogen, H2 0.2388 2.65
reduction in frequency of collisions and the other Nitrogen, N2 1.347 3.87
factor the reduction in the strength of their impulse. Oxygen, O2 1.359 3.19
If the constant of proportionality is written a, we Xenon, Xe 4.135 5.16
can write

9780199608119_C01.indd 38 9/21/12 4:37 PM

 REAL GASES 39

1.5 1.5

1.5
Reduced pressure, p/pc

Reduced pressure, p/pc

1 1 1

0.5 0.5

0.8

0 0
0.1 1 10 0.1 1 10
Reduced volume, V/Vc Reduced volume, V/Vc

Fig. 1.18 Isotherms calculated by using the van der Waals Fig. 1.19 The unphysical van der Waals loops are eliminated
equation of state. The axes are labelled with the ‘reduced by drawing straight lines that divide the loops into areas
pressure’, p/pc , and ‘reduced volume’, V/Vc , where pc = of equal size. With this procedure, the isotherms strongly
a/27b 2 and Vc = 3b. The individual isotherms are labelled resemble the observed isotherms.
with the ‘reduced temperature’, T/Tc , where Tc = 8a/27Rb.
The isotherm labelled 1 is the critical isotherm (the isotherm
at the critical temperature).
8a a
Vc = 3b, Tc = ,p = (1.27)
27Rb c 27b2
The first of these relations shows that the critical
repulsions) can be expected to be large when the
volume is about three times the volume occupied by
molecules are large.
the molecules themselves.
The reliability of the van der Waals equation can
be judged by comparing the isotherms it predicts,
which are shown in Fig. 1.18, with the experimental
Example 1.3
isotherms already shown in Fig. 1.14. Apart from
the waves below the critical temperature they do re- Estimating the critical constants of a gas
semble experimental isotherms quite well. The waves, Estimate the critical constants of carbon dioxide.
which are called van der Waals loops, are unrealistic
Strategy Treat carbon dioxide as a van der Waals gas and use
because they suggest that under some conditions
eqn 1.27 with values of parameters taken from Table 1.6.
compression results in a decrease of pressure. The Convert the parameters to base units before using them.
loops are therefore trimmed away and replaced by
horizontal lines (Fig. 1.19). The van der Waals param- Answer The van der Waals parameters for CO2 are a = 3.460
eters in Table 1.6 were found by fitting the calculated dm6 bar mol−2 and b = 0.004 267 dm3 mol−1. To convert them
to base units we write
curves to experimental isotherms.
Two important features of the van der Waals (10−1 m)6 105 Pa
 
equation should be noted. First, perfect-gas iso- a = 3.658 dm6 bar mol−2 = 0.3658 m6 Pa mol−2
therms are obtained from the van der Waals equa-
(10−1 m)3
tion at high temperatures and low pressures. To 
b = 0.0429 dm3 mol−1 = 4.29 × 10−5 m3 mol−1
confirm this remark, we need to note that when the
temperature is high, RT may be so large that the first Then, by using eqn 1.27, we predict the values of the critical
term on the right in eqn 1.26a greatly exceeds the constants for CO2 to be
second, so the latter may be ignored. Furthermore, Vc = 3b = 3 × (4.29 × 10−5 m3 mol−1) = 1.29 × 10−4 m3 mol−1,
at low pressures, the molar volume is so large that or 0.129 dm3 mol−1
V − nb can be replaced by V. Hence, under these
8a 8 × (0.3658 m6 Pa mol−2)
conditions (of high temperature and low pressure), Tc = =
27Rb 27 × (8.3145 J K −1 mol−1) × (4.29 × 10−5 m3 mol−1)
eqn 1.26a reduces to p = nRT/V, the perfect gas
equation. Second, and as shown in the following = 304 K, or 31 °C
Derivation, the critical constants are related to the a 0.3658 m6 Pa mol−2
pc = = = 7.36 MPa
van der Waals coefficients as follows: 27b 2
27 × (4.29 × 10−5 m3 mol−1)2

9780199608119_C01.indd 39 9/21/12 4:37 PM

 40 CHAPTER 1 THE PROPERTIES OF GASES

The experimental values are 0.094 dm3 mol−1, 304 K, and

7.375 MPa, respectively. The chemist’s toolkit 1.3 Differentiation
An important result from calculus is that
Self-test 1.11
dx n
= nx n −1
The critical pressure and temperature of CH4 are 46.1 bar dx
and 191 K, respectively. Determine the value of the van der
Thus, if y = mx 2 + b, then, because m and b are both
Waals parameter b.
constants, dy/dx = 2mx. In this instance, we see that the
Answer: 0.0431 dm3 mol−1 slope (which is equal to dy/dx) increases with x (Sketch
1.4). The expression for dx n/dx also applies when n is
negative. So, for instance,
Derivation 1.2
n =−1
d 1 d(1/x ) d(x 1) 1
Relating the critical constants to the van der Waals = = = x −2 = −
parameters dx x dx dx x2

For this derivation we need know some of the rules of calcu- Two very important relations are
lus related to differentiation as summarized in The chemist’s d ax d f ⎛ df x ) ⎞ f (x )
toolkit 1.3. We see from Fig. 1.18 that, for T < Tc, the calcu- e eax e x
=⎜ ⎟e
dx dx ⎝ dx ⎠
lated isotherms oscillate, and each one passes through a
minimum followed by a maximum. These extrema converge Two other fundamental results are
as T → Tc and coincide at T = Tc; at the critical point the curve d 1 b d 1 2b
has a flat inflexion (1). From the properties of curves, we =− =−
dx a bx (a bx )2 dxx (a bx )2
d (a + bx
b )3
know that an inflexion of this type occurs when both the
first and second derivatives are zero. Hence, we can find The ‘second derivative’ of a function d(dy/dx )/dx is
the critical temperature by calculating these derivatives and denoted d2y/dx 2, or equivalently (d2/dx 2)y, and is the
setting them equal to zero. First, we use Vm = V/n to write result of taking the derivative a second time by using the
eqn 1.26a as same rule given above. For instance, because the first
derivative of y = mx 2 + b is 2mx, the second derivative
RT a
p= − of the same function is 2m. For Derivation 1.2 you also
Vm − b V m2 need to know that

d2 1 d ⎧ b ⎫ 2b 2
= ⎨− ⎬=
dx a bx dx ⎩ (a bx ) ⎭ (a bx )3
2 2

The first and second derivatives of p with respect to Vm

(with p playing the role of y in The chemist’s toolkit 1.3, and dy/dx = 0
Vm playing the role of x ) are, respectively:
dy/dx < 0
dp RT 2a d2p 2RT 6a
=− + 3 = − 4 y
dVm (Vm − b)2 V m 2
dV m (Vm − b)3 V m

At the critical point T = Tc, Vm = Vc, and both derivatives are dy/dx > 0
equal to zero: dy/dx = 0

RTc 2a 2RTc 6a
− + =0 − =0
(Vc − b)2 V c3 (Vc − b)3 V c4 x

Solving this pair of equations gives (as you should verify) the
expressions for Vc and Tc in eqn 1.27. When they are inserted
in the van der Waals equation itself, we find the expression
for pc given there too.
1.14 The liquefaction of gases
A gas may be liquefied by cooling it below its boiling
point at the pressure of the experiment. For example,
chlorine at 1 atm can be liquefied by cooling it to
below −34 °C in a bath cooled with dry ice (solid
Sketch 1.4 A function and its slope; the slope at any point
x is given by the derivative of the function at that point.
carbon dioxide). For gases with very low boiling points
(such as oxygen and nitrogen, at −183 °C and −186 °C,
respectively), such a simple technique is not prac-
ticable unless an even colder bath is available.
One alternative and widely used commercial tech-
nique makes use of the forces that act between mole-
cules. We saw earlier that the r.m.s. speed of molecules
in a gas is proportional to the square root of the

9780199608119_C01.indd 40 9/21/12 4:37 PM


temperature (eqn 1.17). It follows that reducing the
r.m.s. speed of the molecules is equivalent to cooling
the gas. If the speed of the molecules can be reduced
to the point that neighbours can capture each other
by their intermolecular attractions, then the cooled
gas will condense to a liquid.
To slow the gas molecules, we make use of an
effect similar to that seen when a ball is thrown into
the air: as it rises it slows in response to the gravita-
tional attraction of the Earth and its kinetic energy
is converted into potential energy. Molecules attract
each other, as we have seen (the attraction is not
gravitational, but the effect is the same), and if we
can cause them to move apart from each other, like a
ball rising from a planet, then they should slow. It is
very easy to move molecules apart from each other:
we simply allow the gas to expand, which increases
the average separation of the molecules. To cool a
gas, therefore, we allow it to expand without allow-
ing any heat to enter from outside. As it does so, the
molecules move apart to fill the available volume,
struggling as they do so against the attraction of their
neighbours. Because some kinetic energy must be
converted into potential energy to reach greater separ-
ations, the molecules travel more slowly as their
separation increases. Therefore, because the average
speed of the molecules has been reduced, the gas is
now cooler than before the expansion. This process
of cooling a real gas by expansion through a nar-
row opening called a ‘throttle’ is called the Joule–
Thomson effect. The effect was first observed and
analysed by James Joule (whose name is commemor-
ated in the unit of energy) and William Thomson
Further information 1.1
Kinetic molecular theory
One of the essential skills of a physical chemist is the ability
to turn simple, qualitative ideas into rigid, testable, quanti-
tative theories. The kinetic model of gases is an excellent
example of this technique, as it takes the concepts set out in
the text and turns them into precise expressions. As usual
in model building, there are a number of steps, but each one
is motivated by a clear appreciation of the underlying phys-
ical picture, in this case a swarm of mass points in ceaseless
random motion. The key quantitative ingredients we need
are the equations of classical mechanics, which are covered
in Foundations.
9780199608119_C01.indd 41
FURTHER INFORMATION 1.1 41
Cold
gas
Heat
exchanger
Throttle
Compressor Liquid
Fig. 1.20 The principle of the Linde refrigerator. The gas
is recirculated and cools the gas that is about to undergo
expansion through the throttle. The expanding gas cools still
further. Eventually, liquefied gas drips from the throttle.
(who later became Lord Kelvin). The procedure
works only for real gases in which the attractive
interactions are dominant, because the molecules
have to climb apart against the attractive force in
order for them to travel more slowly. For molecules
under conditions when repulsions are dominant
(corresponding to Z > 1, where Z is the compression
factor), the Joule–Thomson effect results in the gas
becoming warmer.
In practice, the gas is allowed to expand several
times by recirculating it through a device called a
Linde refrigerator (Fig. 1.20). On each successive
expansion the gas becomes cooler, and as it flows
past the incoming gas, the latter is cooled further.
After several successive expansions, the gas becomes
so cold that it condenses to a liquid.
We begin the derivation of eqn 1.11, p = nMv 2rms /3V, by
considering the arrangement in Fig. 1.21. When a particle
of mass m that is travelling with a component of velocity vx
parallel to the x-axis (vx > 0 corresponding to motion to the
right and vx < 0 to motion to the left) collides with the wall
on the right and is reflected, its linear momentum changes
from +m|vx | before the collision to −m|vx | after the collision
(when it is travelling in the opposite direction at the same
speed; |x| means the value of x with the sign discarded, so
|−3| = 3, for instance). The x-component of the momentum
therefore changes by 2m|vx | on each collision (the y- and
z-components are unchanged). Many molecules collide
with the wall in an interval ∆t, and the total change of
9/21/12 4:37 PM
 42 CHAPTER 1 THE PROPERTIES OF GASES

Area, A The total momentum change in the interval ∆t is the

|vx |∆t
product of the number of collisions we have just calculated
and the change of momentum on each collision, 2m|vx |:
Number of collis
sions Momentum change

  on one collision

 
nN A A | vx | t
Will Momentum change = × 2m | vx |
Won’t 2V
M =mN
nmN A Avx2 t MA x2 t
nMAv
= =
V V
Next, to find the force, we calculate the rate of change of
momentum:
x
Momentum change

 
Fig. 1.21 The model used for calculating the pressure of a nMAvx2 t /V nMAvx2
perfect gas according to the kinetic molecular theory. Here, Force = =
∆t V
for clarity, we show only the x-component of the velocity (the

Interval
other two components are not changed when the molecule
collides with the wall). All molecules within the shaded area It follows that the pressure, the force divided by the area, is
will reach the wall in an interval Dt provided they are moving
towards it.
Force
 
nMAvx2 /V nMvx2
Pressure = =
A V

Area
momentum is the product of the change in momentum of
each molecule multiplied by the number of molecules that Not all the molecules travel with the same velocity, so the
reach the wall during the interval. detected pressure, p, is the average (denoted 〈. . .〉) of the
We need to calculate that number. Because a molecule quantity just calculated:
with velocity component vx can travel a distance |vx |∆t nM 〈vx2 〉
along the x-axis in an interval ∆t, all the molecules within a p=
V
distance |vx |∆t of the wall will strike it if they are travelling
towards it. It follows that if the wall has area A, then all the To write an expression of the pressure in terms of the
particles in a volume A × |vx |∆t will reach the wall (if they root-mean-square speed, vrms, we begin by writing the
are travelling towards it). The number density, the number speed of a single molecule, v, as v2 = v x2 + v y2 + v z2. Because
of particles divided by the total volume, is nNA/V (where n the root-mean-square speed, vrms, is defined as vrms = 〈v 2〉1/2
is the total amount in moles of molecules in the container (eqn 1.12), it follows that
of volume V and NA is Avogadro’s constant), so the num- 2
v rms = 〈v 2〉 = 〈v x2〉 + 〈v y2〉 + 〈v z2〉
ber of molecules in the volume A|vx |∆t is (nNA/V) × A|vx |∆t.
At any instant, half the particles are moving to the right However, because the molecules are moving randomly, all
and half are moving to the left. Therefore, the average 2
three averages are the same. It follows that v rms = 3〈v x2〉.
1 2
number of collisions with the wall during the interval ∆t is Equation 1.11 now follows by substituting 〈v x 〉 = 3 v rms into
2

nNAA|vx |∆t/2V. p = nM〈v x2〉/V.

Checklist of key concepts

† 1 An equation of state is an equation relating pressures that each gas would exert if it were
pressure, volume, temperature, and amount of alone in the container at the same temperature.
a substance.
† 4 The partial pressure of any gas is defined as pJ =
† 2 The perfect-gas equation of state is based on xJp, where xJ is its mole fraction in a mixture and
Boyle’s law (p ∝ 1/V ), Charles’s law (V ∝ T ), and p is the total pressure.
Avogadro’s principle (V ∝ n).
† 5 The kinetic model of gases expresses the proper-
† 3 Dalton’s law states that the total pressure of ties of a perfect gas in terms of a collection of
a mixture of perfect gases is the sum of the mass points in ceaseless random motion.

9780199608119_C01.indd 42 9/21/12 4:37 PM

 QUESTIONS AND EXERCISES 43

† 6 The mean speed and root-mean-square speed of † 9 Graham’s law states that the rate of effusion is
molecules are proportional to the square root of inversely proportional to the square root of the
the (absolute) temperature and inversely propor- molar mass.
tional to the square root of the molar mass.
† 10 The Joule–Thomson effect is the cooling of gas
† 7 The properties of the Maxwell distribution of that occurs when it expands through a throttle
speeds are summarized in Figs 1.9 and 1.10. without the influx of heat.

† 8 Diffusion is the spreading of one substance

through another; effusion is the escape of a gas
through a small hole.

Road map of key equations

p = pA + pB + ...
Compression factor
Partial Assessment of real/perfect character
pJ = xJ p pressure
Z = pVm /RT
p ∝ 1/V
pV = nRT(1 + nB/V + n 2C / V 2 +...)
Boyle’s law
Mixtures Empirical
extension
Experimental p∝T pV = nRT
Virial equation

observations Charles’s law Molecular Molecular

repulsions attractions
pV = nRT/(V – nb) pV = nRT/(V – nb) – an 2/V 2
p∝n
Avogadro’s van der Waals equation
principle pV = 1/3nMv rms
2
Mean free path,
collision frequency
Model, Collisions pc = a/27b 2
vrms = (3RT/M)1/2 vrms = λ z Vc = 3b Critical
kinetic theory constants
Tc = 8a/27Rb

Boltzmann P(v,v + ∆v) = 4π(M/2πRT )1/2 v 2 exp(−Mv 2/2RT )∆v

distribution Maxwell–Boltzmann distribution

Blue boxes denote limitation to perfect gases.

Questions and exercises

Discussion questions
1.1 Explain how the experiments of Boyle, Charles, and 1.4 Provide a molecular interpretation for the variation of the
Avogadro led to the formulation of the perfect gas equation rates of diffusion and effusion of gases with temperature.
of state.
1.5 Explain how the compression factor varies with pressure
1.2 Explain the term ‘partial pressure’ and why Dalton’s law and temperature and describe how it reveals information
is a limiting law. about intermolecular interactions in real gases.

1.6 What is the significance of the critical constants of a gas?

1.3 Use the kinetic model of gases to explain why light
gases, such as H2 and He, are rare in the Earth’s atmosphere 1.7 Justify the formulation of the van der Waals equation of
but heavier gases, such as O2, CO2, and N2, are abundant. state.

9780199608119_C01.indd 43 9/21/12 4:37 PM

 44 CHAPTER 1 THE PROPERTIES OF GASES
Exercises
Treat all gases as perfect unless instructed otherwise.
1.1 What pressure is exerted by a sample of nitrogen gas of
mass 3.055 g in a container of volume 3.00 dm3 at 32 °C?
1.2 A sample of neon of mass 425 mg occupies 6.00 dm3 at
77 K. What pressure does it exert?
1.3 Much to everyone’s surprise, nitrogen monoxide (NO)
has been found to act as a neurotransmitter. To prepare to
study its effect, a sample was collected in a container of
volume 300.0 cm3. At 14.5 °C its pressure is found to be
34.5 kPa. What amount (in moles) of NO has been collected?
1.4 A domestic water-carbonating kit uses steel cylinders of
carbon dioxide of volume 250 cm3. They weigh 1.04 kg when
full and 0.74 kg when empty. What is the pressure of gas in
the cylinder at 20 °C?
1.5 The effect of high pressure on organisms, including
humans, is studied to gain information about deep-sea diving
and anaesthesia. A sample of air occupies 1.00 dm3 at 25 °C
and 1.00 atm. What pressure is needed to compress it to
100 cm3 at this temperature?
1.6 You are warned not to dispose of pressurized cans by
throwing them on to a fire. The gas in an aerosol container
exerts a pressure of 125 kPa at 18 °C. The container is thrown
on a fire, and its temperature rises to 700 °C. What is the
pressure at this temperature?
1.7 Until we find an economical way of extracting oxygen
from sea water or lunar rocks, we have to carry it with us to
inhospitable places, and do so in compressed form in tanks.
A sample of oxygen at 101 kPa is compressed at constant
temperature from 7.20 dm3 to 4.21 dm3. Calculate the final
pressure of the gas.
1.8 To what temperature must a sample of helium gas be
cooled from 22.2 °C to reduce its volume from 1.00 dm3 to
100 cm3?
1.9 Hot-air balloons gain their lift from the lowering of den-
sity of air that occurs when the air in the envelope is heated.
To what temperature should you heat a sample of air, initially
at 315 K, to increase its volume by 25 per cent?
1.10 At sea level, where the pressure was 104 kPa and the
temperature 21.1 °C, a certain mass of air occupied 2.0 m3.
To what volume will the region expand when it has risen
to an altitude where the pressure and temperature are
(a) 52 kPa, −5.0 °C, (b) 880 Pa, −52.0 °C?
1.11 A diving bell has an air space of 3.0 m3 when on the
deck of a boat. What is the volume of the air space when the
bell has been lowered to a depth of 50 m? Take the mean
density of sea water to be 1.025 g cm−3 and assume that the
temperature is the same as on the surface.
1.12 Balloons were used to obtain much of the early infor-
mation about the atmosphere and continue to be used today
9780199608119_C01.indd 44
to obtain weather information. In 1783, Jacques Charles
used a hydrogen-filled balloon to fly from Paris 36 km into the
French countryside. What is the mass density of hydrogen
relative to air at the same temperature and pressure? What
mass of payload can be lifted by 10 kg of hydrogen, neglect-
ing the mass of the balloon?
1.13 Atmospheric pollution is a problem that has received
much attention. Not all pollution, however, is from industrial
sources. Volcanic eruptions can be a significant source of air
pollution. The Kilauea volcano in Hawaii emits 200–300 t of
SO2 per day. If this gas is emitted at 800 °C and 1.0 atm, what
volume of gas is emitted?
1.14 A meteorological balloon had a radius of 1.5 m when
released at sea level at 20 °C and expanded to a radius of
3.5 m when it had risen to its maximum altitude where
the temperature was −25 °C. What is the pressure inside the
balloon at that altitude?
1.15 A gas mixture being used to simulate the atmosphere
of another planet consists of 320 mg of methane, 175 mg of
argon, and 225 mg of nitrogen. The partial pressure of nitro-
gen at 300 K is 15.2 kPa. Calculate (a) the volume and (b) the
total pressure of the mixture.
1.16 The vapour pressure of water at blood temperature is
47 Torr. What is the partial pressure of dry air in our lungs
when the total pressure is 760 Torr?
1.17 A determination of the density of a gas or vapour can
provide a quick estimate of its molar mass even though for
practical work mass spectrometry is far more precise. The
density of a gaseous compound was found to be 1.23 g dm−3
at 330 K and 25.5 kPa. What is the molar mass of the
compound?
1.18 In an experiment to measure the molar mass of a gas,
250 cm3 of the gas was confined in a glass vessel. The pres-
sure was 152 Torr at 298 K and the mass of the gas was
33.5 mg. What is the molar mass of the gas?
1.19 A vessel of volume 22.4 dm3 contains 2.0 mol H2 and
1.0 mol N2 at 273.15 K. Calculate (a) their partial pressures
and (b) the total pressure.
1.20 Use the kinetic model to calculate the root-mean-square
speed of (a) N2, (b) H2O molecules in the Earth’s atmosphere
at 273 K.
1.21 Use the equipartition theorem, which is outlined in
Foundations 0.12, to derive eqn 1.17.
1.22 Calculate the mean speed of (a) He atoms, (b) CH4
molecules at (i) 79 K, (ii) 315 K, (iii) 1500 K.
1.23 A 1.0 dm3 glass bulb contains 1.0 × 1023 H2 molecules.
If the pressure exerted by the gas is 100 kPa, what is (a) the
temperature of the gas, (b) the root-mean-square speeds of
the molecules? (c) Would the temperature be different if they
were O2 molecules?
9/21/12 4:37 PM

1.24 Synthesis gas (also known as ‘syngas’) consists of a
mixture of hydrogen, H2, and carbon monoxide, CO. Calculate
the relative rate, as molecules per second, at which the
hydrogen and carbon monoxide escape from a leaking cylin-
der of synthesis gas.
1.25 A cylinder containing gas for a carbon dioxide laser con-
tains equal amounts of carbon dioxide, nitrogen, and helium.
If 1.0 g of carbon dioxide leaks from the cylinder by effusion,
what mass of nitrogen and helium escapes?
1.26 At what pressure does the mean free path of argon
at 25 °C become comparable to the diameter of a spherical
vessel of volume 1.0 dm3 that contains it? Take s = 0.36 nm2.
1.27 At what pressure does the mean free path of argon at
25 °C become comparable to 10 times the diameters of the
atoms themselves? Take s = 0.36 nm2.
1.28 When studying the photochemical processes that can
occur in the upper atmosphere, it is important to know how
often atoms and molecules collide. At an altitude of 20 km
the temperature is 217 K and the pressure 0.050 atm. What
is the mean free path of N2 molecules? Take s = 0.43 nm2.
1.29 How many collisions does a single Ar atom make in
1.0 s when the temperature is 25 °C and the pressure is
(a) 10 bar, (b) 100 kPa, (c) 1.0 Pa?
1.30 Calculate the total number of collisions per second in
1.0 dm3 of argon under the same conditions as in Exercise
1.29.
1.31 How many collisions per second does an N2 molecule
make at an altitude of 20 km? (See Exercise 1.28 for data.)
1.32 How does the mean free path in a sample of a gas vary
with temperature in a constant-volume container?
1.33 The spread of pollutants through the atmosphere is
governed partly by the effects of winds but also by the nat-
ural tendency of molecules to diffuse. The latter depends on
how far a molecule can travel before colliding with another
molecule. Calculate the mean free path of diatomic mole-
cules in air using s = 0.43 nm2 at 25 °C and (a) 10 bar, (b)
103 kPa, (c) 1.0 Pa.
Projects
The symbol ‡ indicates that calculus is required.
1.43‡ In the following you are invited to explore the Maxwell
distribution of speeds in more detail. (a) Confirm that the
mean speed of molecules of molar mass M at a temperature
T is equal to (8RT/pM)1/2. Hint: You will need an integral of
∞ K that has speeds in the range 290 to 300 m s−1.
the form ∫0 x 3e−ax dx = n!/2a2. (b) Confirm that the root-mean-
2
square speed of molecules of molar mass M at a tempera-
ture T is equal to (3RT/M )1/2 and hence confirm eqn 1.17.
9780199608119_C01.indd 45
QUESTIONS AND EXERCISES 45
1.34 The critical point of ammonia, NH3, gas occurs at
111.3 atm, 72.5 cm3 mol−1, and 405.5 K. Calculate the com-
pression factor at the critical point. What can you infer?
1.35 The virial equation of state may also be written as an
expansion in terms of pressure: Z = 1 + B ′p + . . . . The critical
constants for water, H2O, are 218.3 atm, 55.3 cm3 mol−1, and
647.4 K. Assuming that the expansion may be truncated
after the second term, calculate the value of the second virial
coefficient B′ at the critical temperature.
1.36 Calculate the pressure exerted by 1.0 mol C2H6 behaving
as (a) a perfect gas, (b) a van der Waals gas when it is
confined under the following conditions: (i) at 273.15 K in
22.414 dm3, (ii) at 1000 K in 100 cm3. Use the data in Table 1.6.
1.37 How reliable is the perfect gas law in comparison with
the van der Waals equation? Calculate the difference in pres-
sure of 10.00 g of carbon dioxide confined to a container of
volume 100 cm3 at 25.0 °C between treating it as a perfect
gas and a van der Waals gas.
1.38 A certain gas obeys the van der Waals equation with
a = 0.50 m6 Pa mol−2. Its molar volume is found to be
5.00 × 10−4 m3 mol−1 at 273 K and 3.0 MPa. From this infor-
mation calculate the van der Waals constant b. What is the
compression factor for this gas at the prevailing temperature
and pressure?
1.39 Express the van der Waals equation of state as a virial
expansion in powers of 1/Vm and obtain expressions for B
and C in terms of the parameters a and b. Hint: The expan-
sion you will need is (1 − x)−1 = 1 + x + x 2 + . . . .
1.40 Measurements on argon gave B = −21.7 cm3 mol−1 and
C = 1200 cm6 mol−2 for the virial coefficients at 273 K. What
are the values of a and b in the corresponding van der Waals
equation of state? Hint: Use the expression for B derived in
Exercise 1.39.
1.41 Show that there is a temperature at which the second
virial coefficient, B, is zero for a van der Waals gas, and calcu-
late its value for carbon dioxide. Hint: Use the expression for
B derived in Exercise 1.39.
1.42 The critical constants of ethane are pc = 48.20 atm,
Vc = 148 cm3 mol−1, and Tc = 305.4 K. Calculate the van der
Waals parameters of the gas and estimate the radius of the
molecules.
∞
Hint: You will need an integral of the form ∫0 x 4e−ax dx = (3/8a2)
2
(p/a)1/2. (c) Find an expression for the most probable speed of
molecules of molar mass M at a temperature T. Hint: Look for
a maximum in the Maxwell distribution (the maximum occurs
as dF/ds = 0). (d) Estimate the fraction of N2 molecules at 500
1.44‡ Here we explore the van der Waals equation of state.
Using the language of calculus, the critical point of a van der
9/21/12 4:37 PM
 46 CHAPTER 1 THE PROPERTIES OF GASES

Waals gas occurs where the isotherm has a flat inflexion, interior consists of ionized hydrogen atoms, the temperature
which is where dp/dVm = 0 (zero slope) and d2p/dV m 2
= 0 (zero is 3.6 MK, and the mass density is 1.20 g cm−3 (slightly higher
curvature). (a) Evaluate these two expressions using eqn than the density of water). (b) Combine the result from part
1.26b, and find expressions for the critical constants in terms (a) with the expression for the pressure from kinetic model to
of the van der Waals parameters. (b) Show that the value of show that the pressure of the plasma is related to its kinetic
the compression factor at the critical point is 3/8. energy density rk = Ek /V, the kinetic energy of the molecules
in a region divided by the volume of the region, by p = (2/3)rk.
1.45 The kinetic model of gases is valid when the size of the
(c) What is the kinetic energy density halfway to the centre of
particles is negligible compared with their mean free path.
the Sun? Compare your result with the (translational) kinetic
It may seem absurd, therefore, to expect the kinetic theory
energy density of the Earth’s atmosphere on a warm day
and, as a consequence, the perfect gas law, to be applicable
(25 °C): 1.5 × 105 J m−3 (corresponding to 0.15 J cm−3). (d) A
to the dense matter of stellar interiors. In the Sun, for
star eventually depletes some of the hydrogen in its core,
instance, the density is 150 times that of liquid water at its
which contracts and results in higher temperatures. The
centre and comparable to that of water about halfway to its
increased temperature results in an increase in the rates
surface. However, we have to realize that the state of matter
of nuclear reaction, some of which result in the formation
is that of a plasma, in which the electrons have been stripped
of heavier nuclei, such as carbon. The outer part of the star
from the atoms of hydrogen and helium that make up the
expands and cools to produce a red giant. Assume that half-
bulk of the matter of stars. As a result, the particles making
way to the centre a red giant has a temperature of 3500 K, is
up the plasma have diameters comparable to those of nuclei,
composed primarily of fully ionized carbon atoms and elec-
or about 10 fm. Therefore, a mean free path of only 0.1 pm
trons, and has a mass density of 1200 kg m−3. What is the
satisfies the criterion for the validity of the kinetic model and
pressure at this point? (e) If the red giant in part (d) consisted
the perfect gas law. We can therefore use pV = nRT as the
of neutral carbon atoms, what would be the pressure at the
equation of state for the stellar interior. (a) Calculate the pres-
same point under the same conditions?
sure halfway to the centre of the Sun, assuming that the

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