PART ONE

Thermodynamics

Part 1 of the text develops the concepts of thermodynamics, the science of the transformations of
energy. Thermodynamics provides a powerful way to discuss equilibria and the direction of natu-
ral change in chemistry. Its concepts apply to both physical change, such as fusion and vaporiza-
tion, and chemical change, including electrochemistry. We see that through the concepts of energy,
enthalpy, entropy, Gibbs energy, and the chemical potential it is possible to obtain a unified view of
these core features of chemistry and to treat equilibria quantitatively.
The chapters in Part 1 deal with the bulk properties of matter; those of Part 2 show how these
properties stem from the behaviour of individual atoms.

1 The properties of gases

Mathematical background 1: Differentiation and integration

2 The First Law

Mathematical background 2: Multivariate calculus

3 The Second and Third Laws

4 Physical transformations of pure substances

5 Simple mixtures

6 Chemical equilibrium
CHAPTER 1
The properties of gases
A gas is a form of matter that fills whatever container it occu-
pies. This chapter establishes the properties of gases that will be
used throughout the text.
1A The perfect gas
The chapter begins with an account of an idealized version of a
gas, a ‘perfect gas’, and shows how its equation of state may be
assembled from the experimental observations summarized by
Boyle’s law, Charles’s law, and Avogadro’s principle.
1B The kinetic model
One central feature of physical chemistry is its role in building
models of molecular behaviour that seek to explain observed
phenomena. A prime example of this procedure is the devel-
opment of a molecular model of a perfect gas in terms of a
collection of molecules (or atoms) in ceaseless, essentially
random motion. This model is the basis of ‘kinetic molecular
theory’. As well as accounting for the gas laws, this theory can
be used to predict the average speed at which molecules move
in a gas, and that speed’s dependence on temperature. In com-
bination with the Boltzmann distribution (Foundations B),
the kinetic theory can also be used to predict the spread of
molecular speeds and its dependence on molecular mass and
temperature.
1C Real gases
The perfect gas is an excellent starting point for the discussion
of properties of all gases, and its properties are invoked through-
out the chapters on thermodynamics that follow this chapter.
However, actual gases, ‘real gases’, have properties that differ from
those of perfect gases, and we need to be able to interpret these
deviations and build the effects of molecular attractions and
repulsions into our model. The discussion of real gases is another
example of how initially primitive models in physical chemistry
are elaborated to take into account more detailed observations.
What is the impact of this material?
The perfect gas law and the kinetic theory can be applied to the
study of phenomena confined to a reaction vessel or encom-
passing an entire planet or star. We have identified two appli-
cations. In Impact I1.1 we see how the gas laws are used in the
discussion of meteorological phenomena—the weather. In
Impact I1.2 we examine how the kinetic model of gases has a
surprising application: to the discussion of dense stellar media,
such as the interior of the Sun.
To read more about the impact of this
material, scan the QR code, or go to
bcs.whfreeman.com/webpub/chemistry/
pchem10e/impact/pchem-1-1.html
1A The perfect gas

1A.1 Variables of state

Contents
The physical state of a sample of a substance, its physical condi-
1A.1 Variables of state 30
tion, is defined by its physical properties. Two samples of the
(a) Pressure 30
same substance that have the same physical properties are in
Example 1A.1: Calculating the pressure
exerted by a column of liquid 31 the same state. The variables needed to specify the state of a sys-
(b) Temperature 31 tem are the amount of substance it contains, n, the volume it
Brief illustration 1A.1:  Temperature conversion 32 occupies, V, the pressure, p, and the temperature, T.
1A.2 Equations of state 32
(a) The empirical basis 32 (a) Pressure
Example 1A.2: Using the perfect gas law 34
The origin of the force exerted by a gas is the incessant battering
(b) Mixtures of gases 35
of the molecules on the walls of its container. The collisions are
Example 1A.3: Calculating partial pressures 35
so numerous that they exert an effectively steady force, which
Checklist of concepts 36
Checklist of equations 36
is experienced as a steady pressure. The SI unit of pressure, the
pascal (Pa, 1 Pa = 1 N m−2) is introduced in Foundations A. As
discussed there, several other units are still widely used (Table
1A.1). A pressure of 1 bar is the standard pressure for report-
ing data; we denote it p<.
If two gases are in separate containers that share a common
➤➤ Why do you need to know this material? movable wall (a ‘piston’, Fig. 1A.1), the gas that has the higher
Equations related to perfect gases provide the basis for pressure will tend to compress (reduce the volume of) the gas
the development of many equations in thermodynamics. that has lower pressure. The pressure of the high-pressure gas
The perfect gas law is also a good first approximation for will fall as it expands and that of the low-pressure gas will
accounting for the properties of real gases. rise as it is compressed. There will come a stage when the two
pressures are equal and the wall has no further tendency to
➤➤ What is the key idea? move. This condition of equality of pressure on either side of
The perfect gas law, which is based on a series of empirical a movable wall is a state of mechanical equilibrium between
observations, is a limiting law that is obeyed increasingly the two gases. The pressure of a gas is therefore an indica-
well as the pressure of a gas tends to zero. tion of whether a container that contains the gas will be in
mechanical equilibrium with another gas with which it shares
➤➤ What do you need to know already? a movable wall.
You need to be aware of the concepts of pressure and
temperature introduced in Foundations A.
Table 1A.1 Pressure units*

Name Symbol Value

pascal 1 Pa 1 N m−2, 1 kg m−1 s−2
In molecular terms, a gas consists of a collection of molecules bar 1 bar 105 Pa
that are in ceaseless motion and which interact significantly
atmosphere 1 atm 101.325 kPa
with one another only when they collide. The properties of
torr 1 Torr (101 325/760) Pa = 133.32… Pa
gases were among the first to be established quantitatively
(largely during the seventeenth and eighteenth centuries) when millimetres of mercury 1 mmHg 133.322… Pa

the technological requirements of travel in balloons stimulated pounds per square inch 1 psi 6.894 757… kPa
their investigation. * Values in bold are exact.
 1A The perfect gas 31

(a) Movable
High wall Low Note that the hydrostatic pressure is independent of the shape
pressure pressure and cross-sectional area of the column. The mass of the col-
umn of a given height increases as the area, but so does the
(b) area on which the force acts, so the two cancel.
Equal Equal
pressures pressures S elf-test 1A.1 D e r i v e a n
expression for the pressure at θ
(c) the base of a column of liquid
Low High of length l held at an angle θ
pressure pressure (theta) to the vertical (1).
l
1
Figure 1A.1 When a region of high pressure is separated from
a region of low pressure by a movable wall, the wall will be Answer: p = ρgl cos θ
pushed into one region or the other, as in (a) and (c). However,
if the two pressures are identical, the wall will not move (b).
The latter condition is one of mechanical equilibrium between
The pressure of a sample of gas inside a container is
the two regions.
measured by using a pressure gauge, which is a device with
properties that respond to the pressure. For instance, a
The pressure exerted by the atmosphere is measured with Bayard–Alpert pressure gauge is based on the ionization of
a barometer. The original version of a barometer (which was the molecules present in the gas and the resulting current of
invented by Torricelli, a student of Galileo) was an inverted ions is interpreted in terms of the pressure. In a capacitance
tube of mercury sealed at the upper end. When the column of manometer, the deflection of a diaphragm relative to a fixed
mercury is in mechanical equilibrium with the atmosphere, the electrode is monitored through its effect on the capacitance
pressure at its base is equal to that exerted by the atmosphere. It of the arrangement. Certain semiconductors also respond to
follows that the height of the mercury column is proportional pressure and are used as transducers in solid-state pressure
to the external pressure. gauges.

Example 1A.1 Calculating the pressure exerted by a (b) Temperature

column of liquid
Derive an equation for the pressure at the base of a column
of liquid of mass density ρ (rho) and height h at the surface of
the Earth. The pressure exerted by a column of liquid is com-
monly called the ‘hydrostatic pressure’.
Method According to Foundations A, the pressure is the
force, F, divided by the area, A, to which the force is applied:
p = F/A. For a mass m subject to a gravitational field at the sur-
face of the earth, F = mg, where g is the acceleration of free fall.
To calculate F we need to know the mass m of the column of
liquid, which is its mass density, ρ, multiplied by its volume,
V: m = ρV. The first step, therefore, is to calculate the volume of
a cylindrical column of liquid.
Answer Let the column have cross-sectional area A, then its
volume is Ah and its mass is m = ρAh. The force the column of
this mass exerts at its base is
F = mg = ρAhg
The pressure at the base of the column is therefore
F ρAgh
p= = = ρgh Hydrostatic pressure (1A.1)
A A
The concept of temperature is introduced in Foundations A. In
the early days of thermometry (and still in laboratory practice
today), temperatures were related to the length of a column of
liquid, and the difference in lengths shown when the thermo­
meter was first in contact with melting ice and then with boil-
ing water was divided into 100 steps called ‘degrees’, the lower
point being labelled 0. This procedure led to the Celsius scale
of temperature. In this text, temperatures on the Celsius scale
are denoted θ (theta) and expressed in degrees Celsius (°C).
However, because different liquids expand to different extents,
and do not always expand uniformly over a given range, ther-
mometers constructed from different materials showed differ-
ent numerical values of the temperature between their fixed
points. The pressure of a gas, however, can be used to construct
a perfect-gas temperature scale that is independent of the
identity of the gas. The perfect-gas scale turns out to be iden-
tical to the thermodynamic temperature scale introduced in
Topic 3A, so we shall use the latter term from now on to avoid a
proliferation of names.
On the thermodynamic temperature scale, temperatures are
denoted T and are normally reported in kelvins (K; not °K).
Thermodynamic and Celsius temperatures are related by the
exact expression
32 1 The properties of gases
T/K = θ / °C + 273.15 Definition of Celsius scale
This relation is the current definition of the Celsius scale in
terms of the more fundamental Kelvin scale. It implies that a
difference in temperature of 1 °C is equivalent to a difference
of 1 K.
A note on good practice We write T = 0, not T = 0 K for the
zero temperature on the thermodynamic temperature scale.
This scale is absolute, and the lowest temperature is 0 regard-
less of the size of the divisions on the scale (just as we write
p = 0 for zero pressure, regardless of the size of the units we
adopt, such as bar or pascal). However, we write 0 °C because
the Celsius scale is not absolute.
Brief illustration 1A.1 Temperature conversion
To express 25.00 °C as a temperature in kelvins, we use eqn
1A.4 to write
T/K = (25.00 °C)/ °C + 273.15 = 25.00 + 273.15 = 298.15
Note how the units (in this case, °C) are cancelled like num-
bers. This is the procedure called ‘quantity calculus’ in which
a physical quantity (such as the temperature) is the product of
a numerical value (25.00) and a unit (1 °C); see The chemist’s
toolkit A.1 of Foundations. Multiplication of both sides by the
unit K then gives T = 298.15 K.
A note on good practice When the units need to be speci-
fied in an equation, the approved procedure, which avoids
any ambiguity, is to write (physical quantity)/units, which
is a dimensionless number, just as (25.00 °C)/°C = 25.00 in
this illustration. Units may be multiplied and cancelled
just like numbers.
1A.2 Equations of state
Although in principle the state of a pure substance is speci-
fied by giving the values of n, V, p, and T, it has been estab-
lished experimentally that it is sufficient to specify only three
of these variables, for then the fourth variable is fixed. That is,
it is an experimental fact that each substance is described by
an equation of state, an equation that interrelates these four
variables.
The general form of an equation of state is
p = f (T ,V , n) General form of an equation of state
This equation tells us that if we know the values of n, T, and V
for a particular substance, then the pressure has a fixed value.
Each substance is described by its own equation of state, but
(1A.2) we know the explicit form of the equation in only a few special
cases. One very important example is the equation of state of a
‘perfect gas’, which has the form p = nRT/V, where R is a con-
stant independent of the identity of the gas.
The equation of state of a perfect gas was established by com-
bining a series of empirical laws.
(a) The empirical basis
We assume that the following individual gas laws are familiar:
Boyle’s law: pV = constant, at constant n, T (1A.4a)
Charles’s law: V = constant × T , at constant n, p (1A.4b)
       p = constant × T , at constant n, V (1A.4c)
Avogadro’s principle:
V = constant × n at constant p, T (1A.4d)
Boyle’s and Charles’s laws are examples of a limiting law, a law
that is strictly true only in a certain limit, in this case p → 0.
For example, if it is found empirically that the volume of a
substance fits an expression V = aT + bp + cp2, then in the limit
of p → 0, V = aT. Throughout this text, equations valid in this
limit­ing sense are labelled with a blue equation number, as in
these expressions. Although these relations are strictly true
only at p = 0, they are reasonably reliable at normal pressures
(p ≈ 1 bar) and are used widely throughout chemistry.
Avogadro’s principle is commonly expressed in the form
‘equal volumes of gases at the same temperature and pressure
contain the same numbers of molecules’. It is a principle rather
than a law (a summary of experience) because it depends on
the validity of a model, in this case the existence of molecules.
Despite there now being no doubt about the existence of mol-
ecules, it is still a model-based principle rather than a law.
Figure 1A.2 depicts the variation of the pressure of a sam-
ple of gas as the volume is changed. Each of the curves in the
Increasing
temperature, T
Pressure, p
0
(1A.3) 0 Volume, V
Figure 1A.2 The pressure–volume dependence of a fixed
amount of perfect gas at different temperatures. Each curve
is a hyperbola (pV = constant) and is called an isotherm.

Pressure, p
Increasing
temperature, T
Extrapolation
0 0
0 0
1/Volume, 1/V
Figure 1A.3 Straight lines are obtained when the pressure is
plotted against 1/V at constant temperature.
graph corresponds to a single temperature and hence is called
an isotherm. According to Boyle’s law, the isotherms of gases
are hyperbolas (a curve obtained by plotting y against x with
xy = constant, or y = constant/x). An alternative depiction, a
plot of pressure against 1/volume, is shown in Fig. 1A.3. The
linear variation of volume with temperature summarized by
Charles’s law is illustrated in Fig. 1A.4. The lines in this illustra-
tion are examples of isobars, or lines showing the variation of
properties at constant pressure. Figure 1A.5 illustrates the lin-
ear variation of pressure with temperature. The lines in this dia-
gram are isochores, or lines showing the variation of properties
at constant volume.
A note on good practice To test the validity of a relation
between two quantities, it is best to plot them in such a way
that they should give a straight line, for deviations from a
straight line are much easier to detect than deviations from
a curve. The development of expressions that, when plotted,
give a straight line is a very important and common proce-
dure in physical chemistry.
Volume, V
Decreasing
pressure, p
Extrapolation
0 values of NA and k. Table 1A.2 lists the values of R in a variety
0 Temperature, T
Figure 1A.4 The variation of the volume of a fixed amount of
gas with the temperature at constant pressure. Note that in
each case the isobars extrapolate to zero volume at T = 0, or
θ = –273 °C.
1A The perfect gas 33
Pressure, p
Decreasing
volume, V
Extrapolation
Temperature, T
Figure 1A.5 The pressure also varies linearly with the
temperature at constant volume, and extrapolates to zero at
T = 0 (–273 °C).
The empirical observations summarized by eqn 1A.5 can be
combined into a single expression:
pV = constant × nT
This expression is consistent with Boyle’s law (pV = constant)
when n and T are constant, with both forms of Charles’s law
(p ∝ T, V ∝ T) when n and either V or p are held constant, and
with Avogadro’s principle (V ∝ n) when p and T are constant.
The constant of proportionality, which is found experimentally
to be the same for all gases, is denoted R and called the (molar)
gas constant. The resulting expression
pV = nRT Perfect gas law (1A.5)
is the perfect gas law (or perfect gas equation of state). It is the
approximate equation of state of any gas, and becomes increas-
ingly exact as the pressure of the gas approaches zero. A gas that
obeys eqn 1A.5 exactly under all conditions is called a perfect
gas (or ideal gas). A real gas, an actual gas, behaves more like a
perfect gas the lower the pressure, and is described exactly by eqn
1A.5 in the limit of p → 0. The gas constant R can be determined
by evaluating R = pV/nT for a gas in the limit of zero pressure (to
guarantee that it is behaving perfectly). However, a more accurate
value can be obtained by measuring the speed of sound in a low-
pressure gas (argon is used in practice), for the speed of sound
depends on the value of R and extrapolating its value to zero
pressure. Another route to its value is to recognize (as explained
in Foundations B) that it is related to Boltzmann’s constant, k, by
R = NA k The (molar) gas constant (1A.6)
where NA is Avogadro’s constant. There are currently (in 2014)
plans to use this relation as the sole route to R, with defined
of units.
A note on good practice Despite ‘ideal gas’ being the more
common term, we prefer ‘perfect gas’. As explained in Topic
5A, in an ‘ideal mixture’ of A and B, the AA, BB, and AB
34 1 The properties of gases

Table 1A.2 The gas constant (R = NAk) Example 1A.2 Using the perfect gas law
R
In an industrial process, nitrogen is heated to 500 K in a vessel
8.314 47 J K−1 mol−1 of constant volume. If it enters the vessel at 100 atm and 300 K,
8.205 74 × 10−2 dm3 atm K−1 mol−1 what pressure would it exert at the working temperature if it
8.314 47 × 10−2 dm3 bar K−1 mol−1 behaved as a perfect gas?
8.314 47 Pa m3 K−1 mol−1 Method We expect the pressure to be greater on account of
62.364 dm3 Torr K−1 mol−1 the increase in temperature. The perfect gas law in the form
pV/nT = R implies that if the conditions are changed from one
1.987 21 cal K−1 mol−1
set of values to another, then because pV/nT is equal to a con-
stant, the two sets of values are related by the ‘combined gas law’
interactions are all the same but not necessarily zero. In a
p1V1 p2V2
perfect gas, not only are the interactions all the same, they are = Combined gas law (1A.7)
n1T1 n2T2
also zero.
This expression is easily rearranged to give the unknown
The surface in Fig. 1A.6 is a plot of the pressure of a fixed quantity (in this case p2) in terms of the known. The known
amount of perfect gas against its volume and thermodynamic and unknown data are summarized as follows:
temperature as given by eqn 1A.5. The surface depicts the only
possible states of a perfect gas: the gas cannot exist in states that n p V T
do not correspond to points on the surface. The graphs in Figs. Initial Same 100 Same 300
1A.2 and 1A.4 correspond to the sections through the surface Final Same ? Same 500
(Fig. 1A.7).
Answer Cancellation of the volumes (because V1 = V2) and
amounts (because n1 = n 2) on each side of the combined gas
law results in

Surface
Pressure, p

p1 p2
of possible =
T1 T2
states

which can be rearranged into

T2
e,
T p2 = ×p
r T1 1
r atu
Volume, V pe
m
Te Substitution of the data then gives
Figure 1A.6 A region of the p,V,T surface of a fixed amount of
500 K
perfect gas. The points forming the surface represent the only p2 = × (100 atm) = 167 atm
300 K
states of the gas that can exist.

Experiment shows that the pressure is actually 183 atm under

Isotherm
these conditions, so the assumption that the gas is perfect
Isobar
leads to a 10 per cent error.
pV = constant
Self-test 1A.2 What temperature would result in the same
Pressure, p

Isochore
V∝T sample exerting a pressure of 300 atm?
Answer: 900 K

V
Vo
olum
mee, V
e,
p∝T
The perfect gas law is of the greatest importance in physical
e ,T
tur chemistry because it is used to derive a wide range of relations
ra
Volume, V pe that are used throughout thermodynamics. However, it is also
m
Te
of considerable practical utility for calculating the properties of
Figure 1A.7 Sections through the surface shown in Fig. 1A.6 at a gas under a variety of conditions. For instance, the molar vol-
constant temperature give the isotherms shown in Fig. 1A.2, the ume, Vm = V/n, of a perfect gas under the conditions called stand-
isobars shown in Fig. 1A.4, and the isochores shown in Fig. 1A.5. ard ambient temperature and pressure (SATP), which means
 1A The perfect gas 35

298.15 K and 1 bar (that is, exactly 105 Pa), is easily calculated Now, however, the relation between partial pressure (as defined
from Vm = RT/p to be 24.789 dm3 mol−1. An earlier definition, in eqn 1A.8) and total pressure (as given by eqn 1A.10) is true
standard temperature and pressure (STP), was 0 °C and 1 atm; for all gases and the identification of partial pressure with the
at STP, the molar volume of a perfect gas is 22.414 dm3 mol−1. pressure that the gas would exert on its own is valid only for a
The molecular explanation of Boyle’s law is that if a sample of perfect gas.
gas is compressed to half its volume, then twice as many mole-
cules strike the walls in a given period of time than before it was
compressed. As a result, the average force exerted on the walls Example 1A.3 Calculating partial pressures
is doubled. Hence, when the volume is halved the pressure of
The mass percentage composition of dry air at sea level
the gas is doubled, and pV is a constant. Boyle’s law applies to all
is approximately N2: 75.5; O2: 23.2; Ar: 1.3. What is the par-
gases regardless of their chemical identity (provided the pres-
tial pressure of each component when the total pressure is
sure is low) because at low pressures the average separation of 1.20 atm?
molecules is so great that they exert no influence on one another
and hence travel independently. The molecular explanation of Method We expect species with a high mole fraction to
Charles’s law lies in the fact that raising the temperature of a have a proportionally high partial pressure. Partial pres-
gas increases the average speed of its molecules. The molecules sures are defined by eqn 1A.8. To use the equation, we need
collide with the walls more frequently and with greater impact. the mole fractions of the components. To calculate mole frac-
Therefore they exert a greater pressure on the walls of the con- tions, which are defined by eqn 1A.9, we use the fact that the
tainer. For a quantitative account of these relations, see Topic 1B. amount of molecules J of molar mass MJ in a sample of mass
mJ is nJ = mJ/MJ. The mole fractions are independent of the total
mass of the sample, so we can choose the latter to be exactly
(b) Mixtures of gases 100 g (which makes the conversion from mass percentages
very easy). Thus, the mass of N2 present is 75.5 per cent of
When dealing with gaseous mixtures, we often need to know
100 g, which is 75.5 g.
the contribution that each component makes to the total pres-
sure of the sample. The partial pressure, pJ, of a gas J in a mix- Answer The amounts of each type of molecule present in 100 g
ture (any gas, not just a perfect gas), is defined as of air, in which the masses of N2, O2, and Ar are 75.5 g, 23.2 g,
and 1.3 g, respectively, are
pJ = x J p Definition Partial pressure (1A.8)
75.5 g 75.5
n(N2 ) = = mol = 2.69 mol
where xJ is the mole fraction of the component J, the amount of 28.02 g mol −1 28.02
J expressed as a fraction of the total amount of molecules, n, in 23.2 g 23.2
the sample: n(O2 ) = = mol = 0.725 mol
32.00 g mol −1 32.00
1. 3 g 1. 3
nJ n(Ar) = = mol = 0.033 mol
xJ = n = nA + nB + Definition Mole fraction (1A.9) 39.95 g mol −1 39.95
n
The total is 3.45 mol. The mole fractions are obtained by divid-
When no J molecules are present, xJ = 0; when only J molecules
ing each of the above amounts by 3.45 mol and the partial
are present, xJ = 1. It follows from the definition of xJ that, what-
pressures are then obtained by multiplying the mole fraction
ever the composition of the mixture, xA + xB + … = 1 and therefore
by the total pressure (1.20 atm):
that the sum of the partial pressures is equal to the total pressure:
N2 O2 Ar
pA + pB + … = (x A + x B + …) p = p (1A.10)
Mole fraction: 0.780 0.210 0.0096
This relation is true for both real and perfect gases. Partial pressure/atm: 0.936 0.252 0.012
When all the gases are perfect, the partial pressure as defined
in eqn 1A.9 is also the pressure that each gas would exert if it We have not had to assume that the gases are perfect: partial
occupied the same container alone at the same temperature. The pressures are defined as pJ = xJp for any kind of gas.
latter is the original meaning of ‘partial pressure’. That identifica- Self-test 1A.3 When carbon dioxide is taken into account,
tion was the basis of the original formulation of Dalton’s law: the mass percentages are 75.52 (N2), 23.15 (O2), 1.28 (Ar), and
0.046 (CO2). What are the partial pressures when the total
The pressure exerted by a mixture of gases is the pressure is 0.900 atm?
sum of the pressures that each one would exert Answer: 0.703, 0.189, 0.0084, 0.00027 atm
if it occupied the container alone. Dalton’s law
36 1 The properties of gases

Checklist of concepts
☐ 1. The physical state of a sample of a substance, its physi-
cal condition, is defined by its physical properties.
☐ 2. Mechanical equilibrium is the condition of equality of
pressure on either side of a shared movable wall.
☐ 3. An equation of state is an equation that interrelates the
variables that define the state of a substance.
☐ 4. Boyle’s and Charles’s laws are examples of a limiting
law, a law that is strictly true only in a certain limit, in
this case p → 0.
☐ 5. An isotherm is a line in a graph that corresponds to a
single temperature.
☐ 6. An isobar is a line in a graph that corresponds to a sin-
gle pressure.
☐ 7. An isochore is a line in a graph that corresponds to a
single volume.
☐ 8. A perfect gas is a gas that obeys the perfect gas law
under all conditions.
☐ 9. Dalton’s law states that the pressure exerted by a mix-
ture of (perfect) gases is the sum of the pressures that
each one would exert if it occupied the container
alone.

Checklist of equations
Property Equation Comment Equation number

Relation between temperature scales T/K = θ/°C + 273.15 273.15 is exact 1A.2

Equation of state p = f(n,V,T) 1A.3

Perfect gas law pV = nRT Valid for real gases in the limit p → 0 1A.5

Partial pressure pJ = xJp Valid for all gases 1A.8

1B The kinetic model

chemistry, for from a set of very slender assumptions, powerful

Contents
quantitative conclusions can be reached.
1B.1 The model 37
(a) Pressure and molecular speeds 37
Brief illustration 1B.1: Molecular speeds 38
(b) The Maxwell–Boltzmann distribution of speeds 39 1B.1 The model
(c) Mean values 40
Example 1B.1: Calculating the mean speed of The kinetic model is based on three assumptions:
molecules in a gas 41
Brief illustration 1B.2: Relative molecular speeds 42 1. The gas consists of molecules of mass m in ceaseless
1B.2 Collisions 42 random motion obeying the laws of classical mechanics.
(a) The collision frequency 42 2. The size of the molecules is negligible, in the sense that
Brief illustration 1B.3: Molecular collisions 43 their diameters are much smaller than the average
(b) The mean free path 43 distance travelled between collisions.
Brief illustration 1B.4: The mean free path 43
3. The molecules interact only through brief elastic
Checklist of concepts 44
collisions.
Checklist of equations 44
An elastic collision is a collision in which the total translational
kinetic energy of the molecules is conserved.

➤➤ Why do you need to know this material? (a) Pressure and molecular speeds
This material illustrates an important skill in science: From the very economical assumptions of the kinetic model,
the ability to extract quantitative information from a we show in the following Justification that the pressure and vol-
qualitative model. Moreover, the model is used in the ume of the gas are related by
discussion of the transport properties of gases (Topic pV = 13 nM vrms
2
Perfect gas Pressure (1B.1)
19A), reaction rates in gases (Topic 20F), and catalysis
(Topic 22C). where M = mNA, the molar mass of the molecules of mass m,
and vrms is the square root of the mean of the squares of the
➤➤ What is the key idea? speeds, v, of the molecules:
A gas consists of molecules of negligible size in ceaseless
random motion and obeying the laws of classical vrms = 〈v 2 〉1/2 Definition Root-mean-square speed (1B.2)
mechanics in their collisions.

➤➤ What do you need to know already?
You need to be aware of Newton’s second law of motion,
that the acceleration of a body is proportional to the force
acting on it, and the conservation of linear momentum.
In the kinetic theory of gases (which is sometimes called the
kinetic-molecular theory, KMT) it is assumed that the only
contribution to the energy of the gas is from the kinetic ener-
gies of the molecules. The kinetic model is one of the most
remarkable—and arguably most beautiful—models in physical
Justification 1.1B The pressure of a gas according to the
kinetic model
Consider the arrangement in Fig. 1B.1. When a particle of
mass m that is travelling with a component of velocity vx par-
allel to the x-axis collides with the wall on the right and is
reflected, its linear momentum changes from mvx before the
collision to –mvx after the collision (when it is travelling in the
opposite direction). The x-component of momentum therefore
changes by 2mvx on each collision (the y- and z-components
are unchanged). Many molecules collide with the wall in an
interval Δt, and the total change of momentum is the prod-
uct of the change in momentum of each molecule multiplied
38 1 The properties of gases

Next, to find the force, we calculate the rate of change of

Before
mvx momentum, which is this change of momentum divided by
collision the interval Δt during which it occurs:

nMAvx2
Rate of change of momentum =
V
–mvx
This rate of change of momentum is equal to the force (by
After
collision Newton’s second law of motion). It follows that the pressure,
the force divided by the area, is
x
nM vx2
Figure 1B.1 The pressure of a gas arises from the impact Pressure =
V
of its molecules on the walls. In an elastic collision of a
molecule with a wall perpendicular to the x-axis, the Not all the molecules travel with the same velocity, so the
x-component of velocity is reversed but the y- and detected pressure, p, is the average (denoted 〈…〉) of the quan-
z-components are unchanged. tity just calculated:

nM 〈 vx2 〉
p=
V
by the number of molecules that reach the wall during the
interval. This expression already resembles the perfect gas equation of
Because a molecule with velocity component vx can travel state.
a distance vx Δt along the x-axis in an interval Δt, all the mol- To write an expression for the pressure in terms of the root-
ecules within a distance vx Δt of the wall will strike it if they mean-square speed, v rms, we begin by writing the speed of a
are travelling towards it (Fig. 1B.2). It follows that if the wall single molecule, v, as v 2 = vx2 + v 2y + vz2 . Because the root-mean-
has area A, then all the particles in a volume A× v x Δt will square speed is defined as v rms = 〈v2〉1/2, it follows that
reach the wall (if they are travelling towards it). The number
density of particles is nNA /V, where n is the total amount of
2
vrms = 〈 v 2 〉 = 〈 vx2 〉 + 〈 v 2y 〉 + 〈 vz2 〉
molecules in the container of volume V and NA is Avogadro’s However, because the molecules are moving randomly, all three
constant, so the number of molecules in the volume Avx Δt is
(nNA/V) × Avx Δt. averages are the same. It follows that vrms
2
= 〈3vx2 〉. Equation
At any instant, half the particles are moving to the right 1B.1 follows immediately by substituting 〈 vx2 〉 = 13 〈 vrms
2
〉 into
and half are moving to the left. Therefore, the average num- p = nM 〈 vx 〉/V .
2

ber of collisions with the wall during the interval Δt is

1
2
nN A Avx ∆t / V . The total momentum change in that interval Equation 1B.1 is one of the key results of the kinetic model.
is the product of this number and the change 2mvx: We see that, if the root-mean-square speed of the molecules
depends only on the temperature, then at constant temperature
nN A Avx ∆t
Momentum change = × 2mv x pV = constant
2V
 M
nmN A Avx2 ∆t nMAvx2 ∆t which is the content of Boyle’s law. Moreover, for eqn 1B.1 to be
= =
V V the equation of state of a perfect gas, its right-hand side must be
equal to nRT. It follows that the root-mean-square speed of the
molecules in a gas at a temperature T must be
|vx Δt|
1/2
Area, A  3RT 
vrms =  (1B.3)
 M 
Perfect gas RMS speed

Will
Won’t

Brief illustration 1B.1 Molecular speeds

x
For N2 molecules at 25 °C, we use M = 28.02 g mol−1, then
Volume = |vx Δt|A
1/2
 3 × (8.3145 JK −1 mol −1 ) × (298 K ) 
Figure 1B.2 A molecule will reach the wall on the right vrms =   = 515 ms
−1

 0.02802 kg mol −1 
within an interval Δt if it is within a distance vx Δt of the wall
and travelling to the right.
 1B The kinetic model 39

The distribution factorizes into three terms, and we can

Shortly we shall encounter the mean speed, v mean, and the
most probable speed v mp; they are, respectively,
write f(v) = f(vx) f(vy) f(vz) and K = KxKyKz, with

1/2
f (vx ) = K x e − mvx /2 kT
2
 8
vmean =   vrms = 0.921…× (515 ms −1 ) = 475 ms −1
 3π 
1/2 and likewise for the other two axes.
 2 To determine the constant K x , we note that a molecule
vmp =   vrms = 0.816…× (515 ms −1 ) = 420 ms −1
 3 must have a velocity component somewhere in the range
–∞ < vx < ∞, so
Self-test 1B.1 Evaluate the root-mean-square speed of H2 mol-
ecules at 25 °C. ∞
Answer: 1.92 km s −1
∫ −∞
f (v x )dvx = 1

Substitution of the expression for f(vx) then gives

(b)The Maxwell–Boltzmann distribution of Integral G.1 1/2
speeds ∞   2πkT 
1= K x ∫ e − mvx /2 kT dvx = Kx 
2

−∞  m 
Equation 1B.2 is an expression for the mean square speed of
molecules. However, in an actual gas the speeds of individual Therefore, K x = (m/2πkT)1/2 and at this stage we can write
molecules span a wide range, and the collisions in the gas con-
tinually redistribute the speeds among the molecules. Before a 1/2
collision, a molecule may be travelling rapidly, but after a col-  m 
f (vx ) =  e − mv
2
x /2 kT (1B.5)
lision it may be accelerated to a very high speed, only to be  2πkT 
slowed again by the next collision. The fraction of molecules
The probability that a molecule has a velocity in the range vx to
that have speeds in the range v to v + dv is proportional to the vx + dvx, vy to vy + dvy, vz to vz + dvz, is therefore
width of the range, and is written f(v)dv, where f(v) is called
the distribution of speeds. Note that, in common with other 3/2
distribution functions, f(v) acquires physical significance only  m 
e − mvx /2 kT e − mv y /2 kT e − mvz /2 kT ×
2
f (vx ) f (v y ) f (vz ) = 
2 2

after it is multiplied by the range of speeds of interest. In the fol-  2πkT 

lowing Justification we show that the fraction of molecules that dv x dv y dv z
have a speed in the range v to v + dv is f(v)dv, where  m 
3/2

= e − mv dv x dv y dv z
2
/2 kT

3/2
 2πkT 
 M  Perfect
Maxwell–
v 2 e − Mv /2 RT
2
f (v) = 4 π 
 2πRT 
Boltzmann (1B.4)
gas
distribution where v 2 = vx2 + v 2y + vz2 .
The function f(v) is called the Maxwell–Boltzmann distribu- To evaluate the probability that the molecules have a speed
tion of speeds. in the range v to v + dv regardless of direction we think of the
three velocity components as defining three coordinates in
‘velocity space’, with the same properties as ordinary space
except that the coordinates are labelled (v x ,v y,v z) instead
Justification 1B.2 The Maxwell–Boltzmann distribution of (x,y,z). Just as the volume element in ordinary space is
of speeds dxdydz, so the volume element in velocity space is dvxdvydvz.
The sum of all the volume elements in ordinary space that lie
The Boltzmann distribution (Foundations B) implies that the
at a distance r from the centre is the volume of a spherical
fraction of molecules with velocity components v x, v y, and
shell of radius r and thickness dr. That volume is the product
vz is proportional to an exponential function of their kinetic
of its surface area, 4πr2 , and its thickness dr, and is therefore
energy: f(v) = Ke−ε/kT, where K is a constant of proportionality.
4πr2dr. Similarly, the analogous volume in velocity space is
The kinetic energy is
the volume of a shell of radius v and thickness dv, namely
ε = 12 mvx2 + 12 mv 2y + 12 mvz2 4πv 2dv (Fig. 1B.3). Now, because f(v x)f(v y)f(v z), the term in
blue in the last equation, depends only on v 2 , and has the
Therefore, we can use the relation a x+y+z = a xaya z to write same value everywhere in a shell of radius v, the total prob-
ability of the molecules possessing a speed in the range v to
f (v) = Ke −(mvx +mv y +mvz )/2 kT = Ke − mvx /2 kT e − mv y /2 kT e − mvz /2kkT
2 2 2 2
v + dv is the product of the term in blue and the volume of the
2 2
40 1 The properties of gases

vz
Low temperature
Surface area, 4πv 2 Thickness, dv or high molecular mass

Distribution function, f(v)

v Intermediate temperature or
molecular mass

High temperature or
vy low molecular mass
vx

Speed, v
Figure 1B.3 To evaluate the probability that a molecule
has a speed in the range v to v + dv, we evaluate the Figure 1B.4 The distribution of molecular speeds with
total probability that the molecule will have a speed temperature and molar mass. Note that the most probable
that is anywhere on the surface of a sphere of radius speed (corresponding to the peak of the distribution) increases
v = (vx2 + v 2y + vz2 )1/2 by summing the probabilities that it with temperature and with decreasing molar mass, and
is in a volume element dvxdvydvz at a distance v from the simultaneously the distribution becomes broader.
origin.

• A factor v2 (the term before the e) multiplies the

shell of radius v and thickness dv. If this probability is written exponential. This factor goes to zero as v goes to
f(v)dv, it follows that zero, so the fraction of molecules with very low
 m 
3/2 speeds will also be very small whatever their mass.
f (v)dv = 4 πv 2dv  e − mv
2
/2 kT
 2πkT  • The remaining factors (the term in parentheses in
eqn 1B.4 and the 4π) simply ensure that, when we
and f(v) itself, after minor rearrangement, is sum the fractions over the entire range of speeds
3/2 from zero to infinity, then we get 1.
 m 
f (v) = 4 π  v 2e − mv
2
/2 kT
 2πkT  The Maxwell distribution has been verified experimentally.
For example, molecular speeds can be measured directly with
Because m/k = M/R, this expression is eqn 1B.4.
a velocity selector (Fig. 1B.5). The spinning discs have slits that
permit the passage of only those molecules moving through
them at the appropriate speed, and the number of molecules
The important features of the Maxwell–Boltzmann distribu- can be determined by collecting them at a detector.
tion are as follows (and are shown pictorially in Fig. 1B.4):
• Equation 1B.4 includes a decaying exponential (c) Mean values
function (more specifically, a Gaussian function).
Once we have the Maxwell–Boltzmann distribution, we can
Its presence implies that the fraction of molecules
calculate the mean value of any power of the speed by evalu-
with very high speeds will be very small because
ating the appropriate integral. For instance, to evaluate the
e − x becomes very small when x is large.
2

• The factor M/2RT multiplying v2 in the exponent is

Physical interpretation

large when the molar mass, M, is large, so the

exponential factor goes most rapidly towards zero Detector
when M is large. That is, heavy molecules are
unlikely to be found with very high speeds.
• The opposite is true when the temperature, T, is Source
Selector
high: then the factor M/2RT in the exponent is
small, so the exponential factor falls towards zero
relatively slowly as v increases. In other words, a
greater fraction of the molecules can be expected to Figure 1B.5 A velocity selector. Only molecules travelling at
have high speeds at high temperatures than at low speeds within a narrow range pass through the succession of
temperatures. slits as they rotate into position.
 1B The kinetic model 41

∞
vmean = ∫ v f (v)dv
Distribution function, f(v)

with f(v) given in eqn 1B.4. Either use mathematical software

or use the standard integrals in the Resource section.
Answer The integral required is

3/2
 M  ∞
vmean = 4 π  ∫ v 3e − mv dv
2
/2 kT
 2πRT  0

Speed, v Integral G.4 3/2 1/2 1/2

v1 v2   M   2RT   8RT 
= 4π  × 12  =
 2πRT   M   πM 
Figure 1B.6 To calculate the probability that a molecule will
have a speed in the range v1 to v2, we integrate the distribution
Substitution of the data then gives
between those two limits; the integral is equal to the area of
the curve between the limits, as shown shaded here. 1/2
 8 × (8.3145 JK −1 mol −1 ) × (298 K ) 
vmean =  = 475 ms −1
 π × (28.02 ×10 kg mol ) 
−3 −1
fraction of molecules in the range v1 to v2 we evaluate the
integral: We have used 1 J = 1 kg m 2 s −2 (the difference from the earlier
value of 474 is due to rounding effects in that calculation; this
v2

∫
(1B.6) value is more accurate).
F (v1 , v2 ) = f (v)dv
v1
Self-test 1B.2 Evaluate the root-mean-square speed of the
This integral is the area under the graph of f as a function of v molecules by integration. Use mathematical software or use
and, except in special cases, has to be evaluated numerically by a standard integral in the Resource section.
Answer: v rms = (3RT/M)1/2 = 515 m s −1
using mathematical software (Fig. 1B.6). To evaluate the aver-
age value of vn we calculate

∫ (1B.7)
〈vn 〉 = vn f (v)dv
0 As shown in Example 1B.1, we can use the Maxwell–
Boltzmann distribution to evaluate the mean speed, vmean, of
In particular, integration with n = 2 results in eqn 1B.3 for the the molecules in a gas:
mean square speed (v2) of the molecules at a temperature T.
1/2 1/2
We can conclude that the root-mean-square speed of the mol-  8RT   8 Perfect Mean
vmean =  =  vrms (1B.8)
ecules of a gas is proportional to the square root of the tempera-  πM   3π  gas speed
ture and inversely proportional to the square root of the molar
mass. That is, the higher the temperature, the higher the root- We can identify the most probable speed, vmp, from the loca-
mean-square speed of the molecules, and, at a given tempera- tion of the peak of the distribution:
ture, heavy molecules travel more slowly than light molecules.
1/2 1/2 Most
Sound waves are pressure waves, and for them to propagate the  2RT   2 Perfect
probable
vmp =  =  vrms gas (1B.9)
molecules of the gas must move to form regions of high and low  M   3 speed
pressure. Therefore, we should expect the root-mean-square
speeds of molecules to be comparable to the speed of sound in The location of the peak of the distribution is found by differ-
air (340 m s−1). As we have seen, the root-mean-square speed of entiating f(v) with respect to v and looking for the value of v at
N2 molecules, for instance, is 515 m s−1 at 298 K. which the derivative is zero (other than at v = 0 and v = ∞); see
Problem 1B.3. Figure 1B.7 summarizes these results and some
numerical values were calculated in Brief illustration 1B.1.
Example 1B.1 Calculating the mean speed of molecules The mean relative speed, vrel, the mean speed with which
in a gas one molecule approaches another of the same kind, can also be
calculated from the distribution:
Calculate the mean speed, vmean, of N2 molecules in air at 25 °C.
Perfect gas, Mean
Method The mean speed is obtained by evaluating the integral vrel = 21/2 vmean identical relative (1B.10a)
molecules speed
42 1 The properties of gases

Self-test 1B.3 What is the relative mean speed of N2 and H2

vmp = (2RT/M)1/2
molecules in a gas at 25 °C?
vmean= (8RT/πM)1/2
Answer: 1.83 km s −1
f(v)/4π(M/2πRT)1/2

vrms = (3RT/M)1/2

1B.2 Collisions
1 (3/2)1/2 The kinetic model enables us to make the qualitative picture of
a gas as a collection of ceaselessly moving, colliding molecules
(4/π)1/2 v/(2RT/M)1/2 more quantitative. In particular, it enables us to calculate the
frequency with which molecular collisions occur and the dis-
Figure 1B.7 A summary of the conclusions that can be deduced tance a molecule travels on average between collisions.
form the Maxwell distribution for molecules of molar mass M
at a temperature T: vmp is the most probable speed, vmean is the
mean speed, and vrms is the root-mean-square speed. (a) The collision frequency
Although the kinetic-molecular theory assumes that the mol-
This result is much harder to derive, but the diagram in Fig. ecules are point-like, we can count a ‘hit’ whenever the centres
1B.8 should help to show that it is plausible. For the relative of two molecules come within a distance d of each other, where
mean speed of two dissimilar molecules of masses mA and mB: d, the collision diameter, is of the order of the actual diameters
of the molecules (for impenetrable hard spheres d is the diam-
 8kT 
1/2
mA mB Perfect Mean eter). As we show in the following Justification, we can use the
vrel =  μ=
 πμ 
gas relative (1B.10b) kinetic model to deduce that the collision frequency, z, the
mA + mB speed
number of collisions made by one molecule divided by the time
interval during which the collisions are counted, when there
21/2v v are N molecules in a volume V is
v
z =σ vrel N Perfect gas Collision frequency (1B.11a)

v
v v with N = N/V, the number density, and vrel given by eqn 1B.10.
0 21/2v 2v
The area σ = πd2 is called the collision cross-section of the mol-
v v v ecules. Some typical collision cross-sections are given in Table
1B.1. In terms of the pressure (as is also shown in the following
Justification),

Figure 1B.8 A simplified version of the argument to show σ vrel p

that the mean relative speed of molecules in a gas is related z= Perfect gas Collision frequency (1B.11b)
kT
to the mean speed. When the molecules are moving in the
same direction, the mean relative speed is zero; it is 2v when Table 1B.1* Collision cross-sections, σ/nm2
the molecules are approaching each other. A typical mean
direction of approach is from the side, and the mean speed σ/nm2
of approach is then 21/2v. The last direction of approach is the
C6H6 0.88
most characteristic, so the mean speed of approach can be
expected to be about 21/2v. This value is confirmed by more CO2 0.52
detailed calculation. He 0.21
N2 0.43
* More values are given in the Resource section.
Brief illustration 1B.2 Relative molecular speeds
We have already seen (in Brief illustration 1B.1) that the rms Justification 1B.3 The collision frequency according to
speed of N2 molecules at 25 °C is 515 m s −1. It follows from eqn the kinetic model
1B.10a that their relative mean speed is
Consider the positions of all the molecules except one to
vrel = 2 × (515 ms ) = 728 ms
1/2 −1 −1 be frozen. Then note what happens as one mobile molecule
travels through the gas with a mean relative speed v rel for a

Miss
vrelΔt
d
d Hit
Area, σ
Figure 1B.9 The calculation of the collision frequency and
the mean free path in the kinetic theory of gases.
time Δt. In doing so it sweeps out a ‘collision tube’ of cross-
sectional area σ = πd 2 and length v rel Δt and therefore of vol-
ume σ v rel Δt (Fig. 1B.9). The number of stationary molecules
with centres inside the collision tube is given by the volume
of the tube multiplied by the number density N = N/V, and is
Nσ v rel Δt. The number of hits scored in the interval Δt is equal
to this number, so the number of collisions divided by the
time interval is Nσ v rel, which is eqn 1B.11a. The expression
in terms of the pressure of the gas is obtained by using the
perfect gas equation to write
N nN nN A p
N= = A= = In Brief illustration 1B.2 we noted that v rel = 728 m s −1 for
V V nRT /p kT
Equation 1B.11a shows that, at constant volume, the collision
frequency increases with increasing temperature. Equation
1B.11b shows that, at constant temperature, the collision fre-
quency is proportional to the pressure. Such a proportion-
ality is plausible because the greater the pressure, the greater
the number density of molecules in the sample, and the rate at
which they encounter one another is greater even though their
average speed remains the same.
Brief illustration 1B.3 Molecular collisions
For an N2 molecule in a sample at 1.00 atm (101 kPa) and
25 °C, from Brief illustration 1B.2 we know that v rel = 728 m s −1.
Therefore, from eqn 1B.11b, and taking σ = 0.45 nm 2 (corres­
ponding to 0.45 × 10−18 m2) from Table 1B.1,
(0.43 × 10−18 m2 ) × (728 ms −1 ) × (1.01 × 105 Pa )
z=
(1.381 ×10−23 JK −1 ) × (298 K )
= 7.7 ×109 s −1
so a given molecule collides about 8 × 109 times each second.
We are beginning to appreciate the timescale of events in
gases.
Self-test 1B.4 Evaluate the collision frequency between H2
molecules in a gas under the same conditions.
Answer: 4.1 × 109 s −1
1B The kinetic model 43
(b) The mean free path
Once we have the collision frequency, we can calculate the
mean free path, λ (lambda), the average distance a molecule
travels between collisions. If a molecule collides with a fre-
quency z, it spends a time 1/z in free flight between collisions,
and therefore travels a distance (1/z)vrel. It follows that the
mean free path is
vrel
λ= Perfect gas Mean free path (1B.12)
z
Substitution of the expression for z in eqn 1B.11b gives
kT
λ= Perfect gas Mean free path (1B.13)
σp
Doubling the pressure reduces the mean free path by half.
Brief illustration 1B.4 The mean free path
N2 molecules at 25 °C, and in Brief illustration 1B.3 that
z = 7.7 × 109 s −1 when the pressure is 1.00 atm. Under these cir-
cumstances, the mean free path of N2 molecules is
728 ms −1
λ= = 9.5 ×10−8 m
7.7 ×109 s −1
or 95 nm, about103 molecular diameters.
Self-test 1B.5 Evaluate the mean free path of benzene
­molecules at 25 °C in a sample where the pressure is 0.10 atm.
Answer: 460 nm
Although the temperature appears in eqn 1B.13, in a sam-
ple of constant volume, the pressure is proportional to T, so
T/p remains constant when the temperature is increased.
Therefore, the mean free path is independent of the temper-
ature in a sample of gas in a container of fixed volume: the
distance between collisions is determined by the number of
molecules present in the given volume, not by the speed at
which they travel.
In summary, a typical gas (N2 or O2) at 1 atm and 25 °C can
be thought of as a collection of molecules travelling with a
mean speed of about 500 m s−1. Each molecule makes a colli-
sion within about 1 ns, and between collisions it travels about
103 molecular diameters. The kinetic model of gases is valid
and the gas behaves nearly perfectly if the diameter of the
molecules is much smaller than the mean free path (d ≪ λ),
for then the molecules spend most of their time far from one
another.
44 1 The properties of gases

Checklist of concepts
☐ 1. The kinetic model of a gas considers only the contri- ☐ 4. The collision frequency is the number of collisions
bution to the energy from the kinetic energies of the made by a molecule in an interval divided by the length
molecules. of the interval.
☐ 2. Important results from the model include expressions ☐ 5. The mean free path is the average distance a molecule
for the pressure and the root-mean-square speed. travels between collisions.
☐ 3. The Maxwell–Boltzmann distribution of speeds gives
the fraction of molecules that have speeds in a specified
range.

Checklist of equations
Property Equation Comment Equation number
1 2
Pressure of a perfect gas from the kinetic model pV = 3
nM vrms Kinetic model 1B.1

f (v) = 4 π(M /2πRT )3/2 v2 e − M v

2
Maxwell–Boltzmann distribution of speeds /2 RT 1B.4

Root-mean-square speed in a perfect gas vrms = (3RT/M)1/2 1B.3

Mean speed in a perfect gas vmean = (8RT/πM)1/2 1B.8

Most probable speed in a perfect gas vmp = (2RT/M)1/2 1B.9

Mean relative speed in a perfect gas vrel = (8kT/πµ)1/2 1B.10

μ = mAmB/(mA + mB)

The collision frequency in a perfect gas z = σ vrelp/kT, σ = πd2 1B.11

Mean free path in a perfect gas λ = vrel/z 1B.12

1C Real gases

Real gases do not obey the perfect gas law exactly except in the
Contents limit of p → 0. Deviations from the law are particularly impor-
tant at high pressures and low temperatures, especially when a
1C.1 Deviations from perfect behaviour 45
gas is on the point of condensing to liquid.
(a) The compression factor 46
Brief illustration 1C.1: The compression factor 47
(b) Virial coefficients 47
Brief illustration 1C.2: The virial equation of state 47 Deviations from perfect
1C.1
(c) Critical constants
Brief illustration 1C.3: The critical temperature
48
48
behaviour
1C.2 The van der Waals equation 48
Real gases show deviations from the perfect gas law because
(a) Formulation of the equation 48
molecules interact with one another. A point to keep in mind
Example 1C.1: Using the van der Waals equation to
is that repulsive forces between molecules assist expansion and
estimate a molar volume 49
attractive forces assist compression.
(b) The features of the equation 50
Repulsive forces are significant only when molecules are
Brief illustration 1C.4: Criteria for perfect gas
behaviour 52 almost in contact: they are short-range interactions, even on
(c) The principle of corresponding states 52 a scale measured in molecular diameters (Fig. 1C.1). Because
Brief illustration 1C.5: Corresponding states 52 they are short-range interactions, repulsions can be expected
Checklist of concepts 53 to be important only when the average separation of the mol-
Checklist of equations 53 ecules is small. This is the case at high pressure, when many
molecules occupy a small volume. On the other hand, attrac-
tive intermolecular forces have a relatively long range and are
effective over several molecular diameters. They are important
when the molecules are fairly close together but not neces-
sarily touching (at the intermediate separations in Fig. 1C.1).
➤➤ Why do you need to know this material?
Actual gases, so-called ‘real gases’, differ from perfect
gases and it is important to be able to discuss their
Potential energy, Ep

properties. Moreover, the deviations from perfect

Repulsion dominant

behaviour give insight into the nature of the interactions

between molecules. Accounting for these interactions is
also an introduction to the technique of model building
in physical chemistry.
0

➤➤ What is the key idea? Attraction

Attractions and repulsions between gas molecules account
for modifications to the isotherms of a gas and account for
critical behaviour.
➤➤ What do you need to know already?
This Topic builds on and extends the discussion of perfect
gases in Topic 1A. The principal mathematical technique
employed is differentiation to identify a point of inflexion
of a curve.
dominant
Separation
Figure 1C.1 The variation of the potential energy of two
molecules on their separation. High positive potential energy
(at very small separations) indicates that the interactions
between them are strongly repulsive at these distances.
At intermediate separations, where the potential energy
is negative, the attractive interactions dominate. At large
separations (on the right) the potential energy is zero and there
is no interaction between the molecules.
46 1 The properties of gases

Attractive forces are ineffective when the molecules are far
apart (well to the right in Fig. 1C.1). Intermolecular forces are
also important when the temperature is so low that the mol-
ecules travel with such low mean speeds that they can be cap-
tured by one another.
The consequences of these interactions are shown by shapes
of experimental isotherms (Fig. 1C.2). At low pressures, when
the sample occupies a large volume, the molecules are so far
apart for most of the time that the intermolecular forces play
no significant role, and the gas behaves virtually perfectly. At
moderate pressures, when the average separation of the mol-
ecules is only a few molecular diameters, the attractive forces
dominate the repulsive forces. In this case, the gas can be
expected to be more compressible than a perfect gas because
the forces help to draw the molecules together. At high pres-
sures, when the average separation of the molecules is small,
the repulsive forces dominate and the gas can be expected to
be less compressible because now the forces help to drive the
molecules apart.
Consider what happens when we compress (reduce the vol-
ume of) a sample of gas initially in the state marked A in Fig.
1C.2 at constant temperature by pushing in a piston. Near A,
the pressure of the gas rises in approximate agreement with
Boyle’s law. Serious deviations from that law begin to appear
when the volume has been reduced to B.
At C (which corresponds to about 60 atm for carbon
di­oxide), all similarity to perfect behaviour is lost, for sud-
denly the piston slides in without any further rise in pres-
sure: this stage is represented by the horizontal line CDE.
Examination of the contents of the vessel shows that just to the
left of C a liquid appears, and there are two phases separated
by a sharply defined surface. As the volume is decreased from
C through D to E, the amount of liquid increases. There is no
additional resistance to the piston because the gas can respond
by condensing. The pressure corresponding to the line CDE,
when both liquid and vapour are present in equilibrium, is
called the vapour pressure of the liquid at the temperature of
the experiment.
At E, the sample is entirely liquid and the piston rests on its
surface. Any further reduction of volume requires the exertion
of considerable pressure, as is indicated by the sharply rising
line to the left of E. Even a small reduction of volume from E to
F requires a great increase in pressure.
(a) The compression factor
As a first step in making these observations quantitative we
introduce the compression factor, Z, the ratio of the measured
molar volume of a gas, Vm = V/n, to the molar volume of a per-
fect gas, Vm° , at the same pressure and temperature:
°
Vm
Z= Definition Compression factor (1C.1)
Vm°
Because the molar volume of a perfect gas is equal to RT/p, an
equivalent expression is Z = RT / pVm° , which we can write as
pVm = RTZ (1C.2)
Because for a perfect gas Z = 1 under all conditions, deviation
of Z from 1 is a measure of departure from perfect behaviour.
Some experimental values of Z are plotted in Fig. 1C.3. At
very low pressures, all the gases shown have Z ≈ 1 and behave
nearly perfectly. At high pressures, all the gases have Z > 1, sig-
nifying that they have a larger molar volume than a perfect gas.
Repulsive forces are now dominant. At intermediate pressures,
most gases have Z < 1, indicating that the attractive forces are
reducing the molar volume relative to that of a perfect gas.

C2H4
140
CH4
Compression factor, Z

120
50 °C H2
100
40 °C Perfect
80 F 31.1 °C (Tc)
p/atm

H2
20 °C 1
60 Z p/atm
10
E D C 0.98 CH4
40 B
NH3 0.96 C2H4
20 A NH3
0 200 400 600 800
0 p/atm
0 0.2 0.4 0.6
Vm/(dm mol )
3 –1

Figure 1C.3 The variation of the compression factor, Z, with

Figure 1C.2 Experimental isotherms of carbon dioxide at pressure for several gases at 0 °C. A perfect gas has Z = 1 at all
several temperatures. The ‘critical isotherm’, the isotherm at the pressures. Notice that, although the curves approach 1 as p → 0,
critical temperature, is at 31.1 °C. they do so with different slopes.
 1C Real gases 47

Brief illustration 1C.1 The compression factor Table 1C.1* Second virial coefficients, B/(cm3 mol−1)

The molar volume of a perfect gas at 500 K and 100 bar is

Temperature
Vm = 0.416 dm3 mol −1. The molar volume of carbon dioxide
under the same conditions is Vm = 0.366 dm3 mol−1. It follows 273 K 600 K
that at 500 K Ar –21.7 11.9
CO2 –149.7 –12.4
0.366 dm3 mol −1
Z= = 0.880 N2 –10.5 21.7
0.416 dm3 mol −1
Xe –153.7 –19.6
The fact that Z < 1 indicates that attractive forces dominate * More values are given in the Resource section.
repulsive forces under these conditions.
Brief illustration 1C.2 The virial equation of state
Self-test 1C.1 The mean molar volume of air at 60 bar and
400 K is 0.9474 dm 3 mol −1. Are attractions or repulsions To use eqn 1C.3b (up to the B term), to calculate the pressure
dominant? exerted at 100 K by 0.104 mol O2(g) in a vessel of volume 0.225
Answer: Repulsions dm3, we begin by calculating the molar volume:

V 0.225 dm3
Vm = = = 2.16 dm3 mol −1 = 2.16 ×10−3 m3 mol −1
nO2 0.104 mol
(b) Virial coefficients
Then, by using the value of B found in Table 1C.1 of the
Now we relate Z to the experimental isotherms in Fig. 1C.2. At Resource section,
large molar volumes and high temperatures the real-gas iso-
therms do not differ greatly from perfect-gas isotherms. The RT  B 
p= 1+
Vm  Vm 
small differences suggest that the perfect gas law pVm = RT is in
fact the first term in an expression of the form (8.3145 Jmol −1 K −1) × (100 K)  1.975 × 10−4 m 3 mol −1 
=  1 − 2.16 × 10−3 m 3 mol −1 
2.16 × 10−3 m 3 mol −1
pVm = RT (1+ B ′ p + C ′ p2 +) (1C.3a) = 3.50 × 105 Pa, or 350 kPa

This expression is an example of a common procedure in physi-
cal chemistry, in which a simple law that is known to be a good
first approximation (in this case pVm = RT) is treated as the first
term in a series in powers of a variable (in this case p). A more
convenient expansion for many applications is
 B C 
pVm = RT  1 + + +  Virial equation of state (1C.3b)
 Vm Vm2  equation of state?
These two expressions are two versions of the virial equation of
state.1 By comparing the expression with eqn 1C.2 we see that
the term in parentheses in eqn 1C.3b is just the compression
factor, Z.
The coefficients B, C, …, which depend on the temperature,
are the second, third, ... virial coefficients (Table 1C.1); the
first virial coefficient is 1. The third virial coefficient, C, is usu-
ally less important than the second coefficient, B, in the sense
that at typical molar volumes C /Vm2 /B /Vm . The values of the
virial coefficients of a gas are determined from measurements
of its compression factor.
where we have used 1 Pa = 1 J m−3. The perfect gas equation of
state would give the calculated pressure as 385 kPa, or 10 per
cent higher than the value calculated by using the virial equa-
tion of state. The deviation is significant because under these
conditions B/Vm ≈ 0.1 which is not negligible relative to 1.
Self-test 1C.2 What pressure would 4.56 g of nitrogen gas in a
vessel of volume 2.25 dm3 exert at 273 K if it obeyed the virial
Answer: 104 kPa
An important point is that although the equation of state of
a real gas may coincide with the perfect gas law as p → 0, not all
its properties necessarily coincide with those of a perfect gas in
that limit. Consider, for example, the value of dZ/dp, the slope
of the graph of compression factor against pressure. For a per-
fect gas dZ/dp = 0 (because Z = 1 at all pressures), but for a real
gas from eqn 1C.3a we obtain
dZ
= B′ + 2 pC ′ +  → B ′ as p → 0 (1C.4a)
dp

1 The name comes from the Latin word for force. The coefficients are However, B′ is not necessarily zero, so the slope of Z with
sometimes denoted B2, B3, …. respect to p does not necessarily approach 0 (the perfect gas
48 1 The properties of gases

An isotherm slightly below Tc behaves as we have already

Higher described: at a certain pressure, a liquid condenses from the
Compression factor, Z

Boyle temperature gas and is distinguishable from it by the presence of a visible

temperature
surface. If, however, the compression takes place at Tc itself,
Perfect then a surface separating two phases does not appear and the
gas
volumes at each end of the horizontal part of the isotherm
have merged to a single point, the critical point of the gas.
Lower The temperature, pressure, and molar volume at the critical
temperature point are called the critical temperature, Tc, critical pres-
sure, pc, and critical molar volume, Vc, of the substance.
Pressure, p
Collectively, pc, Vc, and Tc are the critical constants of a sub-
Figure 1C.4 The compression factor, Z, approaches 1 at low stance (Table 1C.2).
pressures, but does so with different slopes. For a perfect gas, At and above Tc, the sample has a single phase which occu-
the slope is zero, but real gases may have either positive or pies the entire volume of the container. Such a phase is, by
negative slopes, and the slope may vary with temperature. At definition, a gas. Hence, the liquid phase of a substance does
the Boyle temperature, the slope is zero and the gas behaves not form above the critical temperature. The single phase that
perfectly over a wider range of conditions than at other fills the entire volume when T > Tc may be much denser that we
temperatures. normally consider typical of gases, and the name supercritical
fluid is preferred.
value), as we can see in Fig. 1C.4. Because several physical
properties of gases depend on derivatives, the properties of real
Brief illustration 1C.3 The critical temperature
gases do not always coincide with the perfect gas values at low
pressures. By a similar argument, The critical temperature of oxygen signifies that it is impos-
sible to produce liquid oxygen by compression alone if its tem-
dZ perature is greater than 155 K. To liquefy oxygen—to obtain a
→ B as Vm → ∞ (1C.4b)
d(1/Vm ) fluid phase that does not occupy the entire volume—the tem-
perature must first be lowered to below 155 K, and then the gas
Because the virial coefficients depend on the temperature, compressed isothermally.
there may be a temperature at which Z → 1 with zero slope at
Self-test 1C.3 Under which conditions can liquid nitrogen be
low pressure or high molar volume (as in Fig. 1C.4). At this
formed by the application of pressure?
tempera­ture, which is called the Boyle temperature, TB, the
Answer: At T < 126 K
properties of the real gas do coincide with those of a perfect gas
as p → 0. According to eqn 1C.4b, Z has zero slope as p → 0 if
B = 0, so we can conclude that B = 0 at the Boyle temperature. It
then follows from eqn 1C.3 that pVm ≈ RTB over a more extended
range of pressures than at other temperatures because the first 1C.2 The van der Waals equation
term after 1 (that is, B/Vm) in the virial equation is zero and C/Vm2
and higher terms are negligibly small. For helium TB = 22.64 K; We can draw conclusions from the virial equations of state
for air TB = 346.8 K; more values are given in Table 1C.2. only by inserting specific values of the coefficients. It is often
useful to have a broader, if less precise, view of all gases.
Therefore, we introduce the approximate equation of state
(c) Critical constants suggested by J.D. van der Waals in 1873. This equation is an
The isotherm at the temperature Tc (304.19 K, or 31.04 °C for excellent example of an expression that can be obtained by
CO2) plays a special role in the theory of the states of matter. thinking scientifically about a mathematically complicated
but physically simple problem; that is, it is a good example of
Table 1C.2* Critical constants of gases ‘model building’.
pc/atm Vc/(cm3 mol−1) Tc/K Zc TB/K
Ar 48.0 75.3 150.7 0.292 411.5 (a) Formulation of the equation
CO2 72.9 94.0 304.2 0.274 714.8
The van der Waals equation is
He 2.26 57.8 5.2 0.305 22.64
O2 50.14 78.0 154.8 0.308 405.9
nRT n2
p= −a 2 Van der Waals equation of state (1C.5a)
* More values are given in the Resource section. V − nb V
 1C Real gases 49

and a derivation is given in the following Justification. The Justification 1C.1 The van der Waals equation of state
equation is often written in terms of the molar volume
Vm = V/n as The repulsive interactions between molecules are taken into
account by supposing that they cause the molecules to behave
RT a as small but impenetrable spheres. The non-zero volume of the
p= − (1C.5b) molecules implies that instead of moving in a volume V they
Vm − b Vm2
are restricted to a smaller volume V − nb, where nb is approxi-
The constants a and b are called the van der Waals coeffi- mately the total volume taken up by the molecules themselves.
cients. As can be understood from the following Justification, This argument suggests that the perfect gas law p = nRT/V
should be replaced by
a represents the strength of attractive interactions and b that
of the repulsive interactions between the molecules. They nRT
p=
are characteristic of each gas but independent of the tem- V − nb
perature (Table 1C.3). Although a and b are not precisely
defined molecular properties, they correlate with physical when repulsions are significant. To calculate the excluded
volume we note that the closest distance of two hard-sphere
properties such as critical temperature, vapour pressure, and
molecules of radius r, and volume Vmolecule = 43 πr 3, is 2r, so
enthalpy of vaporization that reflect the strength of inter-
the volume excluded is 43 π(2r )3 , or 8Vmolecule . The volume
molecular interactions. Correlations have also been sought
excluded per molecule is one-half this volume, or 4Vmolecule, so
where intermolecular forces might play a role. For example,
b ≈ 4VmoleculeNA.
the potency of certain general anaesthetics shows a correla- The pressure depends on both the frequency of colli-
tion in the sense that a higher activity is observed with lower sions with the walls and the force of each collision. Both
values of a (Fig. 1C.5). the frequency of the collisions and their force are reduced
by the attractive interaction, which act with a strength pro-
portional to the molar concentration, n/V, of molecules in
Table 1C.3* van der Waals coefficients the sample. Therefore, because both the frequency and the
force of the collisions are reduced by the attractive interac-
a/(atm dm6 mol−2) b/(10−2 dm3 mol−1) tions, the pressure is reduced in proportion to the square of
Ar 1.337 3.20 this concentration. If the reduction of pressure is written
as a(n/V)2 , where a is a positive constant characteristic of
CO2 3.610 4.29
each gas, the combined effect of the repulsive and attractive
He 0.0341 2.38 forces is the van der Waals equation of state as expressed in
Xe 4.137 5.16 eqn 1C.5.
In this Justification we have built the van der Waals equa-
* More values are given in the Resource section.
tion using vague arguments about the volumes of molecules
and the effects of forces. The equation can be derived in other
ways, but the present method has the advantage that it shows
100 He Ne
how to derive the form of an equation out of general ideas. The
Ar derivation also has the advantage of keeping imprecise the
10
significance of the coefficients a and b: they are much better
Kr SF6
N2O regarded as empirical parameters that represent attractions
pisonarcotic/atm

1
N2 and repulsions, respectively, rather than as precisely defined
Xe molecular properties.
0.1 cyclo-C3H6
Halothane
0.01
CHCl3
Example 1C.1 Using the van der Waals equation to
0.001
0 1 2 3 4 5 6 estimate a molar volume
{a/(atm dm6 mol–2)}1/2
Estimate the molar volume of CO2 at 500 K and 100 atm by
Figure 1C.5 The correlation of the effectiveness of a gas as an treating it as a van der Waals gas.
anaesthetic and the van der Waals parameter a. (Based on R.J.
Wulf and R.M. Featherstone, Anesthesiology 18, 97 (1957).) The Method We need to find an expression for the molar vol-
isonarcotic pressure is the pressure required to bring about the ume by solving the van der Waals equation, eqn 1C.5b. To do
same degree of anaesthesia.
50 1 The properties of gases

so, we multiply both sides of the equation by (Vm − b)Vm2 , to 6

obtain
4
(Vm − b)Vm2 p = RTVm2 − (Vm − b)a
2

1000f(x)
Then, after division by p, collect powers of Vm to obtain
0

 RT  2  a 
Vm3 −  b + V + V =0 –2
 p  m  p  m
–4
Although closed expressions for the roots of a cubic equa-
–6
tion can be given, they are very complicated. Unless ana- 0 0.1 0.2 x 0.3 0.4
lytical solutions are essential, it is usually more expedient
to solve such equations with commercial software; graphing Figure 1C.6 The graphical solution of the cubic equation
calculators can also be used to help identify the acceptable for V in Example 1C.1.
root.
Self-test 1C.4 Calculate the molar volume of argon at 100 °C
Answer According to Table 1C.3, a = 3.592 dm 6 atm mol −2 and 100 atm on the assumption that it is a van der Waals gas.
and b = 4.267 × 10 −2 dm 3 mol−1. Under the stated conditions, Answer: 0.298 dm3 mol−1
RT/p = 0.410 dm3 mol−1. The coefficients in the equation for Vm
are therefore

b + RT /p = 0.453 dm3 mol −1 (b) The features of the equation

a/p = 3.61 × 10−2 (dm3 mol −1 )2
ab/p = 1.55 × 10−33 (dm3 mol −1 )3
We now examine to what extent the van der Waals equation
predicts the behaviour of real gases. It is too optimistic to
expect a single, simple expression to be the true equation of
Therefore, on writing x = Vm /(dm 3 mol −1), the equation to
state of all substances, and accurate work on gases must resort
solve is
to the virial equation, use tabulated values of the coefficients
x 3 − 0.453x 2 + (3.61 × 10−2 )x − (1.55 ×10−3 ) = 0 at various temperatures, and analyse the systems numerically.
The advantage of the van der Waals equation, however, is that
The acceptable root is x = 0.366 (Fig. 1C.6), which implies that it is analytical (that is, expressed symbolically) and allows us
Vm = 0.366 dm3 mol−1. For a perfect gas under these conditions, to draw some general conclusions about real gases. When the
the molar volume is 0.410 dm3 mol−1. equation fails we must use one of the other equations of state
that have been proposed (some are listed in Table 1C.4), invent
a new one, or go back to the virial equation.

Table 1C.4 Selected equations of state

Critical constants
Equation Reduced form* pc Vc Tc

Perfect gas nRT

p=
V

van der Waals nRT n2a 8Tr 3 a 3b 8a

p= − pr = −
V − nb V 2 3Vr −1 Vr2 27b2 27bR

8Tr 3 1/2
Berthelot nRT n2a 1  2aR  3b 2  2a 
1/2
p= − pr = −
V − nb TV 2 3Vr −1 TrVr2 12  3b3  3  3bR 

Dieterici nRTe −aRTV /n Tr e2(1−1/TrVr ) a 2b a

p= pr = 4bR
V − nb 2Vr −1 4e2b2

Virial nRT  nB(T ) n2C(T ) 

p= 1+ V + +
V  V2 

* Reduced variables are defined in Section 1C.2(c). Equations of state are sometimes expressed in terms of the molar volume, Vm = V/n.
 1C Real gases 51

That having been said, we can begin to judge the reliability
of the equation by comparing the isotherms it predicts with
the experimental isotherms in Fig. 1C.2. Some calculated iso-
therms are shown in Fig. 1C.7 and Fig. 1C.8. Apart from the
oscillations below the critical temperature, they do resemble
experimental isotherms quite well. The oscillations, the van der
Waals’ loops, are unrealistic because they suggest that under
some conditions an increase of pressure results in an increase of
volume. Therefore they are replaced by horizontal lines drawn
so the loops define equal areas above and below the lines: this
procedure is called the Maxwell construction (1). The van der
Waals coefficients, such as those in Table 1C.3, are found by fit-
ting the calculated curves to the experimental curves.
Equal
areas
1 second represents the effect of the attractive interactions.
1.5
Pressure, p
The principal features of the van der Waals equation can be
summarized as follows.
1. Perfect gas isotherms are obtained at high temperatures
and large molar volumes.
When the temperature is high, RT may be so large that the first
term in eqn 1C.5b greatly exceeds the second. Furthermore,
if the molar volume is large in the sense Vm ≫ b, then the
denominator Vm - b ≈ Vm. Under these conditions, the equation
reduces to p = RT/Vm, the perfect gas equation.
2. Liquids and gases coexist when the attractive and
repulsive effects are in balance.
The van der Waals loops occur when both terms in eqn 1C.5b
have similar magnitudes. The first term arises from the kinetic
energy of the molecules and their repulsive interactions; the
3. The critical constants are related to the van der Waals
coefficients.
For T < Tc, the calculated isotherms oscillate, and each one
passes through a minimum followed by a maximum. These
extrema converge as T→ Tc and coincide at T = Tc; at the criti-
cal point the curve has a flat inflexion (2). From the properties

1.0
of curves, we know that an inflexion of this type occurs when
0.8 both the first and second derivatives are zero. Hence, we can
find the critical constants by calculating these derivatives and
setting them equal to zero at the critical point:
,T
re
atu
Volume, V p er
m
Te

Figure 1C.7 The surface of possible states allowed by the van 2

der Waals equation. Compare this surface with that shown in
Fig. 1C.8.
dp RT 2a
=− + =0
dVm (Vm − b)2 Vm3
1.5
1.5 d2 p 2RT 6a
= − =0
dVm2 (Vm − b)3 Vm4
Reduced pressure, p/pc

1 1
The solutions of these two equations (and using eqn 1C.5b to
calculate pc from Vc and Tc) are

0.5 a 8a
Vc = 3b pc = Tc = (1C.6)
0.8 27b2 27 Rb

0 These relations provide an alternative route to the determina-

0.1 1
Reduced volume, Vm/Vc
10 tion of a and b from the values of the critical constants. They
can be tested by noting that the critical compression factor, Zc,
Figure 1C.8 van der Waals isotherms at several values of T/Tc. is predicted to be equal to
Compare these curves with those in Fig. 1C.2. The van der
Waals loops are normally replaced by horizontal straight lines. pcVc 3
Zc = = (1C.7)
The critical isotherm is the isotherm for T/Tc = 1. RTc 8
52 1 The properties of gases

for all gases that are described by the van der Waals equation 1
near the critical point. We see from Table 1C.2 that although 2.0
Z c < 83 = 0.375, it is approximately constant (at 0.3) and the dis- 0.8

Compression factor, Z
crepancy is reasonably small.
0.6
1.2
Nitrogen
Brief illustration 1C.4 Criteria for perfect gas behaviour 0.4 Methane
1.0
For benzene a = 18.57 atm dm6 mol−2 (1.882 Pa m6 mol−2) and Propane
b = 0.1193 dm 3 mol−1 (1.193 × 10 −4 m 3 mol−1); its normal boil- 0.2
Ethene
ing point is 353 K. Treated as a perfect gas at T = 400 K and
p = 1.0 atm, benzene vapour has a molar volume of Vm = RT/p = 0
0 1 2 3 4 5 6 7
33 dm mol−1, so the criterion Vm ≫ b for perfect gas behaviour Reduced pressure, p/pc
is satisfied. It follows that a / Vm2 ≈ 0.017 atm, which is 1.7 per
cent of 1.0 atm. Therefore, we can expect benzene vapour to Figure 1C.9 The compression factors of four of the gases
deviate only slightly from perfect gas behaviour at this tem- shown in Fig. 1C.3 plotted using reduced variables. The curves
perature and pressure. are labelled with the reduced temperature Tr = T/Tc. The use of
reduced variables organizes the data on to single curves.
Self-test 1C.5 Can argon gas be treated as a perfect gas at 400 K
and 3.0 atm?
Answer: Yes
Brief illustration 1C.5 Corresponding states
The critical constants of argon and carbon dioxide are given in
Table 1C.2. Suppose argon is at 23 atm and 200 K, its reduced
(c) The principle of corresponding states pressure and temperature are then

An important general technique in science for comparing the 23 atm 200 K

pr = = 0.48 Tr = = 1.33
properties of objects is to choose a related fundamental prop- 48.0 atm 150.7 K
erty of the same kind and to set up a relative scale on that basis.
For carbon dioxide to be in a corresponding state, its pressure
We have seen that the critical constants are characteristic prop-
and temperature would need to be
erties of gases, so it may be that a scale can be set up by using
them as yardsticks. We therefore introduce the dimensionless p = 0.48 × (72.9 atm) = 35 atm T = 1.33 × 304.2 K = 405 K
reduced variables of a gas by dividing the actual variable by the
corresponding critical constant: Self-test 1C.6 What would be the corresponding state of
ammonia?
Vm p T Answer: 53 atm, 539 K
Vr = pr = Tr = Definition Reduced variables (1C.8)
Vc pc Tc

If the reduced pressure of a gas is given, we can easily calcu- The van der Waals equation sheds some light on the princi-
late its actual pressure by using p = prpc, and likewise for the ple. First, we express eqn 1C.5b in terms of the reduced vari-
volume and temperature. van der Waals, who first tried this ables, which gives
procedure, hoped that gases confined to the same reduced vol-
ume, Vr, at the same reduced temperature, Tr, would exert the RTrTc a
pr pc = − 2 2
same reduced pressure, pr. The hope was largely fulfilled (Fig. VrVc − b Vr Vc
1C.9). The illustration shows the dependence of the compres-
sion factor on the reduced pressure for a variety of gases at Then we express the critical constants in terms of a and b by
various reduced temperatures. The success of the procedure using eqn 1C.8:
is strikingly clear: compare this graph with Fig. 1C.3, where
similar data are plotted without using reduced variables. The apr 8aTr / 27b a
= −
observation that real gases at the same reduced volume and 27b 2 3bpVr − b 9b 2Vr2
reduced temperature exert the same reduced pressure is called
the principle of corresponding states. The principle is only an which can be reorganized into
approximation. It works best for gases composed of spherical
molecules; it fails, sometimes badly, when the molecules are 8Tr 3
pr = − (1C.9)
non-spherical or polar. 3Vr − 1 Vr2

This equation has the same form as the original, but the coeffi-
cients a and b, which differ from gas to gas, have disappeared. It
follows that if the isotherms are plotted in terms of the reduced
variables (as we did in fact in Fig. 1C.8 without drawing atten-
tion to the fact), then the same curves are obtained whatever
the gas. This is precisely the content of the principle of corre-
sponding states, so the van der Waals equation is compatible
with it.
Looking for too much significance in this apparent triumph
is mistaken, because other equations of state also accommodate
Checklist of concepts
☐ 1. The extent of deviations from perfect behaviour is sum-
marized by introducing the compression factor.
☐ 2. The virial equation is an empirical extension of the per-
fect gas equation that summarizes the behaviour of real
gases over a range of conditions.
☐ 3. The isotherms of a real gas introduce the concepts of
vapour pressure and critical behaviour.
☐ 4. A gas can be liquefied by pressure alone only if its tem-
perature is at or below its critical temperature.
Checklist of equations
Property Equation
Compression factor Z = Vm /Vm
Virial equation of state pVm = RT (1+ B /Vm + C /Vm2 +)
van der Waals equation of state p = nRT/(V – nb) – a(n/V)2
Reduced variables Xr = X/Xc
1C Real gases 53
the principle (like those in Table 1C.4). In fact, all we need are
two parameters playing the roles of a and b, for then the equa-
tion can always be manipulated into reduced form. The obser-
vation that real gases obey the principle approximately amounts
to saying that the effects of the attractive and repulsive interac-
tions can each be approximated in terms of a single parameter.
The importance of the principle is then not so much its theo-
retical interpretation but the way that it enables the properties
of a range of gases to be coordinated on to a single diagram (for
example, Fig. 1C.9 instead of Fig. 1C.3).
☐ 5. The van der Waals equation is a model equation of state
for a real gas expressed in terms of two parameters,
one (a) corresponding to molecular attractions and the
other (b) to molecular repulsions.
☐ 6. The van der Waals equation captures the general fea-
tures of the behaviour of real gases, including their crit-
ical behaviour.
☐ 7. The properties of real gases are coordinated by express-
ing their equations of state in terms of reduced variables.
Comment Equation number
Definition 1C.1
B, C depend on temperature 1C.3
a parameterizes attractions, 1C.5
b parameterizes repulsions
X = p, Vm, or T 1C.8
54 1 The properties of gases
CHAPTER 1 The properties of gases
TOPIC 1A The perfect gas
Discussion questions
1A.1 Explain how the perfect gas equation of state arises by combination of
Boyle’s law, Charles’s law, and Avogadro’s principle.
Exercises
1A.1(a) Could 131 g of xenon gas in a vessel of volume 1.0 dm3 exert a
pressure of 20 atm at 25 °C if it behaved as a perfect gas? If not, what
pressure would it exert?
1A.1(b) Could 25 g of argon gas in a vessel of volume 1.5 dm3 exert a pressure
of 2.0 bar at 30 °C if it behaved as a perfect gas? If not, what pressure would it
exert?
1A.2(a) A perfect gas undergoes isothermal compression, which reduces its
volume by 2.20 dm3. The final pressure and volume of the gas are 5.04 bar
and 4.65 dm3, respectively. Calculate the original pressure of the gas in (i) bar,
(ii) atm.
1A.2(b) A perfect gas undergoes isothermal compression, which reduces its
volume by 1.80 dm3. The final pressure and volume of the gas are 1.97 bar and
2.14 dm3, respectively. Calculate the original pressure of the gas in (i) bar,
(ii) torr.
1A.3(a) A car tyre (i.e. an automobile tire) was inflated to a pressure of
24 lb in−2 (1.00 atm = 14.7 lb in−2) on a winter’s day when the temperature
was − 5 °C. What pressure will be found, assuming no leaks have occurred
and that the volume is constant, on a subsequent summer’s day when the
temperature is 35 °C? What complications should be taken into account in
practice?
1A.3(b) A sample of hydrogen gas was found to have a pressure of 125 kPa
when the temperature was 23 °C. What can its pressure be expected to be
when the temperature is 11 °C?
1A.4(a) A sample of 255 mg of neon occupies 3.00 dm3 at 122 K. Use the perfect
gas law to calculate the pressure of the gas.
1A.4(b) A homeowner uses 4.00 × 103 m3 of natural gas in a year to heat a
home. Assume that natural gas is all methane, CH4, and that methane is a
perfect gas for the conditions of this problem, which are 1.00 atm and 20 °C.
What is the mass of gas used?
1A.5(a) 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.
1A.5(b) What pressure difference must be generated across the length of a 15 cm
vertical drinking straw in order to drink a water-like liquid of density 1.0 g cm−3?
1A.6(a) A manometer consists of a U-shaped tube containing a liquid. One
side is connected to the apparatus and the other is open to the atmosphere.
The pressure inside the apparatus is then determined from the difference
in heights of the liquid. Suppose the liquid is water, the external pressure is
770 Torr, and the open side is 10.0 cm lower than the side connected to the
apparatus. What is the pressure in the apparatus? (The density of water at
25 °C is 0.997 07 g cm−3.)
1.A6(b) A manometer like that described in Exercise 1.6(a) contained mercury
in place of water. Suppose the external pressure is 760 Torr, and the open
side is 10.0 cm higher than the side connected to the apparatus. What is the
pressure in the apparatus? (The density of mercury at 25 °C is 13.55 g cm−3.)
1A.2 Explain the term ‘partial pressure’ and explain why Dalton’s law is a
limiting law.
1A.7(a) In an attempt to determine an accurate value of the gas constant, R,
a student heated a container of volume 20.000 dm3 filled with 0.251 32 g of
helium gas to 500 °C and measured the pressure as 206.402 cm of water in a
manometer at 25 °C. Calculate the value of R from these data. (The density of
water at 25 °C is 0.997 07 g cm−3; the construction of a manometer is described
in Exercise 1.6(a).)
1A.7(b) The following data have been obtained for oxygen gas at 273.15 K.
Calculate the best value of the gas constant R from them and the best value of
the molar mass of O2.
p/atm 0.750 000 0.500 000 0.250 000
Vm/(dm3 mol−1) 29.9649 44.8090 89.6384
1A.8(a) At 500 °C and 93.2 kPa, the mass density of sulfur vapour is
3.710 kg m−3. What is the molecular formula of sulfur under these conditions?
1A.8(b) At 100 °C and 16.0 kPa, the mass density of phosphorus vapour is
0.6388 kg m−3. What is the molecular formula of phosphorus under these
conditions?
1A.9(a) Calculate the mass of water vapour present in a room of volume
400 m3 that contains air at 27 °C on a day when the relative humidity is
60 per cent.
1A.9(b) Calculate the mass of water vapour present in a room of volume
250 m3 that contains air at 23 °C on a day when the relative humidity is
53 per cent.
1A.10(a) Given that the density of air at 0.987 bar and 27 °C is 1.146 kg m−3,
calculate the mole fraction and partial pressure of nitrogen and oxygen
assuming that (i) air consists only of these two gases, (ii) air also contains
1.0 mole per cent Ar.
1A.10(b) A gas mixture consists of 320 mg of methane, 175 mg of argon, and
225 mg of neon. The partial pressure of neon at 300 K is 8.87 kPa. Calculate
(i) the volume and (ii) the total pressure of the mixture.
1A.11(a) The density of a gaseous compound was found to be 1.23 kg m−3 at
330 K and 20 kPa. What is the molar mass of the compound?
1A.11(b) In an experiment to measure the molar mass of a gas, 250 cm3 of the
gas was confined in a glass vessel. The pressure was 152 Torr at 298 K, and
after correcting for buoyancy effects, the mass of the gas was 33.5 mg. What is
the molar mass of the gas?
1A.12(a) The densities of air at − 85 °C, 0 °C, and 100 °C are 1.877 g dm−3,
1.294 g dm−3, and 0.946 g dm−3, respectively. From these data, and assuming
that air obeys Charles’s law, determine a value for the absolute zero of
temperature in degrees Celsius.
1A.12(b) A certain sample of a gas has a volume of 20.00 dm3 at 0 °C and
1.000 atm. A plot of the experimental data of its volume against the Celsius
temperature, θ, at constant p, gives a straight line of slope 0.0741 dm3 °C−1.
From these data determine the absolute zero of temperature in degrees
Celsius.

1A.13(a) A vessel of volume 22.4 dm3 contains 2.0 mol H2 and 1.0 mol N2 at
273.15 K. Calculate (i) the mole fractions of each component, (ii) their partial
pressures, and (iii) their total pressure.
Problems
1A.1 Recent communication with the inhabitants of Neptune have
revealed that they have a Celsius-type temperature scale, but based on the
melting point (0 °N) and boiling point (100 °N) of their most common
substance, hydrogen. Further communications have revealed that the
Neptunians know about perfect gas behaviour and they find that in the
limit of zero pressure, the value of pV is 28 dm 3 atm at 0 °N and 40 dm 3 atm
at 100 °N. What is the value of the absolute zero of temperature on their
temperature scale?
1A.2 Deduce the relation between the pressure and mass density, ρ, of a
perfect gas of molar mass M. Confirm graphically, using the following data on
dimethyl ether at 25 °C, that perfect behaviour is reached at low pressures and
find the molar mass of the gas.
p/kPa 12.223 25.20 36.97 60.37 85.23 101.3
ρ/(kg m−3) 0.225 0.456 0.664 1.062 1.468 1.734
1A.3 Charles’s law is sometimes expressed in the form V = V0(1 + αθ), where
θ is the Celsius temperature, is a constant, and V0 is the volume of the
sample at 0 °C. The following values for have been reported for nitrogen
at 0 °C:
p/Torr 749.7 599.6 333.1 98.6
3.6717 3.6697 3.6665 3.6643
103α/°C−1
For these data calculate the best value for the absolute zero of temperature on
the Celsius scale.
1A.4 The molar mass of a newly synthesized fluorocarbon was measured
in a gas microbalance. This device consists of a glass bulb forming one
end of a beam, the whole surrounded by a closed container. The beam is
pivoted, and the balance point is attained by raising the pressure of gas
in the container, so increasing the buoyancy of the enclosed bulb. In one
experiment, the balance point was reached when the fluorocarbon pressure
was 327.10 Torr; for the same setting of the pivot, a balance was reached when
CHF3 (M = 70.014 g mol−1) was introduced at 423.22 Torr. A repeat of the
experiment with a different setting of the pivot required a pressure of 293.22
Torr of the fluorocarbon and 427.22 Torr of the CHF3. What is the molar mass
of the fluorocarbon? Suggest a molecular formula.
1A.5 A constant-volume perfect gas thermometer indicates a pressure of
6.69 kPa at the triple point temperature of water (273.16 K). (a) What change
of pressure indicates a change of 1.00 K at this temperature? (b) What pressure
indicates a temperature of 100.00 °C? (c) What change of pressure indicates a
change of 1.00 K at the latter temperature?
1A.6 A vessel of volume 22.4 dm3 contains 2.0 mol H2 and 1.0 mol N2 at
273.15 K initially. All the H2 reacted with sufficient N2 to form NH3. Calculate
the partial pressures and the total pressure of the final mixture.
1A.7 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?
Exercises and problems 55
1A.13(b) A vessel of volume 22.4 dm3 contains 1.5 mol H2 and 2.5 mol N2 at
273.15 K. Calculate (i) the mole fractions of each component, (ii) their partial
pressures, and (iii) their total pressure.
1A.8 Ozone is a trace atmospheric gas which plays an important role in
screening the Earth from harmful ultraviolet radiation, and the abundance
of ozone is commonly reported in Dobson units. One Dobson unit is the
thickness, in thousandths of a centimetre, of a column of gas if it were
collected as a pure gas at 1.00 atm and 0 °C. What amount of O3 (in moles) is
found in a column of atmosphere with a cross-sectional area of 1.00 dm2 if the
abundance is 250 Dobson units (a typical mid-latitude value)? In the seasonal
Antarctic ozone hole, the column abundance drops below 100 Dobson units;
how many moles of O3 are found in such a column of air above a 1.00 dm2
area? Most atmospheric ozone is found between 10 and 50 km above the
surface of the earth. If that ozone is spread uniformly through this portion
of the atmosphere, what is the average molar concentration corresponding
to (a) 250 Dobson units, (b) 100 Dobson units?
1A.9 The barometric formula (see Impact 1.1) relates the pressure of a gas
of molar mass M at an altitude h to its pressure p0 at sea level. Derive this
relation by showing that the change in pressure dp for an infinitesimal
change in altitude dh where the density is ρ is dp = − ρgdh. Remember that
ρ depends on the pressure. Evaluate (a) the pressure difference between
the top and bottom of a laboratory vessel of height 15 cm, and (b) the
external atmospheric pressure at a typical cruising altitude of an aircraft
(11 km) when the pressure at ground level is 1.0 atm.
1A.10 Balloons are still used to deploy sensors that monitor meteorological
phenomena and the chemistry of the atmosphere. It is possible to investigate
some of the technicalities of ballooning by using the perfect gas law. Suppose
your balloon has a radius of 3.0 m and that it is spherical. (a) What amount
of H2 (in moles) is needed to inflate it to 1.0 atm in an ambient temperature
of 25 °C at sea level? (b) What mass can the balloon lift at sea level, where the
density of air is 1.22 kg m−3? (c) What would be the payload if He were used
instead of H2?
1A.11‡ The preceding problem is most readily solved with the use of
Archimedes principle, which states that the lifting force is equal to the
difference between the weight of the displaced air and the weight of the
balloon. Prove Archimedes principle for the atmosphere from the barometric
formula. Hint: Assume a simple shape for the balloon, perhaps a right circular
cylinder of cross-sectional area A and height h.
1A.12‡ Chlorofluorocarbons such as CCl3F and CCl2F2 have been linked
to ozone depletion in Antarctica. As of 1994, these gases were found
in quantities of 261 and 509 parts per trillion (1012) by volume (World
Resources Institute, World resources 1996 − 97). Compute the molar
concentration of these gases under conditions typical of (a) the mid-latitude
troposphere (10 °C and 1.0 atm) and (b) the Antarctic stratosphere (200 K
and 0.050 atm).
1A.13‡ The composition of the atmosphere is approximately 80 per cent
nitrogen and 20 per cent oxygen by mass. At what height above the surface of
the Earth would the atmosphere become 90 per cent nitrogen and 10 per cent
oxygen by mass? Assume that the temperature of the atmosphere is constant
at 25 °C. What is the pressure of the atmosphere at that height?
‡ These problems were supplied by Charles Trapp and Carmen Giunta.
56 1 The properties of gases

TOPIC 1B The kinetic model

Discussion questions
1B.1 Specify and analyse critically the assumptions that underlie the kinetic 1B.2 Provide molecular interpretations for the dependencies of the mean free
model of gases. path on the temperature, pressure, and size of gas molecules.

Exercises
1B.1(a) Determine the ratios of (i) the mean speeds, (ii) the mean 1B.5(a) Assume that air consists of N2 molecules with a collision diameter
translational kinetic energies of H2 molecules and Hg atoms at 20 °C. of 395 pm. Calculate (i) the mean speed of the molecules, (ii) the mean free
1B.1(b) Determine the ratios of (i) the mean speeds, (ii) the mean kinetic path, (iii) the collision frequency in air at 1.0 atm and 25 °C.
energies of He atoms and Hg atoms at 25 °C. 1B.5(b) The best laboratory vacuum pump can generate a vacuum of about
1 nTorr. At 25 °C and assuming that air consists of N2 molecules with a
1B.2(a) Calculate the root mean square speeds of H2 and O2 molecules at 20 °C.
collision diameter of 395 pm, calculate (i) the mean speed of the molecules,
1B.2(b) Calculate the root mean square speeds of CO2 molecules and He atoms
(ii) the mean free path, (iii) the collision frequency in the gas.
at 20 °C.
1B.6(a) At what pressure does the mean free path of argon at 20 °C become
1B.3(a) Use the Maxwell–Boltzmann distribution of speeds to estimate
comparable to the diameter of a 100 cm3 vessel that contains it? Take
the fraction of N2 molecules at 400 K that have speeds in the range 200 to
σ = 0.36 nm2.
210 m s−1.
1B.6(b) At what pressure does the mean free path of argon at 20 °C become
1B.3(b) Use the Maxwell–Boltzmann distribution of speeds to estimate the
comparable to 10 times the diameters of the atoms themselves?
fraction of CO2 molecules at 400 K that have speeds in the range 400 to
405 m s−1. 1B.7(a) 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? (σ  = 0.43 nm2).
1B.4(a) Calculate the most probable speed, the mean speed, and the mean
1B.7(b) At an altitude of 15 km the temperature is 217 K and the pressure
relative speed of CO2 molecules in air at 20 °C.
12.1 kPa. What is the mean free path of N2 molecules? (σ  = 0.43 nm2).
1B.4(b) Calculate the most probable speed, the mean speed, and the mean
relative speed of H2 molecules in air at 20 °C.

Problems
1B.1 A rotating slotted-disc apparatus like that in Fig. 1B.5 consists of five 1B.6 What, according to the Maxwell–Boltzmann distribution, is the
coaxial 5.0 cm diameter disks separated by 1.0 cm, the slots in their rims proportion of gas molecules having (a) more than, (b) less than the root mean
being displaced by 2.0° between neighbours. The relative intensities, I, of the square speed? (c) What are the proportions having speeds greater and smaller
detected beam of Kr atoms for two different temperatures and at a series of than the mean speed?
rotation rates were as follows:
1B.7 Calculate the fractions of molecules in a gas that have a speed in a range
Δv at the speed nvmp relative to those in the same range at vm itself? This
ν/Hz 20 40 80 100 120 calculation can be used to estimate the fraction of very energetic molecules
I (40 K) 0.846 0.513 0.069 0.015 0.002 (which is important for reactions). Evaluate the ratio for n = 3 and n = 4.
I (100 K) 0.592 0.485 0.217 0.119 0.057 1B.8 Derive an expression for 〈vn〉1/n from the Maxwell–Boltzmann distribution
of speeds. You will need standard integrals given in the Resource section.
Find the distributions of molecular velocities, f(vx), at these temperatures, and 1B.9 Calculate the escape velocity (the minimum initial velocity that will take
check that they conform to the theoretical prediction for a one-dimensional an object to infinity) from the surface of a planet of radius R. What is the value
system. for (a) the Earth, R = 6.37 × 106 m, g = 9.81 m s−2, (b) Mars, R = 3.38 × 106 m,
1B.2 A Knudsen cell was used to determine the vapour pressure of germanium mMars/mEarth = 0.108. At what temperatures do H2, He, and O2 molecules have
at 1000 °C. During an interval of 7200 s the mass loss through a hole of radius mean speeds equal to their escape speeds? What proportion of the molecules
0.50 mm amounted to 43 µg. What is the vapour pressure of germanium at have enough speed to escape when the temperature is (a) 240 K, (b) 1500 K?
1000 °C? Assume the gas to be monatomic. Calculations of this kind are very important in considering the composition of
planetary atmospheres.
1B.3 Start from the Maxwell–Boltzmann distribution and derive an expression
for the most probable speed of a gas of molecules at a temperature T. Go on to 1B.10 The principal components of the atmosphere of the Earth are diatomic
demonstrate the validity of the equipartition conclusion that the average transla­ molecules, which can rotate as well as translate. Given that the translational
tional kinetic energy of molecules free to move in three dimensions is 23 kT . kinetic energy density of the atmosphere is 0.15 J cm−3, what is the total kinetic
energy density, including rotation? The average rotational energy of a linear
1B.4 Consider molecules that are confined to move in a plane (a two-
molecule is kT.
dimensional gas). Calculate the distribution of speeds and determine the
mean speed of the molecules at a temperature T. 1B.11 Plot different Maxwell–Boltzmann speed distributions by keeping the
molar mass constant at 100 g mol−1 and varying the temperature of the sample
1B.5 A specially constructed velocity-selector accepts a beam of molecules
between 200 K and 2000 K.
from an oven at a temperature T but blocks the passage of molecules with a
speed greater than the mean. What is the mean speed of the emerging beam, 1B.12 Evaluate numerically the fraction of molecules with speeds in the range
relative to the initial value, treated as a one-dimensional problem? 100 m s−1 to 200 m s−1 at 300 K and 1000 K.

TOPIC 1C Real gases
Discussion questions
1C.1 Explain how the compression factor varies with pressure and
temperature and describe how it reveals information about intermolecular
interactions in real gases.
1C.2 What is the significance of the critical constants?
Exercises
1C.1(a) Calculate the pressure exerted by 1.0 mol C2H6 behaving as 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 1C.3.
1C.1(b) Calculate the pressure exerted by 1.0 mol H2S behaving as a van der
Waals gas when it is confined under the following conditions: (i) at 273.15 K
in 22.414 dm3, (ii) at 500 K in 150 cm3. Use the data in Table 1C.3.
1C.2(a) Express the van der Waals parameters a = 0.751 atm dm6 mol−2 and
b = 0.0226 dm3 mol−1 in SI base units.
1C.2(b) Express the van der Waals parameters a = 1.32 atm dm6 mol−2 and
b = 0.0436 dm3 mol−1 in SI base units.
1C.3(a) A gas at 250 K and 15 atm has a molar volume 12 per cent smaller
than that calculated from the perfect gas law. Calculate (i) the compression
factor under these conditions and (ii) the molar volume of the gas. Which are
dominating in the sample, the attractive or the repulsive forces?
1C.3(b) A gas at 350 K and 12 atm has a molar volume 12 per cent larger than
that calculated from the perfect gas law. Calculate (i) the compression factor
under these conditions and (ii) the molar volume of the gas. Which are
dominating in the sample, the attractive or the repulsive forces?
1C.4(a) In an industrial process, nitrogen is heated to 500 K at a constant
volume of 1.000 m3. The gas enters the container at 300 K and 100 atm. The
mass of the gas is 92.4 kg. Use the van der Waals equation to determine the
approximate pressure of the gas at its working temperature of 500 K. For
nitrogen, a = 1.352 dm6 atm mol−2, b = 0.0387 dm3 mol−1.
1C.4(b) Cylinders of compressed gas are typically filled to a pressure of 200 bar.
For oxygen, what would be the molar volume at this pressure and 25 °C based
on (i) the perfect gas equation, (ii) the van der Waals equation? For oxygen,
a = 1.364 dm6 atm mol−2, b = 3.19 × 10−2 dm3 mol−1.
1C.5(a) Suppose that 10.0 mol C2H6(g) is confined to 4.860 dm3 at 27 °C.
Predict the pressure exerted by the ethane from (i) the perfect gas and (ii) the
van der Waals equations of state. Calculate the compression factor based on
these calculations. For ethane, a = 5.507 dm6 atm mol−2, b = 0.0651 dm3 mol−1.
Problems
1C.1 Calculate the molar volume of chlorine gas at 350 K and 2.30 atm using
(a) the perfect gas law and (b) the van der Waals equation. Use the answer to
(a) to calculate a first approximation to the correction term for attraction and
then use successive approximations to obtain a numerical answer for part (b).
1C.2 At 273 K measurements on argon gave B = − 21.7 cm3 mol−1 and
C = 1200 cm6 mol−2, where B and C are the second and third virial coefficients
in the expansion of Z in powers of 1/Vm. Assuming that the perfect gas law
holds sufficiently well for the estimation of the second and third terms of the
expansion, calculate the compression factor of argon at 100 atm and 273 K.
From your result, estimate the molar volume of argon under these conditions.
1C.3 Calculate the volume occupied by 1.00 mol N2 using the van der Waals
equation in the form of a virial expansion at (a) its critical temperature, (b) its
Boyle temperature, and (c) its inversion temperature. Assume that the pressure
Exercises and problems 57
1C.3 Describe the formulation of the van der Waals equation and suggest a
rationale for one other equation of state in Table 1C.6.
1C.4 Explain how the van der Waals equation accounts for critical behaviour.
1C.5(b) At 300 K and 20 atm, the compression factor of a gas is 0.86. Calculate
(i) the volume occupied by 8.2 mmol of the gas under these conditions and
(ii) an approximate value of the second virial coefficient B at 300 K.
1C.6(a) The critical constants of methane are pc = 45.6 atm, Vc = 98.7 cm3 mol−1,
and Tc = 190.6 K. Calculate the van der Waals parameters of the gas and
estimate the radius of the molecules.
1C.6(b) 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.
1C.7(a) Use the van der Waals parameters for chlorine in Table 1C.3 of the
Resource section to calculate approximate values of (i) the Boyle temperature
of chlorine and (ii) the radius of a Cl2 molecule regarded as a sphere.
1C.7(b) Use the van der Waals parameters for hydrogen sulfide in Table
1C.3 of the Resource section to calculate approximate values of (i) the Boyle
temperature of the gas and (ii) the radius of a H2S molecule regarded as a
sphere.
1C.8(a) Suggest the pressure and temperature at which 1.0 mol of (i) NH3, (ii)
Xe, (iii) He will be in states that correspond to 1.0 mol H2 at 1.0 atm and 25 °C.
1C.8(b) Suggest the pressure and temperature at which 1.0 mol of (i) H2S,
(ii) CO2, (iii) Ar will be in states that correspond to 1.0 mol N2 at 1.0 atm and
25 °C.
1C.9(a) A certain gas obeys the van der Waals equation with a = 0.50 m6 Pa
mol−2. Its volume is found to be 5.00 × 10−4 m3 mol−1 at 273 K and 3.0 MPa.
From this information calculate the van der Waals constant b. What is the
compression factor for this gas at the prevailing temperature and pressure?
1C.9(b) A certain gas obeys the van der Waals equation with a = 0.76 m6 Pa
mol−2. Its volume is found to be 4.00 × 10−4 m3 mol−1 at 288 K and 4.0 MPa.
From this information calculate the van der Waals constant b. What is the
compression factor for this gas at the prevailing temperature and pressure?
is 10 atm throughout. At what temperature is the gas most perfect? Use the
following data: Tc = 126.3 K, a = 1.352 dm6 atm mol−2, b = 0.0387 dm3 mol−1.
1C.4‡ The second virial coefficient of methane can be approximated by the
empirical equation B(T ) = a + be −c /T , where a = − 0.1993 bar−1, b = 0.2002 bar−1,
2
and c = 1131 K2 with 300 K < T < 600 K. What is the Boyle temperature of methane?
1C.5 The mass density of water vapour at 327.6 atm and 776.4 K is 133.2 kg
m−3. Given that for water Tc = 647.4 K, pc = 21.3 atm, a = 5.464 dm6 atm mol−2,
b = 0.03049 dm3 mol−1, and M = 18.02 g mol−1, calculate (a) the molar volume.
Then calculate the compression factor (b) from the data, (c) from the virial
expansion of the van der Waals equation.
1C.6 The critical volume and critical pressure of a certain gas are 160 cm3
mol−1 and 40 atm, respectively. Estimate the critical temperature by assuming
58 1 The properties of gases
that the gas obeys the Berthelot equation of state. Estimate the radii of the gas
molecules on the assumption that they are spheres.
1C.7 Estimate the coefficients a and b in the Dieterici equation of state from
the critical constants of xenon. Calculate the pressure exerted by 1.0 mol Xe
when it is confined to 1.0 dm3 at 25 °C.
1C.8 Show that the van der Waals equation leads to values of Z < 1 and Z > 1,
and identify the conditions for which these values are obtained.
1C.9 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. The expansion you will need is (1 − x)−1 = 1 + x + x2 + .... 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?
1C.10‡ Derive the relation between the critical constants and the Dieterici
equation parameters. Show that Zc = 2e−2 and derive the reduced form of the
Dieterici equation of state. Compare the van der Waals and Dieterici predictions
of the critical compression factor. Which is closer to typical experimental values?
1C.11 A scientist proposed the following equation of state:
RT B C p/MPa
p= − +
Vm Vm2 Vm3
Show that the equation leads to critical behaviour. Find the critical constants
of the gas in terms of B and C and an expression for the critical compression
factor.
1C.12 Equations 1C.3a and 1C.3b are expansions in p and 1/Vm, respectively.
Find the relation between B, C and B′, C′.
1C.13 The second virial coefficient B′ can be obtained from measurements
of the density ρ of a gas at a series of pressures. Show that the graph of p/ρ
against p should be a straight line with slope proportional to B′. Use the data
on dimethyl ether in Problem 1A.2 to find the values of B′ and B at 25 °C.
1C.14 The equation of state of a certain gas is given by p = RT/Vm +
(a + bT)/Vm2, where a and b are constants. Find (∂V/∂T)p.
1C.15 The following equations of state are occasionally used for approximate
calculations on gases: (gas A) pVm = RT(1 + b/Vm), (gas B) p(Vm− b) = RT.
Assuming that there were gases that actually obeyed these equations of state,
would it be possible to liquefy either gas A or B? Would they have a critical
temperature? Explain your answer.
1C.16 Derive an expression for the compression factor of a gas that obeys the
equation of state p(V − nb) = nRT, where b and R are constants. If the pressure
and temperature are such that Vm = 10b, what is the numerical value of the
compression factor?
1C.17‡ The discovery of the element argon by Lord Rayleigh and Sir
William Ramsay had its origins in Rayleigh’s measurements of the density
of nitrogen with an eye toward accurate determination of its molar mass.
Rayleigh prepared some samples of nitrogen by chemical reaction of
nitrogen-containing compounds; under his standard conditions, a glass
globe filled with this ‘chemical nitrogen’ had a mass of 2.2990 g. He prepared
other samples by removing oxygen, carbon dioxide, and water vapor
from atmospheric air; under the same conditions, this ‘atmospheric nitrogen’
had a mass of 2.3102 g (Lord Rayleigh, Royal Institution Proceedings 14, 524
(1895)). With the hindsight of knowing accurate values for the molar masses
of nitrogen and argon, compute the mole fraction of argon in the latter sample
on the assumption that the former was pure nitrogen and the latter a mixture
of nitrogen and argon.
1C.18‡ A substance as elementary and well known as argon still receives
research attention. Stewart and Jacobsen have published a review of
thermodynamic properties of argon (R.B. Stewart and R.T. Jacobsen, J. Phys.
Chem. Ref. Data 18, 639 (1989)) which included the following 300 K isotherm.
0.4000 0.5000 0.6000 0.8000 1.000
Vm/(dm3 mol−1) 6.2208 4.9736 4.1423 3.1031 2.4795
p/MPa 1.500 2.000 2.500 3.000 4.000
Vm/(dm3 mol−1) 1.6483 1.2328 0.98357 0.81746 0.60998
(a) Compute the second virial coefficient, B, at this temperature. (b) Use non-
linear curve-fitting software to compute the third virial coefficient, C, at this
temperature.
1C.19 Use mathematical software, a spreadsheet, or the Living graphs on the
web site for this book to: (a) Explore how the pressure of 1.5 mol CO2(g)
varies with volume as it is compressed at (a) 273 K, (b) 373 K from 30 dm3 to
15 dm3. (c) Plot the data as p against 1/V.
1C.20 Calculate the molar volume of chlorine gas on the basis of the van der
Waals equation of state at 250 K and 150 kPa and calculate the percentage
difference from the value predicted by the perfect gas equation.
1C.21 Is there a set of conditions at which the compression factor of a van der
Waals gas passes through a minimum? If so, how does the location and value
of the minimum value of Z depend on the coefficients a and b?
 Differentiation and integration 59

Mathematical background 1 Differentiation and integration

Two of the most important mathematical techniques in the The derivatives of some common functions are as follows:
physical sciences are differentiation and integration. They
occur throughout the subject, and it is essential to be aware of d n
x = nx n−1 (MB1.3a)
the procedures involved. dx

d ax
MB1.1 Differentiation: definitions e = ae ax (MB1.3b)
dx
Differentiation is concerned with the slopes of functions, such d d
as the rate of change of a variable with time. The formal defini- sin ax = a cos ax cos ax = −a sin ax (MB1.3c)
dx dx
tion of the derivative, df/dx, of a function f(x) is
d 1
ln ax = (MB1.3d)
df f ( x + δx ) − f ( x ) dx x
= lim Definition First derivative (MB1.1)
dx δx→0 δx
When a function depends on more than one variable, we
As shown in Fig. MB1.1, the derivative can be interpreted as the need the concept of a partial derivative, ∂f/∂x. Note the change
slope of the tangent to the graph of f(x). A positive first deriva- from d to ∂: partial derivatives are dealt with at length in
tive indicates that the function slopes upwards (as x increases), Mathematical background 2; all we need know at this stage is
and a negative first derivative indicates the opposite. It is some- that they signify that all variables other than the stated variable
times convenient to denote the first derivative as f ′(x). The sec- are regarded as constant when evaluating the derivative.
ond derivative, d2f/dx2, of a function is the derivative of the
first derivative (here denoted f ′): Brief illustration MB1.1 Partial derivatives
d2 f f ′( x + δx ) − f ′( x ) Suppose we are told that f is a function of two variables, and
= lim Definition Second derivative (MB1.2)
dx 2 δx→0 δx specifically f = 4x 2y3. Then, to evaluate the partial derivative of
f with respect to x, we regard y as a constant (just like the 4),
It is sometimes convenient to denote the second derivative f ″. and obtain
As shown in Fig. MB1.1, the second derivative of a function can ∂f ∂ ∂ 2
be interpreted as an indication of the sharpness of the curva- = (4 x 2 y 3 ) = 4 y 3 x = 8 xy 3
∂x ∂x ∂x
ture of the function. A positive second derivative indicates that
the function is ∪ shaped, and a negative second derivative indi- Similarly, to evaluate the partial derivative of f with respect to
cates that it is ∩ shaped. y, we regard x as a constant (again, like the 4), and obtain
∂f ∂ ∂ 3
= (4 x 2 y 3 ) = 4 x 2 y = 12 x 2 y 2
∂y ∂y ∂y

df/dx d2f/dx2

MB1.2 Differentiation: manipulations

f df/dx
0
It follows from the definition of the derivative that a variety of
combinations of functions can be differentiated by using the
following rules:
(a) x (b) x
d d u dv
(u + v) = + (MB1.4a)
Figure MB1.1 (a) The first derivative of a function is equal to the dx dx dx
slope of the tangent to the graph of the function at that point.
The small circle indicates the extremum (in this case, maximum) d dv du
uv = u + v (MB1.4b)
of the function, where the slope is zero. (b) The second dx dx dx
derivative of the same function is the slope of the tangent to a
graph of the first derivative of the function. It can be interpreted d u 1 du u dv
= − (MB1.4c)
as an indication of the curvature of the function at that point. dx v v dx v 2 dx
60 Mathematical background 1

Brief illustration MB1.2 Derivatives Brief illustration MB1.3 Series expansion

To differentiate the function f = sin 2 ax/x 2 use eqn MB1.4 to To evaluate the expansion of cos x around x = 0 we note that
write
 d   d2 
 dx cos x  = (− sin x)0 = 0  dx 2 cos x  = (− cos x)0 = −1
d sin 2 ax d  sin ax   sin ax   sin ax  d  sin ax  0 0
=  =2
dx x 2 dx  x   x   x  dx  x 
and in general
 sin ax   1 d d 1
= 2  sin ax + sin ax
 x   x dx dx x   dn   0 for n odd
 dx n cos x  = (−1)n/2 for n even
a sin 2 ax  0 
= 2  2 sin ax cos ax −
x x 3 
Therefore,
∞
The function and this first derivative are plotted in Fig. MB1.2. (−1)n/2 n
cos x = ∑
n even
n!
x = 1 − 12 x 2 + 241 x 4 −

f(x)

0.5
The following Taylor series (specifically, Maclaurin series)
are used at various stages in the text:

∞
0 (1+ x)−1 = 1− x + x 2 − = ∑(−1) x
n=0
n n
(MB1.7a)

df(x)/dx ∞

∑ n!
xn
–0.5 e x = 1+ x + 12 x 2 + = (MB1.7b)
n=0
–10 –5 0 5 1
x
∞

∑
Figure MB1.2 The function considered in Brief illustration xn
ln(1+ x) = x − 12 x 2 + 13 x 3 − = (−1)n+1 (MB1.7c)
MB1.2 and its first derivative. n
n=1

Taylor series are used to simplify calculations, for when

x ≪ 1 it is possible, to a good approximation, to terminate the
MB1.3 Series expansions
series after one or two terms. Thus, provided x ≪ 1 we can write
One application of differentiation is to the development of
power series for functions. The Taylor series for a function f(x) (1 + x)−1 ≈ 1− x (MB1.8a)
in the vicinity of x = a is
e x ≈ 1+ x (MB1.8b)

 df  1  d2 f  ln(1+ x) ≈ x (MB1.8c)
f (x) = f (a) +   (x − a) +  2  (x − a)2 +
 dx  a 2 !  dx  a
∞ A series is said to converge if the sum approaches a finite,
1  dn f 
= ∑ n!  dx n 
a
(x − a)n Taylor series (MB1.5) definite value as n approaches infinity. If the sum does not
n=0 approach a finite, definite value, then the series is said to
diverge. Thus, the series in eqn MB1.7a converges for x < 1 and
where the notation (…)a means that the derivative is evaluated diverges for x ≥ 1.There are a variety of tests for convergence,
at x = a and n! denotes a factorial given by which are explained in mathematics texts.

n ! = n(n - 1)(n - 2)…1, 0! = 1 (MB1.6)

Factorial
MB1.4 Integration: definitions
The Maclaurin series for a function is a special case of the Integration (which formally is the inverse of differentiation)
Taylor series in which a = 0. is concerned with the areas under curves. The integral of a
 Differentiation and integration 61

transform it into one of the forms by using integration tech-

niques such as:
δx
Substitution. Introduce a variable u related to the
independent variable x (for example, an algebraic relation
f(x) such as u = x2 − 1 or a trigonometric relation such as u = sin x ).
Express the differential dx in terms of du (for these
substitutions, du = 2x dx and du = cos x dx, respectively).
Then transform the original integral written in terms of x
into an integral in terms of u upon which, in some cases, a
a x b standard form such as one of those listed in the Resource
section can be used.
Figure MB1.3 A definite integral is evaluated by forming the
product of the value of the function at each point and the
increment δx, with δx → 0, and then summing the products Brief illustration MB1.4 Integration by substitution
f(x)δx for all values of x between the limits a and b. It follows
that the value of the integral is the area under the curve To evaluate the indefinite integral ∫cos2 x sin x dx we make the
between the two limits. substitution u = cos x. It follows that du/dx = –sin x, and there-
fore that sin x dx = –du. The integral is therefore

function f(x), which is denoted ∫f dx (the symbol ∫ is an elon- ∫ cos x sin x dx = −∫u du = −
2 2
3 u +C
1 3
= − 13 cos3 x + C
gated S denoting a sum), between the two values x = a and x = b
is defined by imagining the x axis as divided into strips of width To evaluate the corresponding definite integral, we have to
δx and evaluating the following sum: convert the limits on x into limits on u. Thus, if the limits are
x = 0 and x = π, the limits become u = cos 0 = 1 and u = cos π = –1:

∑ f ( x ) δx
b

∫
π −1 −1
u2 du = {− 13 u3 + C }
2
a
f (x)dx = lim
δx→0
i
i Definition Integration (MB1.9)
∫ 0
cos2 x sin x dx = − ∫1 1
=
3

As can be appreciated from Fig. MB1.3, the integral is the area

under the curve between the limits a and b. The function to
be integrated is called the integrand. It is an astonishing math- Integration by parts. For two functions f(x) and g(x):
ematical fact that the integral of a function is the inverse of the
differential of that function in the sense that if we differentiate dg df
f and then integrate the resulting function, then we obtain the ∫ f dx dx = fg − ∫ g dx dx Integration by parts (MB1.11a)

original function f (to within a constant). The function in eqn

MB1.9 with the limits specified is called a definite integral. If it which may be abbreviated as:
is written without the limits specified, then we have an indefi-
nite integral. If the result of carrying out an indefinite integra-
tion is g(x) + C, where C is a constant, the following notation is ∫ fdg = fg − ∫ gdf (MB1.11b)

used to evaluate the corresponding definite integral:

Brief illustration MB1.5 Integration by parts
b

∫
b
I= f (x)dx = {g (x) + C} = {g (b) + C} − {g (a) + C}
a Integrals over xe−ax and their analogues occur commonly in
a
the discussion of atomic structure and spectra. They may be
= g (b) − g (a) Definite integral (MB1.10)
integrated by parts, as in the following:
g g
dg /dx  ∞

Note that the constant of integration disappears. The definite ∞
f  f e − ax ∞
e x
− ax df/d

and indefinite integrals encountered in this text are listed in the ∫ 0

x e − ax dx = x
−a
0
− ∫ 0 −a
1 dx
Resource section. ∞ ∞
xe − ax 1 ∞
e − ax
=−
a
+
a ∫0
e − ax dx = 0 −
a2
Integration: manipulations
0 0
MB1.5 1
= 2
When an indefinite integral is not in the form of one of those a
listed in the Resource section it is sometimes possible to
62 Mathematical background 1

MB1.6 Multiple integrals Brief illustration MB1.6 A double integral

A function may depend on more than one variable, in which Double integrals of the form
case we may need to integrate over both the variables: L1 L2

b d
I= ∫ ∫
0 0
sin 2 (πx /L1)sin 2 (πy /L2 )dxdy
I= ∫∫
a c
f (x , y )dxdy (MB1.12)
occur in the discussion of the translational motion of a par-
ticle in two dimensions, where L1 and L 2 are the maximum
We (but not everyone) adopt the convention that a and b are extents of travel along the x- and y-axes, respectively. To eval-
the limits of the variable x and c and d are the limits for y (as uate I we use eqn MB1.13 and an integral listed in the Resource
depicted by the colours in this instance). This procedure is sim- section to write
ple if the function is a product of functions of each variable and Integral T.2
 L1 L2
of the form f(x,y) = X(x)Y(y). In this case, the double integral is
just a product of each integral:
I = ∫
0
sin 2 (πx /L1)dx ∫
0
sin 2 (πy /L2 )dy
L1 L2
 sin(2πx /L1)  1 sin(2πy /L2 ) 
=  12 x − +C  2 y − 4 π /L +C
b d b d 4 π /L
I= ∫∫ X (x)Y ( y )dxdy = ∫ ∫ Y (y)dy    
1 2
X (x)dx (MB1.13) 0 0
a c a c
= L1L21
4