1.

3 MOLECULAR INTERACTIONS 15
[1.16]
Because the molar volume of a perfect gas is equal to RT/p, an equivalent expression
is Z RT/pV om
, which we can write as
pVm RTZ (1.17)
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. 1.14. At very low pressures, all
the gases shown have Z 1 and behave nearly perfectly. At high pressures, all the
gases have Z 1, signifying 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.
(b) Virial coefficients
Figure 1.15 shows the experimental isotherms for carbon dioxide. At large molar
volumes and high temperatures the real-gas isotherms do not differ greatly from
perfect-gas isotherms. The small differences suggest that the perfect gas law is in fact
the first term in an expression of the form
pVm RT(1 + Bp + Cp2+ ) (1.18)
This expression is an example of a common procedure in physical chemistry, in which
a simple law that is known to be a good first approximation (in this case pV nRT) is
Z
V
V
m
mo
H2
CH4
C H 24
NH3
p/atm
2
1
0 200 400 600 800
Perfect
0
Compression factor, Z
1.00
0.98
0.96
10
H2
CH4
C H 2 4 NH3
p/atm
140
120
100
80
60
40
20
0
0 0.2 0.4 0.6
50C
40C
31.04C (T ) c
0C
p/atm
Vm/(dm mol ) 3 1
EDC
B
A
F
*
20C
-

Fig. 1.14 The variation of the compression

factor, Z, with pressure for several gases at
0C. A perfect gas has Z 1 at all pressures.
Notice that, although the curves approach
1 as p0, they do so with different slopes.
Fig. 1.15 Experimental isotherms of carbon
dioxide at several temperatures. The
critical isotherm, the isotherm at the
critical temperature, is at 31.04C. The
critical point is marked with a star.

16 1 THE PROPERTIES OF GASES

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
(1.19)
These two expressions are two versions of the virial equation of state.4 By comparing
the expression with eqn 1.17 we see that the term in parentheses can be identified with
the compression factor, Z.
The coefficients B, C, . . . , which depend on the temperature, are the second, third,
. . . virial coefficients (Table 1.4); the first virial coefficient is 1. The third virial
coefficient, C, is usually less important than the second coefficient, B, in the sense that
at typical molar volumes C/V2m
B/Vm.
We can use the virial equation to demonstrate the important point that, although
the equation of state of a real gas may coincide with the perfect gas law as p0, 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 perfect gas dZ/dp 0 (because Z 1 at all pressures), but for a real gas
from eqn 1.18 we obtain
2pC Bas p0 (1.20a)
However, Bis not necessarily zero, so the slope of Z with respect to p does not necessarily
approach 0 (the perfect gas value), as we can see in Fig. 1.14. Because several
physical properties of gases depend on derivatives, the properties of real gases do not
always coincide with the perfect gas values at low pressures. By a similar argument,
B as Vm, corresponding to p0 (1.20b)
Because the virial coefficients depend on the temperature, there may be a temperature
at which Z1 with zero slope at low pressure or high molar volume (Fig. 1.16).
At this temperature, which is called the Boyle temperature, TB, the properties of the
real gas do coincide with those of a perfect gas as p0. According to eqn 1.20b, Z has
zero slope as p0 if B 0, so we can conclude that B 0 at the Boyle temperature.
It then follows from eqn 1.19 that pVm RTB over a more extended range of pressures
than at other temperatures because the first term after 1 (that is, B/Vm) in the
virial equation is zero and C/V2m
and higher terms are negligibly small. For helium
TB 22.64 K; for air TB 346.8 K; more values are given in Table 1.5.
d
dm
Z
(1/V )
d
d
Z
p
B
pV RT
B
V
C
Vm
mm

1
2
Comment 1.4
Series expansions are discussed in
Appendix 2.
4 The name comes from the Latin word for force. The coefficients are sometimes denoted B2, B3, . . . .
Synoptic Table 1.4* Second virial
coefficients, B/(cm3 mol1)
Temperature
273 K 600 K
Ar 21.7 11.9
CO2 149.7 12.4
N2 10.5 21.7
Xe 153.7 19.6
* More values are given in the Data section.
Synoptic Table 1.5* Critical constants of gases
pc/atm Vc/(cm3 mol1) Tc/K Zc TB/K
Ar 48.0 75.3 150.7 0.292 411.5
CO2 72.9 94.0 304.2 0.274 714.8
He 2.26 57.8 5.2 0.305 22.64
O2 50.14 78.0 154.8 0.308 405.9
* More values are given in the Data section.
Pressure, p
Higher
temperature
Lower
temperature
Perfect
gas
Boyle
temperature
1
Compression factor, Z
0
Fig. 1.16 The compression factor, Z,
approaches 1 at low pressures, but does so
with different slopes. For a perfect gas, the
slope is zero, but real gases may have either
positive or negative slopes, and the slope
may vary with temperature. At the Boyle
temperature, the slope is zero and the gas
behaves perfectly over a wider range of
conditions than at other temperatures.
1.4 THE VAN DER WAALS EQUATION 17
(c) Condensation
Now consider what happens when we compress a sample of gas initially in the state
marked A in Fig. 1.15 at constant temperature (by pushing in a piston). Near A, the
pressure of the gas rises in approximate agreement with Boyles 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 suddenly the piston slides in without any further rise in pressure:
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.
(d) Critical constants
The isotherm at the temperature Tc (304.19 K, or 31.04C for CO2) plays a special role
in the theory of the states of matter. An isotherm slightly below Tc behaves as we have
already described: at a certain pressure, a liquid condenses from the gas and is distinguishable
from it by the presence of a visible surface. If, however, the compression
takes place at Tc itself, then a surface separating two phases does not appear and the
volumes at each end of the horizontal part of the isotherm have merged to a single
point, the critical point of the gas. The temperature, pressure, and molar volume
at the critical point are called the critical temperature, Tc, critical pressure, pc, and
critical molar volume, Vc, of the substance. Collectively, pc, Vc, and Tc are the critical
constants of a substance (Table 1.5).
At and above Tc, the sample has a single phase that occupies the entire volume
of the container. Such a phase is, by definition, a gas. Hence, the liquid phase of a
substance does not form above the critical temperature. The critical temperature of
oxygen, for instance, signifies that it is impossible to produce liquid oxygen by compression
alone if its temperature is greater than 155 K: to liquefy oxygento obtain a
fluid phase that does not occupy the entire volumethe temperature must first be
lowered to below 155 K, and then the gas compressed isothermally. The single phase
that fills the entire volume when T Tc may be much denser than we normally consider
typical of gases, and the name supercritical fluid is preferred.
1.4 The van der Waals equation
We can draw conclusions from the virial equations of state 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 suggested by J.D.
van der Waals in 1873. This equation is an excellent example of an expression that can
be obtained by thinking scientifically about a mathematically complicated but physically
simple problem, that is, it is a good example of model building.
The van der Waals equation is
p (1.21a)
nRT
V nb
a
n
V

18 1 THE PROPERTIES OF GASES

Synoptic Table 1.6* van der Waals
coefficients
a/(atm dm6 mol2) b/(102 dm3 mol1)
Ar 1.337 3.20
CO2 3.610 4.29
He 0.0341 2.38
Xe 4.137 5.16
* More values are given in the Data section.
and a derivation is given in Justification 1.1. The equation is often written in terms of
the molar volume Vm V/n as
(1.21b)
The constants a and b are called the van der Waals coefficients. They are characteristic
of each gas but independent of the temperature (Table 1.6).
Justification 1.1 The van der Waals equation of state
The repulsive interactions between molecules are taken into account by supposing
that they cause the molecules to behave as small but impenetrable spheres. The nonzero
volume of the molecules implies that instead of moving in a volume V they are
restricted to a smaller volume V nb, where nb is approximately the total volume
taken up by the molecules themselves. This argument suggests that the perfect gas
law p nRT/V should be replaced by
when repulsions are significant. The closest distance of two hard-sphere molecules
of radius r, and volume Vmolecule , is 2r, so the volume excluded is (2r)3, or
8Vmolecule. The volume excluded per molecule is one-half this volume, or 4Vmolecule,
so b 4VmoleculeNA.
The pressure depends on both the frequency of collisions with the walls and
the force of each collision. Both the frequency of the collisions and their force
are reduced by the attractive forces, which act with a strength proportional to the
molar concentration, n/V, of molecules in the sample. Therefore, because both
the frequency and the force of the collisions are reduced by the attractive forces,
the pressure is reduced in proportion to the square of this concentration. If the
reduction of pressure is written as a(n/V)2, where a is a positive constant characteristic
of each gas, the combined effect of the repulsive and attractive forces is the
van der Waals equation of state as expressed in eqn 1.21.
In this Justification we have built the van der Waals equation 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 how
to derive the form of an equation out of general ideas. The derivation also has the
advantage of keeping imprecise the significance of the coefficients a and b: they are
much better regarded as empirical parameters than as precisely defined molecular
properties.
Example 1.4 Using the van der Waals equation to estimate a molar volume
Estimate the molar volume of CO2 at 500 K and 100 atm by treating it as a van der
Waals gas.
Method To express eqn 1.21b as an equation for the molar volume, we multiply
both sides by (Vm b)V2m
, to obtain
(Vm b)V2m
p RTV2m
(Vm b)a
and, after division by p, collect powers of Vm to obtain
Vb
RT
p
V
a
p
V
ab
p mmm
3 2 0

4
3 4
3
r3
p
nRT
V nb

p
RT
Vb
a
V

mm
2

1.4 THE VAN DER WAALS EQUATION 19

Table 1.7 Selected equations of state
Critical constants
Equation Reduced form* pc Vc Tc
Perfect gas
van der Waals 3b
Berthelot 3b
Dieterici 2b
Virial
* Reduced variables are defined in Section 1.5.
p
RT
V
BT
V
CT
V
()()

mmm
12
a
4bR
a
4e2b2
p
T
V
/T V

e2 e
r
r
2 rr
21
p
RT
Vb
a/RTV

em
m
2
3
2
3
12
a
bR

/
1
12
2
33
12
aR
b

/
p
T
V TV

8
31
3
2
r
rrr
p
RT
Vb
a
TV

mm
2
8
27
a
bR
a
27b2 p
T
VV

8
31
3
2
r
rr
p
RT
Vb
a
V

mm
2
p
RT
V

m
Although closed expressions for the roots of a cubic equation can be given, they
are very complicated. Unless analytical solutions are essential, it is usually more
expedient to solve such equations with commercial software.
Answer According to Table 1.6, a 3.592 dm6 atm mol2 and b 4.267 102
dm3 mol1. Under the stated conditions, RT/p 0.410 dm3 mol1. The coefficients
in the equation for Vm are therefore
b + RT/p 0.453 dm3 mol1
a/p 3.61 102 (dm3 mol1)2
ab/p 1.55 103 (dm3 mol1)3
Therefore, on writing x Vm/(dm3 mol1), the equation to solve is
x3 0.453x2 + (3.61 102)x (1.55 103) 0
The acceptable root is x 0.366, which implies that Vm 0.366 dm3 mol1. For a
perfect gas under these conditions, the molar volume is 0.410 dm 3 mol1.
Self-test 1.5 Calculate the molar volume of argon at 100C and 100 atm on the
assumption that it is a van der Waals gas. [0.298 dm 3 mol1]
(a) The reliability of the equation
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 state of all substances, and accurate work on gases must resort to the virial
equation, use tabulated values of the coefficients at various temperatures, and analyse
the systems numerically. The advantage of the van der Waals equation, however, is
that it is analytical (that is, expressed symbolically) and allows us to draw some general
conclusions about real gases. When the equation fails we must use one of the
other equations of state that have been proposed (some are listed in Table 1.7), invent
a new one, or go back to the virial equation.
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. 1.15. Some

1 THE PROPERTIES OF GASES

calculated isotherms are shown in Figs. 1.17 and 1.18. 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 (3). The
van der Waals coefficients, such as those in Table 1.7, are found by fitting the calculated
curves to the experimental curves.
(b) The features of the equation
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 1.21b
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 cohesive and dispersing effects are in balance.
The van der Waals loops occur when both terms in eqn 1.21b have similar magnitudes.
The first term arises from the kinetic energy of the molecules and their repulsive
interactions; the second represents the effect of the attractive interactions.
(3) The critical constants are related to the van der Waals coefficients.
Pressure
Temperature
1.0
1.5
0.8
Volume
1.5
1.0
0.5
0
0.1 1 10
1.5
1
0.8
Reduced pressure, /ppc
Reduced volume, V/Vc
Fig. 1.17 The surface of possible states
allowed by the van der Waals equation.
Compare this surface with that shown in
Fig. 1.8.
Fig. 1.18 Van der Waals isotherms at several values of T/Tc. Compare these curves with those
in Fig. 1.15. The van der Waals loops are normally replaced by horizontal straight lines. The
critical isotherm is the isotherm for T/Tc 1.
Exploration 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.
Equal
areas
3

1.5 THE PRINCIPLE OF CORRESPONDING STATES 21

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 critical point the curve has a flat inflexion (4). From the properties of
curves, we know that an inflexion of this type occurs when 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. The solutions of these two equations (and using eqn 1.21b to
calculate pc from Vc and Tc) are
(1.22)
These relations provide an alternative route to the determination of a and b from the
values of the critical constants. They can be tested by noting that the critical compression
factor, Zc, is predicted to be equal to
(1.23)
for all gases. We see from Table 1.5 that, although Zc , it is approximately
constant (at 0.3) and the discrepancy is reasonably small.
1.5 The principle of corresponding states
An important general technique in science for comparing the properties of objects is
to choose a related fundamental property of the same kind and to set up a relative
scale on that basis. We have seen that the critical constants are characteristic properties
of gases, so it may be that a scale can be set up by using them as yardsticks. We
therefore introduce the dimensionless reduced variables of a gas by dividing the
actual variable by the corresponding critical constant:
[1.24]
If the reduced pressure of a gas is given, we can easily calculate its actual pressure by
using p prpc, and likewise for the volume and temperature. Van der Waals, who first
tried this procedure, hoped that gases confined to the same reduced volume, Vr, at the
same reduced temperature, Tr, would exert the same reduced pressure, pr. The hope
was largely fulfilled (Fig. 1.19). The illustration shows the dependence of the compression
factor on the reduced pressure for a variety of gases at various reduced temperatures.
The success of the procedure is strikingly clear: compare this graph with
Fig. 1.14, where similar data are plotted without using reduced variables. The observation
that real gases at the same reduced volume and reduced temperature exert the
same reduced pressure is called the principle of corresponding states. The principle
is only an approximation. It works best for gases composed of spherical molecules;
it fails, sometimes badly, when the molecules are non-spherical or polar.
The van der Waals equation sheds some light on the principle. First, we express
eqn 1.21b in terms of the reduced variables, which gives
pp
RT T
VV b
a
V V rc
rc
rcrc

2 2
p
p
p
V
V
V
T
T
Tr
c
r
m
c
r
c

3
8 0.375
Z
pV
RT c
cc
c
3
8
Vbp
a
b
T
a
Rb c c c 3
27
8
2 27
d
d
2
mmm
p
V
RT
Vb
a
2 3 V4
26
0
()

d
d mmm
p
V
RT
Vb
a
()V

2 3
2
0
4

22 1 THE PROPERTIES OF GASES

2.0
1.2
1.0
1.0
0.8
0.6
0.4
0.2
0
1357
Reduced pressure, p
r

Compression factor, Z
0246
Nitrogen
Methane
Propane
Ethene
Fig. 1.19 The compression factors of four of the gases shown in Fig. 1.14 plotted using reduced
variables. The curves are labelled with the reduced temperature Tr T/Tc. The use of reduced
variables organizes the data on to single curves.
Exploration 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?
Then we express the critical constants in terms of a and b by using eqn 1.22:
which can be reorganized into
(1.25)
This equation has the same form as the original, but the coefficients 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. 1.18 without drawing attention
to the fact), then the same curves are obtained whatever the gas. This is precisely the
content of the principle of corresponding 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 the principle (Table 1.7). In fact, all we
need are two parameters playing the roles of a and b, for then the equation can always
be manipulated into reduced form. The observation that real gases obey the principle
approximately amounts to saying that the effects of the attractive and repulsive interactions
can each be approximated in terms of a single parameter. The importance of
the principle is then not so much its theoretical 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. 1.19 instead of Fig. 1.14).