Part I: Basic

Concepts of
Thermodynamics
Lecture 4:
• Kinetic Theory of Gases
• Kinetic Theory for real
gases

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 Kinetic Theory for real gases
Recall that for real gases:

(i) The volume occupied by the molecules under ordinary conditions

may not be negligible compared with the total volume of the gas.

(ii) The force exerted by the molecules on one another may not be
negligible.

Let us now consider these assumptions in some detail.

(i) Volume of molecules: Under normal temperature and pressure, the

volume of the molecules is less than 0.1 % of the total volume of the
gas.
It has been found that at a pressure of about 10 MPa the molecules
would occupy a volume which is only about 12 times their own volume.
The effect of the finite size of the molecules will be to reduce the
available free space for movement. As a result, the number of impacts
on the walls of the container, and therefore the pressure on them, will be
greater than that obtained by the use of the kinetic theory of gases.

(ii) Force exerted by the molecules on one another: Liquids possess the
cohesive property. The fact that gases can be transformed into liquids
implies that the molecules of a gas possess attractive force. The
consequence of attractive forces among the molecules is to make the
pressure less than that to be expected theoretically.

Note: The Joule-Thomson experiment provides direct experimental

proof of molecular attraction. The general observation of this
experiment is that a gas cools itself on passing through a porous plug. In
passing from a high to a low pressure the gas does not perform any

4-2
 external work. Therefore, the cooling observed must be due to the work
done in overcoming the mutual attraction of the molecules.

The Van der Waals Equation

In 1873, J. D. Van der Waals made the first successful attempt to

modify the ideal-gas equation in order to correct for the volume and
molecular attraction. When gases at ordinary pressures and
temperatures are compressed, the volume is reduced by reducing the
intermolecular space. Because the molecules themselves are not
compressible, at very high pressures the entire volume is not
inversely proportional to the pressure.
• At comparatively low pressures, the molecules of a real gas do not exert
any force on one another, because they are widely separated. Therefore,
at relatively low pressures, real gases behave like ideal gases.

• At high pressures the molecules are brought closer together and

consequently the attractive force between the molecules increases,
which has the same effect as an increase in external pressure. It then
follows that, if external pressure is applied to a volume of gas,
particularly at low temperatures, the decrease in volume is slightly
greater than would be obtained by pressure only. This effect is more
pronounced at low temperatures for the simple reason that at such
temperatures the molecules move more slowly and have less tendency
to move apart on colliding with one another.

• To derive the ideal-gas equation PV = nRT from the kinetic theory of

gases, a number of assumptions were made. Van der Waals modified
the ideal-gas equation to take into account that two of these assumptions
may not be valid. The modified assumptions which are applicable to

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 real gases are as follows.
o (i) The volume of the molecules may not be negligible in relation
to the volume V occupied by the gas.
o (ii) The attractive forces between the molecules may not be
negligible.

Pressure correction

Although there is no net force acting on a molecule inside a container from the rest of
the molecules, when next to the wall, all the rest of the molecules reside on one side, thus
producing a net (attractive) force and consequently the pressure on the wall will be
diminished.
The measured pressure P is thus less than the ideal pressure given
by the kinetic theory of gases.
It is, therefore, necessary to add a correction term P’ to the
measured pressure P, so, the ideal pressure is P + P’.

P’ is proportional to the product of

• the number of molecules striking unit area of the wall per second at
any instant and
• the number of molecules per unit volume behind them.

• For a given volume of gas, both these numbers are proportional to the
density ρ of the gas. Therefore, the total attractive force which is
related to the correction term P' is proportional to ρ2.

ρ2∝ 1/V2

Thus, the corrected pressure becomes:

P + P’ = P + a/V2 1-67

where a is a constant depending on the gas.

4-4
 The term a/V2 is called the cohesion pressure.

Volume correction

The volume of a gas cannot be compressed indefinitely because of the final

size of the molecules. A correction term b, known as the co-volume, must be
subtracted from the measured volume V, so that the corrected volume is V -b.
The term b is a factor depending on the actual volume of the molecules.

Note: b might be thought that as being equal to the volume of the

molecules but this is not the case. According to van der Waals, the
co-volume is equal to four times the actual volume of the
molecules; other slightly different estimates have also been made.

The equation for the ideal gases becomes (for one mole of gas):

⎛ a ⎞
⎜ P + 2 ⎟(V − b ) = RT 1-68
⎝ V ⎠

When V is large, both b and a/V2 become negligible and the van der Waals
equation reduces to the ideal-gas equation PV = RT (for n = 1).

Note: At low pressures, the correction a for intermolecular attraction is

more important than the correction b for molecular volume. At high
pressures and small volumes, the correction for the volume of the
molecules becomes important, since the molecules are relatively incom-
pressible and they form an appreciable part of the total volume.
Under ordinary conditions, the deviations from the gas laws are
negligible.

A Van der Waals gas can be liquefied and it possesses a critical point
which is given by the conditions

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 ⎛ ∂P ⎞
⎜ ⎟ =0
⎝ ∂V ⎠T
⎛ ∂2 P ⎞
⎜ ⎟ =0
⎜ ∂V 2 ⎟
⎝ ⎠T

The critical pressure, volume and temperature are given by:

Pc = a / 27 b2

Vc = 3b

Tc = 8a / 27bR

The van der Waals constants

• At very low pressures, both a and b may be neglected, and Eq. 1-68
becomes
PV = RT.

and under these conditions the gas obeys the ideal-gas law, which may be
considered as representing the limiting behavior of gases at extremely low
pressures.

• At slightly higher pressures, it is generally possible to ignore b relative

to V. Then Eq. 1-68 becomes

⎛ ⎞
⎟(V ) = RT
a
⎜P+ 2 1-69
⎝ V ⎠
or
PV = RT – a/V 1-70

Eq. 1-70 shows that PV < RT and decreases with increasing pressure.

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• At moderately high pressures, V becomes smaller, so b cannot be
ignored. However, a/V2 is small compared with the high value of P.
Thus Eq. 1-68 becomes

P (V – b) = RT
or
PV = RT + P b 1-71

Eq.6 shows that PV > RT and increases with increasing pressure.

• It can be shown that when the product PV is plotted against P, it has a

minimum (for P = 0) called Boyle Point TB.

Rewriting van der Waals equation for P:

RT a
P= − 2
V −b V
or
V a
PV = RT −
V −b V
Differentiating the equation with respect to P at constant temperature

∂f ∂f ∂V
=
Note: ∂P ∂V ∂P where f = RT
V
−
a
V −b V
We get
∂ ⎛ ⎞
(PV )T = ⎜⎜ RT − RTV 2 + a2 ⎟⎟⎛⎜ ∂V ⎞⎟ 1-72
∂P ⎝ V − b (V − b) V ⎠⎝ ∂P ⎠T

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 ∂
For a minimum, ∂P (PV )T = 0
which gives
⎛ RT RTV a ⎞
⎜ − + ⎟ =0
⎜ V − b (V − b)2 V 2 ⎟
⎝ ⎠
or,
2
a ⎛V − b ⎞
RT = ⎜ ⎟
b⎝ V ⎠ 1-73
When P=0, V>>0,
a
RTB =
b
and
a
TB =
Rb 1-74

At all temperatures greater than the Boyle point the value of PV will
always increase as pressure increases. Since the values of a for hydrogen
and helium are very small, for these two gases, TB will be relatively low.
If we substitute the values of a and b for hydrogen (a = 2.5 x 10-2
Jm3/mol; b = 2.67 x 10-5 m3/mol and R = 8.31 J/mol.K), we obtain TB =
112 K. The experimental value is found to be 106 K.

Conclusion: The Boyle point TB is defined as the lowest temperature above

which PV increases continuously with increasing P. It can be shown that if the
pressure is not too large, van der Waals equation reduces to:

PV = RTB 1-75

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 Virial Equation of State

If the pressure P and the volume V of n moles of a gas held at a constant

temperature are measured over a wide range of values of the pressure, and the
product Pυ, where υ = V / n, is plotted as a function of 1/υ. The relation
between Pυ and 1/ υ may be expressed by means of a power series or virial
expansion of the form

B C D
Pυ = RT (1 + + + + ...) 1-75
υ υ2 υ3
And the other a series in powers of P:

Pυ = RT+B’P + C’P2 + … . 1-76

where B, C, . . ., are called second, third, etc. virial coefficients; their values
depend on the substance and are function of the temperature. The first virial
coefficient is 1 because Pυ must approach RT as 1/υ approaches zero.
This type of equation is useful for purpose of extrapolation. All the known
forms of equation of state, i.e. the Clausius, the Berthelot, etc. can be
expressed in the virial form if desired, the virial coefficients being determined
by the constants of the various equations. Of all the virial coef. The second
coef. Is the most important; it depends on the molecular interaction.
In the pressure range 0-40 atms, the relation between Pυ and 1/υ is almost
linear, so that only the first two terms in the expansion are significant. In
general, the greater the pressure range, the greater are the number of terms in
the virial expansion.

The virial equation may be derived from some assumptions. For example, if
we assume T and P to be independent variables, then PV is a function of T and
P. Mathematically,

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 PV = f(T, P)

where f denotes some function. As P →0, PV → RT with no appreciable

deviation even at several atmospheres.

Therefore, it is possible to expand f(T, P) in a Maclaurin series about P = 0

at constant temperature. Thus,

∂ 1 ∂2
f (T , P) = f (T ,0 ) + f (T , P) P =0 ,T =T P + f (T , P) P =0 ,T =T P 2 + ...
∂P 2 ! ∂P 2

where f(T, 0) = RT. If we take

∂
f (T , P) P =0 ,T =T P ≡ B
∂P

1 ∂2
2
f (T , P) P =0 ,T =T P 2 ≡ C
2 ! ∂P

and so on, then the Maclaurin series becomes

PV = f(T, P) = f(T, 0) + BP + CP2 + . . .

PV = RT + BP + CP2 + . . .

This equation is identical with the virial Equation 1-76. If there are no
attractive and repulsive intermolecular forces within a mass of gas, then it
can be shown from statistical mechanics that the virial coefficients B, C, . ..
identically vanish, and the virial equation reduces to PV = RT (for 1 mol of
gas), which is the ideal-gas law. Therefore, we can say that a gas which
obeys PV = RT at all pressures has no intermolecular forces acting between
its molecules. However, it should be remembered that, in reality, null
intermolecular forces never occur. Consequently some properties of real
gases do not approach their ideal-gas values as pressure tends to zero.

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Note: The Maclaurin series

A function f(x) expanded in the power series

f(x) = a0 + a1x + a2x2 + a3x3 + …

By differentiating the series term by term,

df
= f ′( x) = a1 + 2 a2 x + 3 a3 x 2 + ...
dx

d2 f
2
= f ′′( x) = 2 a2 + 6 a3 x + ...
dx

By substituting x = 0 in f(x), f’(x), f’’(x), we get

f(0) = a0; f’(0) = a1; f’’(0) = 2!a2; …

Thus, the above series becomes (in the range where it is convergent)

⎛ x2 ⎞ ⎛ n ⎞ n
f ( x) = f (0 ) + xf ′(0 ) + ⎜ ⎟ f ′′(0 ) + ... + ⎜ x ⎟ f (0 ) + ...
⎜ 2! ⎟ ⎜ n! ⎟
⎝ ⎠ ⎝ ⎠

which is Maclaurin series.

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Enthalpy – preliminary considerations

The quantity enthalpy was introduced into thermodynamics by the

American physicist and physical chemist J. Willard Gibbs, who was
one of the founders of modem chemical thermodynamics.

Chemical reactions are usually performed at constant pressure. In

these situations usually the volume changes with work being done.

2
− ∫ PdV = − P∆V 1-77
1

The net work being done can be separated into two terms, one at
constant pressure and the rest:

Wnet = Wtotal + P∆V

For isobaric processes, the function Enthalpy is:

H = U + PV 1-78

and is a state function.

• If we replace for ideal gases PV = nRT,

H = U + nRT 1-79

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