REAL GASES: DEVIATIONS FROM IDEALITY

 Ideal behaviour of gases does not depend on the identity of a gas. So ideal gas law is
applicable to all gases.
 Under ordinary, conditions most real gases do behave ideally. Thus, they do obey the
postulates of the kinetic–molecular theory.
 Recall assumptions 1 and 3 (gas molecules have negligible volume in comparison with
distances between them, and the molecules of ideal gases do not attract one another.
 Under some conditions, however, most gases can have pressures and/or volumes that are not
accurately predicted by the ideal gas law. That is under these conditions they are not
behaving entirely as postulated by the kinetic–molecular theory.
 Non-ideal gas behavior is most significant at high pressures and/or low temperatures, that is,
near the conditions under which the gas liquefies.
 At low pressures, the volume of molecules is a small fraction of the total volume that each
molecule can move through virtually the entire measured volume of the container, Vmeasured
and volume of molecule can be neglected, (Figure 1.8a) as in the ideal gas law.

Figure 1.8 A molecular representation of deviations from ideal behavior.

 At high pressures, a gas is compressed so that the volume of the molecules themselves
becomes a significant fraction of the total volume occupied by the gas and cannot be
neglected. The ideal gas law is no longer a good approximation (Figure 1.8b).

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 As a result, the available volume, Vavailable, for any molecule to move in is less than the
measured volume by an amount that depends on the volume excluded by the presence of the
other molecules. To account for this, we subtract a correction factor, nb.
Videally available = Vmeasured - nb
 The factor nb corrects for the volume occupied by the molecules themselves.
 Larger molecules have greater values of b, and the greater the number of molecules in a
sample (higher n), the larger is the volume correction.
 The correction term becomes negligibly small, however, when the volume is large.
 Recall that pressure is as a resulting of molecular collisions with the walls of the
container; Kinetic theory assumes that between collision molecules do not influence each
other (attractive forces between molecules are not significant).
 For any real gas, the molecules can attract one another. At higher temperatures, the
potential energy due to intermolecular attractions is negligibly small compared with
the high kinetic energy due to the rapid motion of the molecules and to the great distances
between them.
 When the temperature is quite low (low kinetic energy), the molecules move so slowly
that the potential energy due to even small attractive forces becomes important.
 This disturbance becomes even more important at high pressure when the molecules are
very close together.
 Consequently, the molecules deviate from their straight- line paths and take longer to reach
the walls, so fewer collisions take place in a given time interval. Furthermore for a molecule
about to collide with the wall, the attraction by its neighbors causes the collision to be less
energetic than it would otherwise be.
 Consequently, the pressure that the gas exerts, Pmeasured, is less than the pressure it would
exert if attractions were truly negligible, Pideally exerted.
 To correct for this, we subtract a correction factor, n2a/V2, from the ideal pressure.
Pmeasured = Pideally exerted – (n2a/V2measured)

Pideally exerted = Pmeasured + (n2a/V2measured)

 In this correction term, large values of a indicate strong attractive forces.
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  When more molecules are present (greater n) and when the molecules are close together
(smaller V2 in the denominator), the correction term becomes larger. The correction term
becomes negligibly small, however, when the volume is large.
 When we substitute these two expressions for corrections into the ideal gas equation, we
obtain the equation
(Pmeasured + n2a/V2measured)( Vmeasured - nb) = nRT

(P + n2a/V2)( V - nb) = nRT

 This is called the van der Waals equation.
 In this equation, P, V, T, and n represent the measured values of pressure, volume,
temperature, and number of moles, respectively, just as in the ideal gas equation.
 The quantities a and b are experimentally derived constants that differ for different gases
(Table 1.1).
 When a and b are both zero, the van der Waals equation reduces to the ideal gas equation.

Table 1.1 A table of van der Waals constants of some common gases
Gas a (L2.atm/ mol2) b (L/ mol)
H2 0.244 0.0266
He 0.034 0.0237
Ne 0.0213 0.0171
Ar 1.35 0.0322
Xe 4.23 0.0266
N2 1.39 0.0391
NH3 4.17 0.0371
CO2 3.59 0.0427
CH4 2.25 0.0428
Cℓ2 6.55 0.0562
CCℓ4 20.6 0.138

 Relative values of a and b in Table 1.1 can be understood in terms of molecular properties.
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 Note that a for helium is very small. This is the case for all noble gases and many other non-
polar molecules, because only very weak attractive forces exist between them, (dispersion
forces).
 Ammonia, NH3, has high value of a since it is made up of polar molecules that have dipole -
dipole interactions which exhibit greater forces of attraction for one another.
 Larger molecules have greater values of b. For instance, H2, a first-row diatomic molecule,
has a greater b value than the first-row monatomic He.

Example
Calculate the pressure exerted by 1.00 mole of methane, CH4, in a 500.-mL vessel at 25.0°C
assuming
a. ideal behavior and,
b. Non-ideal behavior.
Solution
Using the ideal gas law
PV = nRT
= (1.00 mol) (0.08206 L.atm mol-1 K-1)(298 K)
0.500 L
= 48.9 atm

Using van der Waals equation

(P + n2a/V2)( V - nb) = nRT

From the table For CH4, a = 2.25 L2.atm/ mol2 and b = 0.0428 L mol-1

[P + (1.00 mol)2(2.25 L2.atm/ mol2)/(0.0500 L)2][0.500 L - (1.00 mol)(0.0428 l mol-1)]

= (1.00 mol) (0.08206 L.atm mol-1 K-1)(298 K)
0.500 L
P + 9.00 atm = 53.6 atm
= 44.6 atm