Gases

The perfect gas

1. Explain how the perfect gas equation of state arises by combination of Boyles law, Charless law and Avogadros Principle.
An equation of state is an equation that relates the variables that define the state of a system to each other. Boyle,
Charles, and Avogadro established these relations for gases at low pressures (perfect gases) by appropriate experiments.
1
Boyle determined how volume varies with pressure ( ), Charles how volume varies with temperature ( ), and

Avogadro how volume varies with amount of gas ( ). Combining all of these proportionalities into one we find

Inserting the constant of proportionality, R, yields the perfect gas equation

= =

Real gases
2. Explain how the compression factor varies with pressure and temperature and describe how it reveals information about
intermolecular interactions in gases.

Consider three temperature regions:

< . At very low pressures, all gases show a compression factor, 1. At high pressures, all gases have
> 1 signifying that they have a molar volume greater than a perfect gas, which implies that repulsive forces
are dominant. At intermediate pressures, most gases show < 1, indicating that attractive forces reducing the
molar volume below the perfect value are dominant
, 1 At low pressures, slightly greater than I at intermediate pressures, and significantly greater than 1
only at high pressures. There is a balance between the attractive and repulsive forces at low to intermediate
pressures, but the repulsive forces predominate at high pressures where the molecules are very close to each
other.
> , > 1 At all pressures because the frequency of collisions between mol-ecules increases with
temperature.

3. Describe the formulation of the van der Waals equation.

The van der Waals equation 'corrects' the perfect gas equation for both attractive and repulsive interactions between
the molecules in a real gas.
The repulsive interactions between molecules are taken into account by supposing that they cause the molecules
to behave as small but impenetrable spheres. The non-zero 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 = should be replaced by = when repulsions are

significant.
The pressure depends on both the frequency of collisions with the walls and the force of each collisions with the wall and the
force of each collision. Both the frequency of the collisions and their force are reduced by attractive interaction, which act
with a strength proportional to the molar concentration /, of the molecules in sample. Therefore, because both the
frequency and the force of collisions are reduced by attractive interactions, the pressure is reduced in proportion to the square
of this concentration.
2
If the reduction of pressure is written as () where a is a positive constant characteristic of each gas, the combined
effect of repulsive and attractive forces is the van der Waal equation
2
= ( )


In terms of molar volume =

= 2

The constants a and b are called the van der Waals coefficients. As can be understood from aboves discussion, a represents the
strength of attractive interactions and b that of the repulsive interactions of between the molecules. They are characteristic of
each gas but independent of the temperature.
Simple Mixtures
The thermodynamic description of mixtures
1. Are there any circumstances under which two (real gases) will not mix spontaneously?

Perfect gases spontaneously mix in all proportions. There are, however, conceivable circumstances under which two real
gases might not mix spontaneously. Con-sider allowing two gases initially at the same pressure p to mix (so that mixing them
would not change the pressure). Consider carrying out this process at constant temperature as well. Then mixing would be
spontaneous if < 0. Consider entropic and enthalpic contributions:

Now > 0 would be positive, so mixing would always be favoured entropically. The only circumstances under which
mixing might not be spontaneous would be if > , that is if interactions between the species were so
energetically unfavorable as to outweigh the entropic term. We might consider such unfavorable interactions unlikely in
gases; after all = 0 for perfect gases. At the same time, we know that there are liquids for which such unfavorable
interactions prevent mixing at least in some proportions and at some temperatures (the proverbial oil and water). Consider
two such species at a temperature above the critical temperature of both and at a pressure high enough to make their
densities more typical of liquids than gases. Under such circumstances, the species are technically gases, although the term
supercritical fluid is more informative [Section 1C.I(c)]. One might find examples of immiscibility among such supercritical
fluids.

2. Explain the molecular origin of Raoults law and Henrys law.

Raoult's law defines the behaviour of ideal solutions. Like ideal gases, what makes the behaviour ideal can be expressed in
terms of intermolecular interactions. Unlike ideal gases, however, the interactions in an ideal solution cannot be neglected.
Instead, ideal behaviour amounts to having the same interactions among molecules of the mixture's different components as
molecules of each component have with other molecules of that same component. In shorthand, ideal behaviour consists of
A-B interactions being the same as A-A and B-B interactions. If that is the case, then the cohesive forces that would keep a
molecule in the liquid phase would be the same in the solution as in a pure liquid, and the vapor pressure of a component
will differ from that of a pure liquid only in proportion to its abundance (mole fraction). Thus, we expect Raoult's law to be
valid for mixtures of components that have very similar chemical structures. Similar structures imply both similar
intermolecular interactions (governed largely by polarity) and similar sizes (implying that the mole fraction is a good
approximation to the relative proportion of the surface area occupied by each componenta factor that is relevant to rates
of evaporation and condensation).

In an ideal dilute solution, on the other hand, Raoult's law holds for the solvent in the limit as x A approaches 1, not because
A-B interactions are like A-A interactions, but because there are so many more A-A interactions than A-B interactions that A-
A interactions dominate the behaviour of the solvent. For the solute, on the other hand, there are many more A-B interactions
than B-B interactions in the limit as xB approaches zero. Thus, only one kind of interaction (A-B) is important in determining
the affinity of the solute for the solution.
Properties of Solutions
3. Explain what is meant by a regular solution; what additional features distinguish a real solution from a regular solution?
A regular solution has excess entropy of zero, but an excess enthalpy that is non-zero and dependent on composition. We
can think of a regular solution as one in which the different molecules of the solution are distributed randomly, as in an ideal
solution, but have different energies of interaction with each other. Real solutions that are not regular may also have a non-
random distribution of molecules. This is particularly likely in the case of ionic solutions, in which ions of one charge are more
likely to be surrounded by ions on the opposite charge than of the same charge.