10

Based on the Maxwell-Boltzmann distribution, three different speeds have been derived: (i) the
root mean squared speed, vrms; (ii) the mean speed, vmean; and (iii) the most probable speed,
vmp.Note that vrms > vmean > vmp.

Example: What is the probability that a He atom will be found within ±10 m s−1 of its RMS
speed at 298 K?
vr ms +10

∫v
Solution: we need to calculate, Probability = f (v)d v
r ms−10
However, rather than solving the integral, we are going to assume that the distribution is
approximately constant over the small range of speeds considered around the root mean squared
speed [CHECK: f(vrms ± 10 m/s) are within 1% of f(vrms) so this approximation is very good].
Hence, we will solve

( 2π RT )
3/2
M 2 2
Probability ≈ f (vrms )Δv = 4π vrms e −Mvr ms /(2RT )Δv
We had in a previous example determined the RMS speed for He atoms at 298 K to be
vrms = 1.36 × 103m s −1, therefore substituting this value, along with the other known data and
constants into the above equation, we have
3/2

( 2π × 8.3144621JK −1m ol −1 × 298K )

4.003 × 10−3kgm ol −1 −3 −1 3 2 −1 −1
Probability = 4π (1.36 × 103m /s)2e −(4.003×10 kgmol )×(1.36×10 m/s) /(28.3144621JK mol ×298)20m /s = 0.0136

So 1 in 74 He atoms will have a speed within 10 m s-1 of the RMS speed at 298 K.

Section 1C Real Gases

Real gases do not behave as perfect gases because atoms and molecules can interact and they
have finite volume. However, in certain conditions (low p, high T, away from condensation
point), interactions can be neglected and the perfect gas equation is a good approximation.
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1C.1 Deviations from perfect gas behaviour

See below for a schematic view of the intermolecular interaction potential for real gases.

Note that the strength of the interaction (depth of the potential energy well) and the distance at
which this minimum occurs depends on the two species involved. Of course, for interactions of
molecules, which have 3-dimensional structure, the figure shown above represents some average
potential over the anisotropic (angle dependent) interaction.

Note that if one knows the potential energy between pairs of atoms or molecules, V , as depicted
above, one can determine the forces acting on the atoms or molecules, F = −dV/dR. Given
positions and momenta (velocities) for all the atoms or molecules, one can solve Newton’s
equation of motion to determine the motions of all the atoms or molecules - this is the basis of
the field of “molecular dynamics.”

How does the effect of the interactions manifest itself at the macroscopic level?

1C.1(a) Compression factor: Z


The compression factor Z is the ratio of the measured molar volume, Vm = V/n, to the molar
volume, Vm∘ , of a perfect gas at the same pressure and temperature:
Vm pVm
Z= =
Vm∘ RT


since the molar volume of a perfect gas is Vm∘ = RT /p. For a perfect gas, Z = 1.
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A deviation of Z from one is a measure of non-ideality. We can plot Z versus p (at fixed T) for a
number of different gases and observe 3 regimes.

1. at very low pressure Z ≈ 1.

2. at very high pressure, Z >> 1, which indicates that it is harder to compress the gas (repulsive
forces dominate).
3. at intermediate pressures, most gases have Z < 1 which indicates that attractive forces
dominate and favor compression.

1C.1(b) Virial Coefficients

How do we describe the deviations from perfect gas behaviour that are observed experimentally?
We know that at low pressure (p → 0), the perfect gas law is reasonable. Therefore, write an
empirical expression for the equation of state as a power series expansion in the pressure, i.e.,
pVm = RT (1 + B′p + C′p 2 + …)
where B′ and C′ are (temperature-dependent) virial coefficients. The virial equation of state is
most commonly expressed in terms of the molar volume rather than the pressure, i.e.,

( )
B C
pVm = RT 1 + + 2 +…
Vm V m
Again B and C are experimentally determined, temperature dependent coefficients. To use the
virial equation of state, one must look up the virial coefficients for the specific gas of interest and
at the specific temperature of interest.
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If we consider the compression factor for a given gas at different temperatures, we observe