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CH353 Physical Chemistry I, Spring 2016

Thermodynamics, Statistical Mechanics, & Chemical Equilibria


Problem Set 1: Ideal and Nonideal Gases
1) Modern surface science research is often carried out in ultra-high vacuum (UHV) chambers
that can typically reach pressures on the order of 10-11 torr.
a. How many gas molecules are there in each cubic centimeter of a UHV chamber at this
pressure at room temperature?
b. What is the chambers molar volume?
c. The average density of interstellar space is roughly 1 H atom/cm3 and its temperature is
typically on the order of 10 K. What are the pressure and molar volume of this interstellar
medium?

2) a. Why do all gasses display ideal behavior as their pressure is lowered?


b. Explain in your own words why the energy of an ideal gas should only depend on its
temperature.
c.

For a nonideal gas, what other parameters might you expect to affect the energy of the
gas?

3) a. Write out in your own words what the van der Waals a and b parameters represent.
b. Rank in increasing order the van der Waals a and b parameters for the following four
gases: He, propane, isopropanol, and toluene. Check your intuition by looking up these
values and explaining the observed trends in a and b.

4) A colleague of yours calibrates a pressure gauge for a 1.00 L cylinder that will hold Argon at
150 K. The calibration run, however, used Helium instead of Argon and assumed the ideal
gas equation of state.
How many moles of Argon can be placed in the cylinder before the pressure reading is in error
by 10%?
For Ar, B2V(150 K) = 20.9 cm3/mol. For He, B2V(150 K) = -80.6 cm3/mol

5) The interaction potential between two atoms can be described by a Lennard-Jones potential:
12 6
U r 4
r
r
a. Sketch this potential. Why does it represent a reasonable approximation for the interaction
between two atoms?
b. Prove that represents the point where U r crosses zero and that - represents the
lowest value of the potential.
c. Would you expect He or Ar to have a larger value of ? What about ?

d. The typical strength of a covalent bond tends to be on the order of 100-500 kJ/mol
depending on the nature of the two atoms that form the bond. For small molecules such
as CO, O2, and N2, /kB ~ 100 K. How strong are the attractive interactions described by
the Lennard-Jones potential relative to the covalent bonds that hold these molecules
together?

6) The virial equation can be written either as a perturbative expansion in pressure or inverse
molar volume:

B T B3V T
PVm
1 2V

...
RT
Vm
Vm2
Compared to the van der Waals equation, the virial equation tends to be more accurate as it
can more naturally describe competition between the attractive and repulsive interactions that
shape the gass behavior change as you alter the pressure, temperature, and volume of the
gas. Well compare the van der Waals equation and the virial equation in this problem.
a. Compare the virial equation to the van der Waals equation to show that B2V T b

a
RT

where a & b are the parameters that appear in the van der Waals equation of state. To do
this, youll likely find both the binomial expansion
van der Waals equation as P

1
1 x x 2 ... and rewriting the
1 x

RT 1 a
useful.

Vm 1 b Vm Vm2

b. The Boyle Temperature is a special temperature where B2V T = 0. What is the


significance of this temperature?
c. The van der Waals parameters for O2 are a = 1.360 L2atm/mol2 and b = 31.83 cm3/mol.
Calculate the Boyle Temperature for O2 based on van der Waals parameters and compare
its value to the experimental value of 405 K.
d. You should find that your value for part c is of the same order of magnitude as the
experimental value, but still differs from it by a significant amount. This highlights one of
the shortcomings of the van der Waals equation: its parameters are not temperature
dependent. Given the physical meaning of the van der Waals a & b parameters, why might
you expect that a more natural description of a gas would allow them to vary with
temperature?

7) In class, we will see that the second virial coefficient can be related to the bimolecular
interaction potential of a gas through:

B2V T 2 N A r 2 1 e U r kBT dr
0

This equation is important since it lets us relate a parameter we can measure in lab, B2V, to
something that we cant directly measure but governs the interaction between gas molecules,
U(r). In practice, we determine U(r) by guessing a functional form for it, and integrating the
above equation to calculate B2V which we then compare to experiment.

In problem 5, you saw that a Lennard-Jones function can provide a reasonable description for
U(r) and contains two adjustable parameters, and , that can be used to match experiment.
However, integrating the Lennard-Jones function analytically using the above equation is
difficult. Thus, in this problem well use an approximation of the Lennard-Jones potential where
we replace the repulsive portion with a hard-wall potential.

U r 6

r
r

a. Sketch this potential. Be sure to label your axes and the values of the potential at points
where it intersects the axes.
b. Why does this model represent a reasonable approximation of the interaction of two gas
molecules? What aspects of the interaction between two gas molecules will this potential
capture?
c. For gas molecules that interact with this potential, find an analytical expression for the
second virial coefficient, B2V T , in terms of the molecular parameters and d. To simplify
this process, you can assume that the gas is at high temperature, which will allow you to
expand the exponential that appears in the expression for B2V T above in the attractive
region (& only in the attractive region!) using a Taylor series (i.e. e ar 1 ar ).
d. Determine the Boyle temperature of Argon using d = 3.0 and = 115 cm-1. How does
this value compare with experiment (TB = 410 K). Does our simplified potential give you a
better estimate of the Boyle temperature than the van der Waals equation (Problem 6d)?
The van der Waals parameters for Ar are: a = 1.3307 L2atm/mol2; b = 31.83 cm3/mol.