BG 2142 Biological Thermodynamics_ Homework #1 (Due 1:00 pm Aug 25

(Wednesay), 2021, please make a copy of your solution before submitting the
ORIGINAL copy to the pigeonhole #11 outside the general office area)

Question 1.

Calculate the pressure exerted by Ar for a molar volume 1.42 L at 300 K using the van der Waals
equation of state. The van der Waals parameters a and b for Ar are 1.355 bar dm6 mol–2 and 0.0320
dm3 mol–1, respectively. Is the attractive or repulsive portion of the potential dominant under these
conditions?

Question 2. (Engel P1.9)

Consider a 20.0-L sample of moist air at 60 ºC and 1 atm in which the partial pressure of water vapor is
0.120 atm. Assume that dry air has the composition 78.0 mole percent N2, 21.0 mole percent O2, and
1.00 mole percent Ar.

a) What are the mole percentages of each of the gases in the sample?
PH O
b) The percent relative humidity is defined as % RH = *2 where PH2O is the partial pressure of water
PH 2O
in the sample and PH2O = 0.197 atm is the equilibrium vapor pressure of water at 60 ºC. The gas is
compressed at 60 ºC until the relative humidity is 100%. What volume does the mixture now occupy?

c) What fraction of the water will be condensed if the total pressure of the mixture is isothermally
increased to 200 atm?

Question 3. (you might refer to Example 7.1 in Engel, P160)

Like the van deer Waals equation, another useful equation of state is the Redlich-Kwong (RK)
equation as follows:

RT a 1
P= −
Vm − b T Vm (Vm + b)

 P   2P 
At T = Tc ,   = 0 and  2  = 0 .
 Vm Tc   Vm Tc
(a) Use above information to determine the constants a and b in terms of experimentally determined
values Tc and Pc, that is to derive the following forms and find the values of constants x and y: (You

1
might need to use the following formula at some point, X 3 + 3 X 2Y + 3 XY 2 + Y 3 = ( X + Y )3 ) (This
part is quite difficult. This derivation was published in a paper in 1970s, you might be able to get
some useful information online). The analytic forms of a and b are given in Example 7.1 (given in the
end below). Most likely you won’t be able to derive the analytic forms, by a normal way of solution, it
will be great if you can get the values for x and y in the expressions below.
5
R 2Tc 2
a=x
Pc
RTc
b= y
Pc

(b) Without calculation, draw three representative isotherms in a P-Vm diagram, and explain the main
features. For isotherms at T  Tc , explain why they are unphysical.

(c) For a CO2 gas at T = 40 oC, calculate the pressure exerted for a molar volume of 0.1 L and 100 L
using both ideal gas law and the RK equation (be careful of the unit conversions). Compare the results,
what can you conclude? For CO2, the RK equation constants are given as:
1
a = 64.63 dm 6 bar mol − 2 K 2

b = 0.02971 dm 3mol −1

Question 4. (Engel P1.37)

 df ( x ) dx 
lim  f ( x ) g ( x )  x →0 = lim  
 dg ( x ) dx  x →0
Use L’Hôpital’s rule, to show that the expression derived
for Pf in part b of Example Problem 1.1 has the correct limit as γ → 0.

(In case, you don’t have the textbook yet, I attach below the scan of the Examples 1.1 and 7.1 for your
reference.)

Question 5. For the Lennard-Jones potential energy, please find the expression for rmin and ULJmin.

Question 6. For the Van der Waals constant, b, is called the excluded volume. As we discussed in
lecture, this excluded volume is related to the volume of molecules. For CO2, please estimate the size
of a single molecule assuming it is spherical.

2
Question 7. (Engel P1.24)

When Julius Caesar expired, his last exhalation had a volume of 500. cm3 and contained 1.00 mole
percent argon. Assume that T = 300. K and P = 1.00 atm at the location of his demise. Assume further
that T has the same value throughout the Earth’s atmosphere. If all of his exhaled Ar atoms are now
uniformly distributed throughout the atmosphere, how many inhalations of 500. cm3 must we make to
inhale one of the Ar atoms exhaled in Caesar’s last breath? Assume the radius of the Earth to be 6.37 ×
106 m. [Hint: Calculate the number of Ar atoms in the atmosphere in the simplified geometry of a plane
of area equal to that of the Earth’s surface.] from Problem 1.20 for the dependence of the barometric
pressure on the height above the Earth’s surface as
P = P0 e−M ave gz RT where Mave is the mean molecular weight
of air.

3
4
5
6