CHM 3410 Problem Set 1

Due date: Friday, September 3rd

Do all of the following problems. Show your work.
1) Consider 1.0000 mol of carbon dioxide (CO 2) at a temperature T = 273.0 K and confined in a volume V =
1.0000 L. Find the pressure of the gas using
a) the ideal gas law (eq 1.8)
b) the van der Waals equation (eq 1.21a or 1.21b)
c) the virial equation (eq 1.19b)
Give your values for pressure (to four significant figures) in units of bar. Values for the van der Waals a and b
coefficients for carbon dioxide are given in Table 1.6, p 916 of Atkins. The value for the virial coefficient B for
carbon dioxide is given in Table 1.4, p 915 of Atkins.
2) Dinitrogen tetroxide will dissociate in the gas phase to form nitrogen dioxide. The reaction may be written as
follows:
N2O4(g) 2 NO2(g)

K=

[p(NO2)]2
p(N2O4)

(2.1)

Note that the "pressures" appearing in the expression for the equilibrium constant are actually the pressure of the
gas divided by standard pressure, p = 1.000 bar = 0.9869 atm. K therefore has no units (this will be discussed in
detail when we cover Chapter 6 of Atkins).
In a series of experiments the following data were obtained. All data are for T = 25.0 C and a gas bulb of
volume V = 1.000 L. n represents the initial number of moles of N 2O4 present in the bulb before dissociation
occurs, and p is the total pressure of NO2 and N2O4 at equilibrium, after dissociation has taken place.
n(mmol)
p(atm)

6.28
0.2118

12.59
0.3942

18.99
0.5719

29.68
0.8550

a) Assuming the ideal gas law and Daltons law are valid, calculate the value for K for each set of data
above. (HINT: It might be easiest to find a general equation for K in terms of n , p, and other parameters, and
then use the general expression to find the value for K for each data set).
b) Since NO2 and N2O4 are not ideal gases the values found for K in part a will not be correct, as they do
not account for nonideal gas behavior. However, since all gases obey the ideal gas law in the limit p 0, a plot of
K vs p will extrapolate to the correct value for K in the limit p 0. Plot K vs p, extrapolate your plot to p = 0,
and find the true value for K for the dimerization of dinitrogen tetroxide at T = 25.0 C.
3) The isothermal compressibility, T, for a substance is defined by the relationship
T = - (1/V) (V/p)T

(3.1)

a) What are the correct SI units for T?

b) Show that T may also be defined as
T = - (1/Vm) (Vm/p)T
where Vm = V/n, is molar volume.
c) Find the value for T for an ideal gas and a van der Waals gas.

Also do the following from Atkins:

(3.2)

Exercises
1.7b
The following data have been obtained for oxygen gas at 273.15K. Calculate
the best value of the gas constant R from them and the best value of the molar mass of O 2.
p(atm)
Vm(L/mol)

0.750000
29.8649

44.8090

0.500000
89.6384

0.250000

(This is another example of a problem where you need to extrapolate data to a limit where ideal gas behavior
occurs.)
1.19b The critical constants of ethane are p C = 48.20 atm, VC = 148. cm3/mol, and TC
= 305.4 K. Calculate the van der Waals parameters for the gas and estimate the radius of the molecule.
(As a check you can compare your values for the van der Waals a and b coefficients to the values given in Table 1.6,
p. 916 of Atkins.)
Problems

1.17

A scientist proposed the following equation of state

p = (RT/Vm) - (B/Vm2) + (C/Vm3)

Show that the equation leads to critical behavior. Find the critical constants of the gas in terms of B and C and an
expression for the critical compression factor, Z.
(See the discussion on p. 36 of Atkins, where the critical constants are found for a van der Waals gas. The same
general procedure can be used in this problem.)

Solutions
1)

a) From the ideal gas law

p = nRT = (1.0000 mol) (0.083145 L.bar/mol.K) (273.00 K) = 22.70 bar

(1.0000 L)

b) From the van der Waals equation ( a = 3.610 L2.atm/mol2 ; b = 0.0429 L/mol )
p =

nRT - an 2
(V - nb)
V2
= (1.000 mol) (0.083145 L.bar/mol.K) (273.00 K) - (3.610 L 2.atm/mol2) (1.0000 mol)2 1.01325

bar

(1.0000 L) 2

[1.0000 L - (1.000 mol) (0.0429 L/mol)]

atm

1.

= (23.716 3.658) bar = 20.06 bar

c) From the virial equation ( B = - 142. x 10-3 L/mol )
p = nRT { 1 + (B/Vm) }

Vm = V/n = (1.0000 L)/(1.0000 mol) = 1.0000 L/mol

= (1.0000 mol) (0.083145 L.bar/mol.K) (273.00 K) { 1 + (- 142. x 10-3 L/mol) }

(1.0000 L/mol)
= (22.699 bar) (1.0000 0.142) = 19.48 bar
Notice that there are significant (~ 10 - 15%) differences among the three results. This is because the conditions
selected for the calculation are not that far from the critical point for CO 2 (pC = 72.85 atm, TC = 304.2 K) and so
substantial nonideal behavior is expected.
2)

a) It is useful to find a general expression for K that we can then insert our data into

Let

n = initial moles of N2O4 before dissociation

n t = n(NO 2) + n(N 2O4) = (pV/RT) = total number of moles of gas present at equilibrium, after dissociation
has occurred. n(NO2) and n(N 2O4) are the equilibrium moles of NO2 and N2O4, respectively. The ideal gas law can
be used to find n t from the equilibrium pressure of the gas mixture.
= fraction of the initial N2O4 that dissociates.
stoichiometry of hte reaction
n(NO2) = 2n
n(N2O4) = (1 - )n

This means that at equilibrium, based on the

So n t = 2n+ (1 - )n = (1 + )n ; and so = (n t/n) 1. Note that n t = pV/RT, and so n t and can be

calculated from the experimental data.
If we know n(NO 2) and n(N 2O4) we can find the corresponding partial pressures of NO 2 and N2O4 from the ideal
gas law and Daltons law
p(N2O4) = (1 - )nRT/V

p(NO2) = 2nRT/V

Substituting into the expression for K (equn 2.1) we get

K=

[2nRT/V]2 =
[(1 - )nRT/V]

42nRT
(1 - )V

The data and the values found for K are given below. Note that since the experimental data are in atm and the
standard pressure unit used in finding K is the bar, a conversion factor must be included (1.000 bar = 0.9869 atm)
n (mmol)

p(atm)

nt (mmol)

6.28
12.59

0.2118
0.3942

8.657
16.113

0.3785
0.2798

0.1435
0.1357

18.99
29.68

0.5719
0.8550

23.376
34.947

0.2310
0.1775

0.1307
0.1127

The data are plotted below. The best fit to the data, using linear least squares, is
K = 0.1546 - 0.0471 atm -1 p

Plot of K vs p
0.18
0.17
0.16
0.15
0.14
0.13
0.12
0.11
0.1
0

0.2

0.4

0.6

0.8

p (atm)

Based on the plot, the value of K at p = 0.000 atm is K = 0.155, which corresponds to the value obtained in the
limit of ideal gas behavior.
3)

a) (1/volume) (volume/pressure) = 1/(pressure) , and so atm -1, bar-1, etc.

b) T = - (1/V) (V/p)T

T = - (n/n) (1/V) (V/p)T

If we multiply and divide by n, we get

= - (n/V) ((V/n)/p)T = - (1/Vm) (Vm/p)T

c) For an ideal gas pVm = RT , and so Vm = RT/p

So (Vm/p)T = /p)T RT/p = - RT/p2
And so T = - (1/Vm) ( -RT/p2) = RT/p2Vm. But pVm = RT, and so
T = RT/(pRT) = 1/p
c) For a van der Waals gas
p =

RT (Vm - b)

a
Vm2

It is difficult to solve the van der Waals equation for Vm. We will instead use one of our partial derivative
relationships

(V/p)T = 1/(p/Vm)T
So (p/Vm)T = /Vm)T
And so (V/p)T =
T = - (1/Vm)

RT - a
(V m - b)

= 2
m

RT
+
(Vm - b)2

2a = [ 2a (Vm - b)2 RTVm3 ]

Vm3
(Vm - b)2 Vm3

(Vm - b)2 Vm3

[ 2a (V m - b)2 - RTVm3 ]

(Vm - b)2 Vm3

=
(Vm - b)2 Vm2
2
3
[ 2a (Vm - b) - RTVm ]
[ RTVm3 - 2a (Vm - b)2 ]

As a check, note that if we set a = b = 0, we get

T =

Vm4
= Vm = 1
RTVm3
RT
p

the result previously obtained for an ideal gas. That doesnt prove our result for the van der Waals gas is correct,
but it does show that it is consistent with expectations.
Exercise 1.7b
Assuming the ideal gas law applies, pV = nRT, so
R = pV/nT = pVm/T. We can use each data set to find a value for R, and then extrapolate a plot of R vs p to p = 0,
where ideal gas behavior is expected.
p (atm)

R (L.atm/mol.K)

Vm (L/mol)

0.750000
0.500000
0.250000

29.8649
44.8090
89.6384

0.0820014
0.0820227
0.0820414

The data are plotted below. The best fit to the data, using linear least squares, is
R = 0.082062 L.atm/mol.K - (8.0 x 10-5 L/mol.K) p

Plot of R vs p

R (L.atm/mol.K)

0.08208
0.08206
0.08204
0.08202
0.082
0

0.2

0.4
p (atm)

0.6

0.8

Based on the plot, the value of R at p = 0.0000 atm is R = 0.082062 L.atm/mol.K, which corresponds to the value
obtained in the limit of ideal gas behavior.
NOTE In some of the textbooks data on (density) are also given. One can use these data to find M, the
molecular mass of O2. By plotting M vs p and extrapolating to p = 0, the value of M in the limit of ideal gas
behavior may be found. Since my book does not give these data (and I am too lazy to borrow another book to find
them) I will not do those calculations.
Exercise 1.19b

There are three critical constants

pC = a/27b2

Vm,C = 3b

TC = 8a/27Rb

Since there are only two van der Waals constants, that means that they are overdetermined (we have more
equations than unknowns). We can pick any two critical constants to find a and b. The most straightforward way
to proceed is to use Vm,C and pC, as they are the two more simple relationships. However, it is well known (among
physical chemists!) that the van der Waals equation gives relatively good agreement for p C and TC, but poor
agreement for Vm,C, and so it is best to find a and b using p C and TC. In the present case, we will find a and b using
all three possible pairs of critical constants.
Vm,C and pC
b = Vm,C/3

a = 27b2pC = 3(Vm,C)2pC

Vm,C and TC
b = Vm,C/3

a = 9RTCVm,C/8

pC and TC
Solve both critical constants for a
a = 27b2pC

a = 27RbTC/8

Set a = a, and solve for b. This gives b = RTC/8pC

Now substitute for b to find a
a = 27R2TC2/64pC
Values of a and b using each possible combination of critical constants are given below, as well as the values from
Table 1.6 of Atkins.
a (L2.atm/mol2)

b (L/mol)

Using Vm,C and pC

3.167

0.0493

Using Vm,C and TC

4.173

0.0493

Using pC and TC

5.497

0.0650

Table 1.6, ethane

5.507

0.0651

As can be seen above, using pC and TC to find a and b gives very good agreement with the values listed in Table 1.6
(this is actually less impressive than it seems. While the best way to find values for a and b is to fit a wide range of
experimental data, scientists often use the relationship between p C, TC and a,b to obtain the van der Waals constants
using just the critical constants. That may well have been the method used to obtain the values in Table 1.6).

To estimate r, the (average) radius of an ethane molecule, we use the relationship at the bottom of page 33
of Atkins
b 4 Vmol NA

where Vmol = 4r3/3 is the volume of a molecule, and NA = Avogadros number

r = [3b/16NA]1/3 = [3(0.0651 x 10-3 m3/mol) / 16(6.022 x 1023 mol-1) ]1/3

= 1.86 x 10-10 m = 0.186 nm
Problem 1.17
The equation of state for the gas is
p = (RT/Vm) - (B/Vm2) + (C/Vm3)
At the critical point dp/dVm = d2p/dVm2 = 0 (these are really partial derivatives)
dp/dVm = - RT/Vm2 + 2B/Vm3 - 3C/Vm4 = 0
d2p/dVm2 = 2RT/Vm3 - 6B/Vm4 + 12C/Vm5 = 0
If we multiply both sides of the expression for dp/dV m by 2/Vm, we get
- 2RT/Vm3 + 4B/Vm4 - 6C/Vm5 = 0
If we add the above equation to the equation obtained for d 2p/dVm2, we get
- 2B/Vm4 + 6C/Vm5 = 0
6C/Vm5 = 2B/Vm4 ; Vm,C = 3C/B
We may substitute the value for Vm,C into the equation for dp/dV, to get
- RT (B/3C)2 + 2B (B/3C)3 - 3C (B/3C)4 = 0
- B2RT/9C2 + 2B4/27C3 - B4/27C3 = 0
B4/27C3 = B2RT/9C2
B2/3C = RT , and so TC = B2/3RC
Finally, we may find pC by substituting Vm,C and TC into our original equation of state
pC = R (B2/3RC) (B/3C) - B (B/3C)2 + C (B/3C)3 ; pC = B3/27C2
Finally, Z = pCVm,C/RTC = (B3/27C2) (3C/B) (1/R) (3RC/B2) = 9/27 , so Z = 1/3 .