Chem 4511

Problem Set 7   Due by Monday, November 7th @ 5pm 

Assume all gases to behave ideally and all temperatures to be 298K unless stated otherwise 

1. In the reaction of N2(g) + 3H2(g) Æ 2NH3(g), the following data was collected from a
1.0 L vessel at 298K:
Time (sec) 0 15 30 45 60 75
P of NH3 (torr) 0 18.67 37.38 56.06 74.62 93.33

a) What is the average rate of production of NH3(g)

Average rate of production is
Because we don’t have a total pressure or mol fraction, we convert to
concentration using the ideal gas law.
93.33 1
760
0.00502
0.0821 298

0.00502
6.69 10
75
b) Based on the rate of production of NH3(g), find the rate of reaction and the rates
of consumption of N2(g) and H2(g).

Recall that

Using the relation above: 3.346 10 (negative sign is implicit in

the wording)

3
1.004 10
2

3.346 10
 2. The reaction of 2NO2(g) Æ N2O4(g) was found to be second order in NO2(g). A 2.0L
vessel at 298K charged to 1.5 atm was allowed to react. After 15 min the total
pressure in the vessel had dropped to 1.1 atm.
a. Calculate the rate constant (based on the initial concentration of NO2) for the
reaction (be sure to include units!)
b. Calculate the half life of NO2(g) at this temperature.
One way to calculate the final and initial concentrations is to use a reaction
table using the moles of reactants and products:
2NO2 Æ N2O4 Initially all pressure is caused by NO2 so
Initial 0.123 0 ntotal=nNO2.
Change -2x +x 1.5 2.0
Final 0.123-2x x
0.0821 298
0.1226

After 15min, the pressure is caused by both NO2 and N2O4, but total moles should be the sum
of the moles of each.
0.123 2 0.123
We also know that after 15 min ntot is related to Ptot by the ideal gas law

0.08992 0.123 0.03308

Now we can find the [NO2]t and [NO2]0
0.123 0.1226 2 0.03308
0.0613 0.02823
2.0 2.0
Because this is a second order reaction we can use the relation,
1 1
.
Solving this for k we get,
1 1 1 1
2.12 10
900 . 02842 0.0615
. To find the half life we can plug our k value into the 2nd order half life eq,

/ 769 sec = 12.8 min

. .
 3. In a study of reaction of pyridine (C5H5N) with methyl iodide (CH3I) in a benzene
solution, the following set of initial reaction rates was measured at 298 K for different
initial concentrations of the two reactants:
Expt # [C5H5N]i (mol⋅L-1) [CH3I] i (mol⋅L-1) Rate i (mol⋅L-1⋅s-1)
1 1.36x10-4 5.76x10-3 2.49x10-7
2 2.72x10-4 5.76x10-3 4.98x10-7
3 5.44x10 -4 1.15x10 -2 1.99x10-6
a. Write the rate law for the reaction.
b. Calculate the rate constant k, and report it with units.

a. From experiment #1 to #2, we see that the [C5H5N] doubles, while the [CH3I] remains the
same and this caused the rate to double. Therefore the order with respect to [C5H5N] must
be first.

From experiment #2 to #3 the [C5H5N] doubles, which we know should double the rate.
Then we see that the [CH3I] also doubles. Overall the rate goes up by a factor of four. Since
doubling [C5H5N] should double the rate, the effect of doubling [CH3I] must have been to
double the rate, making the order with respect to [CH3I] first. That gives us a rate law of:

v=k[C5H5N] [CH3I]

b. To calculate the rate constant k we simply plug in some of the experimental values. Using
experiment 1 we get:

2.49 10
0.318
1.36 10 5.76 10
4. Atkins 9th Ed. Problem 21.8 (reproduced here)
The ClO radical decays rapidly by way of the reaction, 2ClO ÆCl2 + O2. The following
data have been obtained:
Time (10-3 sec) 0.12 0.62 0.96 1.60 3.20 4.00 5.75
[ClO] (10 mol/L)
-6 8.49 8.09 7.10 5.79 5.20 4.77 3.95

Determine the rate constant of the reaction and the half-life of a ClO radical.
To determine the order of this reaction we can look at equal time slices to see if the
reaction is zero order: In the first 1.6x10-3sec we lose 2.7x10-6M, but in the next
1.6x10-3sec we lose 5.9x10-7 M, therefore the reaction is not first order.

To check if the reaction is first order we can look to see if the half lives are dependent
on concentration, or at least equal drops by the same percentage over the same time
period. From 6.2x10-4 sec to 9.6x10-4 sec, a time difference of 3.4x10-4sec the
concentration drops by 12.2%. From 1.6x10-3 sec to 1.6x10-3 sec, a time difference of
1.6x10-3 sec, the concentration drops by 10.2%. Over a much longer time difference,
the concentration drops by a lower percentage, therefore the half life must be
concentration dependent and so the reaction cannot be first order.

To check if the reaction is second order (plausible if we hypothesize that this is an

elementary reaction), then we must graph 1/[ClO] vs time. A straight line will tell us
that the reaction is second order with a slope of k and an intercept of 1/[ClO]0.

2nd Order Plot of ClO reaction
300000
1/[ClO] (1/M)

200000
100000 y = 2.37E+07x + 1.18E+05
R² = 9.74E‐01
0
0 0.001 0.002 0.003 0.004 0.005 0.006 0.007
time (sec)

This is a linear plot and it gives m=k=2.37x107 M-1sec-1

To find the half life we can plug the slope and intercept into the 2nd order half life
equation. / 0.0050
.
.