Chemistry 123

Introduction to Inorganic Chemistry Exam 4 Practice

April 2008
Name

Useful info: k = Ae-Ea/RT R = 8.314 J/mol*K

NOTE: The practice is exam is longer than usual. Consider it extra practice. Your exam on
Friday will not be this long!

1. Consider the following reaction:

2 N2O (g)  2 N2 (g) + O2 (g)
a. Express the rate of the reaction with respect to each of the reactants and products.

b. In the first 10.0 s of the reaction, 0.018 mol of O2 is produced in a reaction vessel
with a volume of 0.250 L. What is the average rate of the reaction (with respect to
O2) over this time interval?

c. Predict the rate of change in the concentration of N2O over this time interval.

2. A reaction in which A, B, and C react to form products is first order in A, second order in
B, and zero order in C.
a. Write the rate law for the reaction.
rate = k[A][B]2[C]0 = k[A][B]2

b. What is the overall order of the reaction? 3rd order overall

c. By what factor does the reaction rate change if the other reactant concentrations are
held constant, but
[A] is doubled?
The rate will double.
[B] is halved?
The rate will decrease by one-fourth.
[C] is doubled?
The rate will not change.

d. By what factor does the rate of the reaction change if the concentrations of all three
reactants are doubled?

The rate will increase by a factor of eight.

e. What are the units of the rate constant for this reaction?
k = (M/s)/M3 = M-2s-1

3. The data below were collected for the following reaction:

2 NO2 (g) + F2(g)  NO2F (g)
[NO2], M [F2], M Initial rate, M/s
 0.100 0.100 0.026
0.200 0.100 0.051
0.200 0.200 0.103
0.400 0.400 0.411

For NO2: experiment 2:1

For F2: experiment 3:2

Write an expression for the reaction rate law:

rate = k[NO2][F2]

What is the overall order of the reaction?

2nd order overall (1st order with respect to each reactant)

Calculate the value of the rate constant, k (with units).

Using data from experiment 1:
k = (0.026 M/s)/(0.100 M)(0.100 M)= 2.6 s-1M-1

4. A reaction has a rate constant of 0.0117 s-1 at 400. K and 0.689 s-1 at 450. K.

a. Determine the activation energy (Ea) for the reaction

b. What is the value of the rate constant at 425 K?

5. Consider the following two gas-phase reactions:

a. AA (g) + BB (g)  2 AB (g)

b. AB (g) + CD (g)  AC (g) + BD (g)

If the two reactions have identical activation energies and are carried out under the
same conditions, which one would you expect to have a faster rate, and why?

Reaction (a) should have a faster rate. The two reactions differ in orientation factors.
Since AA and BB (in reaction a) are symmetric, the collision of AA and BB should not
have a specific orientation requirement. In reaction b, both reactants are asymmetric, so
they must collide in a specific orientation before a reaction can occur. This will cause a
slower rate for reaction b.

6. The graphs below represent different order plots for the decomposition of cyclobutane:
C4H8  2 C2H4
From these plots, determine the order of the reaction and the value of the rate constant
(with units). What is the rate of reaction when [C4H8]o = 0.25 M?
 The first order plot (ln[C4H8] versus time)
1/[C4H8] versus time is linear, so the reaction is 1st order.
3.2
The value of the rate constant can be
3
determined from the slope of the line:
2.8
2.6
2.4
1/[C4H8], M-1

2.2
2
Because the reaction is 1st order, we can
1.8
1.6
express the rate law as:
1.4
1.2 ln[C4H8]t = ln[C4H8]o – kt
1 [C4H8] versus time (the integrated rate law expression)
0 20 40 60 80 100 120
1 Time, s Or, as
0.9 rate = k[C4H8] (the differential rate law)
0.8
Using the first-order differential rate
law, we find that when [C4H8]o = 0.25 M
[C4H8], M

0.7

0.6
Rate = (0.011 s-1)(0.25 M) = 0.0028
M/s
0.5

0.4

0.3
0 20 ln[C40
4H 8] versus
60 time 80 100 120
Time, s
0
-0.1
-0.2
-0.3
-0.4
-0.5
ln[C4H8]

-0.6
-0.7
-0.8
-0.9
-1
-1.1
-1.2
0 20 40 60 80 100 120
Time, s
7. The half-life for radioactive decay of U-238 is 4.5 billion years and is independent of
initial concentration. How long will it take for 10% of the U-238 atoms in a sample of U-
238 to decay?
A first-order reaction has a half-life that is independent of concentration: t ½ = ln2/k
The rate constant for this reaction is: k = ln2/t½ =ln2/(4.5 x 109 yr) = 1.54 x 10-10 yr-1

Now, using the 1st order integrated rate law:

If a sample of U-238 initially contained 1.5 x 1018 atoms 13.8 billion years ago, how many
U-238 atoms are present today?

8. A rise in reaction temperature increases the rate of reaction. Using a catalyst can also
increase the rate of reaction. Do catalysts and temperature increase change the
reaction rate by the same means? Explain.

Temperature change and catalysts affect the reaction rate in two different ways. When
the temperature of a reaction increases, the number of molecules that collide with
sufficient energy (greater than the activation energy) increases, so the rate increases.
There is no change to the activation barrier for the reaction.

When a catalyst is added to the reaction, the activation energy of the reaction
decreases. A catalyst does this by changing the mechanism, or sequence of reaction
steps, of the reaction such that the pathway from reactants to products is lower in
energy.

Both of these factors (temperature and change in Ea) are accounted for in the Arrhenius
equation: k = Ae-Ea/RT

9. A reaction is believed to occur by the flowing mechanism:

step 1: A2  A + A

step 2: A + A + B  A2B

step 3: A2B + C  A2 + BC

a. Write the overall reaction.

B + C  BC

b. Write the rate law for each step and indicate its molecularity.

rate1 = k1[A2] unimolecular

rate2 = k2[A]2[B] termolecular
rate3 = k3[A2B][C] bimolecular

c. Identify the reaction intermediates.

A and A2B are intermediates

d. Is a catalyst used in this reaction? If so, what is it?

Yes: A2 is a catalyst
10. Three mechanisms for the reaction NO2 (g) + CO (g)  CO2 (g) + NO (g) have been
proposed:

a. Step 1: NO2 + CO  CO2 + NO

b. Step 1: NO2 + NO2  NO + NO3 (slow)

Step 2: NO3 + CO  NO2 + CO2 (fast)

c. Step 1: NO2 + NO2  NO + NO3 and its reverse (both fast, equilibrium)

Step 2: NO3 + CO  NO2 + CO2 (slow)

Which mechanism agrees with the following rate law: rate = k[NO 2]2? Explain your
reasoning.

Mechanism (a) cannot be correct. It is a single-step mechanism and would have the rate
law: rate = k[NO2][CO], which does not agree with the proposed rate law.

For mechanism (b), the rate-determining step gives the rate law, rate = k[NO 2]2. Since
this matches the proposed rate law, the mechanism agrees with the rate law. This is a
plausible mechanism for the reaction.

The rate determining step in mechanism (c) would be rate = k[NO 3][CO].
The faster, equilibrium step (1) has a rate law: rate1 = k1[NO2]2 and rate-1 = k-1[NO][CO2].
Since this step is in equilibrium (rate of forward and reverse are matched, we can say:
k1[NO2]2 = k-1[NO][CO2].

This allows us to substitute [NO3] = k1[NO2]2/(k-1[NO]) in order to remove an intermediate

from the rate law expression.

Thus, rate = k2k1[NO2]2[CO]/([k-1[NO]). This does not agree with the proposed rate law,
so this mechanism should be rejected.

Mechanism (b) is the only one consistent with the rate law rate = k[NO 2]2.