Tutorial 1: Chemical Kinetics

1. Consider the following concentration-time data for the reaction of iodide ion and hypochlorite
ion (OCl-). The products are chloride ion and hypoiodite ion (OI-).

Experiment Time (s) [I-] [OCl-] [OH-]

1 0 2.40 × 10-4 1.60 × 10-4 1.00
10 2.16 × 10-4 1.36 × 10-4 1.00
2 0 1.20 × 10-4 1.60 × 10-4 1.00
10 1.08 × 10-4 1.48 × 10-4 1.00
3 0 2.40 × 10-4 4.00 × 10-5 1.00
10 2.34 × 10-4 3.40 × 10-5 1.00
4 0 1.20 × 10-4 1.60 × 10-4 2.00
10 1.14 × 10-4 1.54 × 10-4 2.00

(a) Write a balanced equation for the reaction.

(b) Determine the rate law, and calculate the value of the rate constant.
(c) Does the reaction occur by a single-step mechanism? Explain.
(d) Propose a mechanism that is consistent with the rate law, and express the rate
constant in terms of the rate constants for elementary steps in your mechanism. (Hint:
Transfer of an H+ ion between H2O and OCl- is a rapid reversible reaction.)

2. Assume that you are studying the first-order conversion of a reactant X to products in a
reaction vessel with a constant volume of 1.000 L. At 1:00 pm, you start the reaction at 25°C
with 1.000 mol of X. At 2:00 pm, you find that 0.500 mol of X remains, and you immediately
increase the temperature of the reaction mixture to 32°C. At 3:00 pm, you discover that 0.200
mol of X is still present. You want to finish the reaction by 4:00 pm but need to continue it
until only 0.010 mol of X remains, so you decide to increase the temperature once again. What
is the minimum temperature required to convert all but 0.010 mol of X to products by 4:00
pm?

3. The half-life for the first-order decomposition of N2O4 is 1.3 × 10-5 s.

N2O4 (g)  2 NO2 (g)

If N2O4 is introduced into an evacuated flask at a pressure of 19.0 mm Hg, how many seconds
are required for the pressure of NO2 to reach 1.3 mm Hg?

4. Some reactions are so rapid that they are said to be diffusion-controlled; that is, the reactants
react as quickly as they can collide. An example is the neutralization of H3O+ by OH-, which has
a second-order rate constant of 1.3 × 1011 M-1s-1 at 25°C.

(a) If equal volumes of 3.2 M HCl and 3.2 M NaOH are mixed instantaneously, how much
time is required for 99.999% of acid to be neutralized?
(b) Under normal lab conditions, would you expect the rate of the acid-base
neutralization to be limited by the rate of the reaction or by speed of mixing?

5. The reaction 2 NO (g) + O2 (g)  2 NO2 (g) has the third-order rate law: rate = k[NO]2[O2],
where k = 25 M-2s-1. Under the condition that [NO] = 2 [O2], the integrated rate law is
 1 1
=8 +
[ ] ([ ] )

What are the concentrations of NO, O2, and NO2 after 120.0 s if the initial concentrations are
[NO] = 0.0200 M and [O2] = 0.0100 M?

6. Consider the following data for the gas-phase decomposition of NO2:

2 NO2 (g)  2 NO (g) + O2 (g)

Temperature (K) Initial [NO2] Initial Rate of Decomposition

of NO2 (M/s)
600 0.0010 5.4 × 10-7
600 0.0020 2.2 × 10-6
700 0.0020 5.2 × 10-5

If 0.0055 mol of NO2 is introduced into a 1.0 L flask and allowed to decompose at 660 K, how
many seconds does it take for NO2 concentration to drop to 0.0010 M?

7. Use the following initial rate data to determine the activation energy (in kJ/mol) for the
reaction A + B  C:

Experiment Temperature (K) Initial [A] Initial [B] Initial Reaction

Rate (M/s)
1 700 0.20 0.10 1.5 × 10-5
2 700 0.40 0.10 3.1 × 10-5
3 700 0.10 0.20 3.1 × 10-5
4 600 0.50 0.50 1.1 × 10-5

8. The reaction AC is first order in the reactant A and is known to go to completion. The
product C is colored and absorbs light strongly at 550 nm, while the reactant and
intermediates are colorless. A solution of A was prepared, and the absorbance of C at 550 nm
was measured as a function of time. (Note that the absorbance of C is directly proportional to
its concentration.) Use the following data to determine the half-life of the reaction:

Time (s) Absorbance

0 0.000
10 0.444
20 0.724
100 1.188
200 1.200
500 1.200

9. The following experimental data were obtained in a study of the reaction 2 HI (g)  H2 (g) +
I2 (g). Predict the concentration of HI that would give a rate of 1.2 × 10-5 M/s at 660 K.
 Experiment Temperature (K) Initial [HI] Initial Reaction Rate
(M/s)
1 700 0.10 1.8 × 10-5
2 700 0.30 1.6 × 10-4
3 800 0.20 3.9 × 10-3
4 660 ? 1.2 × 10-5

10. Polytetrafluoroethylene (Teflon) decomposes when heated above 500°C. Rate constants for
the decomposition are 2.60 × 10-4 s-1 at 530°C and 9.45 × 10-3 s-1 at 620°C.

(a) What is the activation energy in kJ/mol?

(b) What is the half-life of this substance at 580°C?