CHEM 102/105 Dr. M.
Gedik
Problem Set #2: Kinetics Part II and Equilibrium (warm-up)
DISCLAIMER: Questions marked with asterisk (*) are meant to be challenging and test your ability to
apply concepts learned in lectures.
1. For the reaction A ® products, successive half-lives are obtained to be 10.0, 20.0 and 40.0 min for
an experiment in which [A]o = 0.10 M. Calculate the concentration of A after 25 min.
HINT: Think about what order the reaction should be based on the given information.
2. A reaction is carried out at 25 °C. When the temperature is increased by 15°C, the rate doubles.
(a) What is the activation energy of the reaction?
(b) Given that the enthalpy of the reaction is +23 kJ mol-1, sketch the reaction profile. Your diagram
should include axis labels, units, the value of Ea (both directions) and DH.
3. For a given reaction, the rate constant, k, was measured at two different temperatures. The two data
points determined in this experiment are as follows:
(1) 25 °C, 1.1 x 10–5 min–1 and (2) 225 °C, 2.4 x 10-2 min–1
The student who performed the experiment then plotted the logarithmic (linearized) form of the
Arrhenius equation.
(a) What value of Ea did the student get from the experimental data?
(b) What is the value of A?
(c) What is the order of this reaction?
4. Even when a mechanism is consistent with the rate law, later experiments may show it to be incorrect.
For example, the reaction between hydrogen and iodine has this rate law: rate = k[H2][I2]. The long
accepted mechanism had a single bimolecular step, that is, the overall reaction was thought to be
elementary: H2 (g) + I2 (g) ® 2 HI (g)
In the 1960s however, spectroscopic evidence showed the presence of free I atoms during the reaction.
Kineticists have since proposed a three-step mechanism:
®
(1) I2 (g) ¬ 2 I (g) fast
®
(2) H2 (g) + I (g) ¬ H2I (g) fast
(3) H2I (g) + I (g) ® 2 HI (g) slow
Show that this mechanism is consistent with the rate law.
5. The following three step mechanism has been proposed for the reaction of chlorine and chloroform.
k1
®
(1) Cl2 (g) ¬ 2 Cl (g)
k –1
k2
(2) Cl (g) + CHCl3 (g) ¾® HCl (g) + CCl3 (g)
k3
(3) CCl3 (g) + Cl (g) ¾® CCl4 (g)
The numerical values of the rates for these steps are: k1 = 4.8 x 103, k –1 = 3.6 x 103, k2 = 1.3 x 10–2,
k3 = 2.7 x 102. Derive the rate law and the magnitude of k for the overall reaction.
[O3]2
*6. A simplified rate law for ozone depletion in the atmosphere, 2 O3 (g) ® 3 O2 (g) is rate = k [O ] .
2
For this reaction, propose a two-step mechanism that consists of a fast, reversible first step, followed
by a slow second step.
*7. The following mechanism is proposed for the reaction of gaseous nitric oxide and bromine to form
nitrosyl bromide:
k1
®
NO (g) + Br2 (g) ¬ NOBr2 (g)
k –1
k2
NOBr2 (g) + NO (g) ¾® 2 NOBr (g)
Derive the theoretical rate law for the above mechanism.
HINT: You need to use the steady state approximation for this since you have no information on the
relative rates of the steps…
8. Write the equilibrium expression for the following reactions:
®
a) Br2 (l) ¬ Br2 (g)
®
b) H2O (s) ¬ H2O (g)
®
c) HF (aq) + H2O (l) ¬ H3O+ (aq) + F– (aq)
®
d) HCOO– (aq) + H2O (l) ¬ HCOOH (aq) + OH– (aq)
®
e) Na2SO4×10H2O (s) ¬ Na2SO4 (s) + 10 H2O (g)
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f) BaF2 (s) ¬ Ba2+ (aq) + 2 F– (aq)
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g) O2 (aq) ¬ O2 (g)
®
h) I2 (in CCl4) ¬ I2 (aq)
®
i) Cu2+ (aq) + 4 NH3 (aq) ¬ [Cu(NH3)4]2+ (aq)