SCHOOL OF MEDICINE AND HEALTH SCIENCES

DEPARTMENT OF BASIC SCIENCES

CHEMISTRY UNIT
2025 ACADEMIC YEAR

BMCH 120 TUTORIAL SHEET 3&4

SECOND SEMESTER
3RD MARCH 2025
TOPIC: CHEMICAL KINETICS & CHEMICAL EQUILIBRIUM

CHEMICAL KINETICS
1. How is the activation energy determined from the Arrhenius equation?

2. For the following reaction

N2O5 (g)⟶NO2(g) + O2(g)
Has a rate constant of 1.35x10-4 s-1 at 308K. The pre-exponential factor for this reaction is
4.79x1013s-1. Calculate the activation energy of this reaction.
3. Show the rate expression for the reaction below:
CH4(g) + 2O2(g) ⟶ CO2(g) + 2H2O(g)

4. Consider the reaction

4NO2(g) + O2(g) ⟶ 2N2O5(g)
At a particular time during the reaction, nitrogen dioxide is being consumed at the rate of
0.00130 M/s.
(a) At what rate is molecular oxygen being consumed?
(b) At what rate is dinitrogen pentoxide being produced?
5. The reaction between bromate ions and bromide ions in acidic aqueous solution is given
by the equation
BrO3- (aq) + 5Br- (aq) + 6H+ (aq) ⟶ 3Br- (l) + 3H2O(l)
Use the data below to determine the value of the rate constant.

Experiment Initial Initial Initial Measured

Concentration Concentration Concentration Initial Rate
of BrO3- of Br- (mol/L) of H+ (mol/L) (mol/L .s)
(mol/L)
1 0.10 0.10 0.10 8.0 x 10-4
2 0.20 0.10 0.10 1.6 x 10-3
3 0.20 0.20 0.10 3.2 x 10-3
4 0.10 0.10 0.20 3.2 x 10-3

6. Define half-life. Write the equations relating the half-life of a first, second and zeroth
order reaction to the rate constant. How do equations differ from one another?
7. For the reaction A ⟶ products, successive half-lives are observed to be 10.0, 20.0, and
40.0 min for an experiment in which [A]0 = 0.10 M. Calculate the concentration of A at
the following times.
a) 80.0 min
b) 30.0 min

8. Theophylline is a pharmaceutical drug that is sometimes used to help with lung function.
You observe a case where the initial lab results indicate that the concentration of
theophylline in a patient’s body decreased from 2.0 x 10-3 M to 1.0 x 10-3 M in 24 hours.
In another 12 hours the drug concentration was found to be 5.0 x 10-4 M. What is the
value of the rate constant for the metabolism of this drug in the body?

9. The rate constant for the reaction below is 0.54/M.s at 300°C

2NO2(g) ⟶ 2NO(g) + O2(g)
How long (in seconds) would it take for the concentration of NO2 to decrease from 0.62
M to 0.28 M?

10. Iodine atoms combine to form molecular iodine in the gas phase:
I(g) + I(g) ⟶ I2(g)
This reaction has a rate constant of 7.0 x 109 M-1. s-1 at 23°C.
(a) If the initial concentration of I is 0.086 M, calculate the concentration after 2.0
min.
(b) Calculate the half-life of the reaction when the initial concentration of I is 0.60
M and when the initial concentration of I is 0.42 M.

11. In a first-order decomposition reaction, 50.0% of a compound decomposes in 10.5 min.

 (a) What is the rate constant of the reaction?
(b) How long does it take for 75.0% of the compound to decompose?

12. For the reaction A ⟶products, the following data were obtained:

a) Make appropriate plots or perform linear regression using these data to test them
for fitting zero-, first-, and second-order rate laws. Test all three even if you
happen to guess the correct rate law on the first trial.
b) Determine the rate constant for the reaction.
c) Using the rate law that you have determined, calculate the half-life for the
reaction.
d) At what time will the concentration of A be 0.380?

13. The rate constant of a reaction is 4.7 X 10-3 s -1 at 25°C, and the activation energy is 33.6
kJ/mol. What is k at 75°C?

14. Assuming the activation energies are equal, which of the following reactions will occur
at a higher rate at 50°C? Explain:
NH3 (g) + HCl (g) ⟶ NH4Cl (s)
N(CH3) (g) + HCl (g) ⟶ (CH3)3NHCl (s)

15. Consider the reaction

N2(g) + 3H2(g) ⟶ 2NH3(g)
Suppose that at a particular moment during the reaction of molecular hydrogen is reacting
at the rate of 0.074 M/s.
a) At what rate is ammonia being formed?
b) At what rate is molecular nitrogen reacting?
16. The iodide ion catalyzes the decomposition of aqueous hydrogen peroxide, H2O2. This
decomposition is believed to occur in two steps.

H2O2 + I- ⟶ H2O + IO- (elementary step)

H2O2 + IO-⟶ H2O + O2 + I- (elementary step)

What is the overall equation representing this decomposition?

17. The iodide-ion-catalyzed decomposition of hydrogen peroxide, H2O2, is believed to

follow the mechanism

H2O2 + I- ⟶ H2O + IO- (slow)

H2O2 + IO-⟶ H2O + O2 + I- (fast)

What rate law is predicted by this mechanism? Explain.

18. A proposed mechanism for a reaction is

C4H9Br ⟶ C4H9+ + Br2 (slow)

C4H9+ + H2O ⟶ C4H9OH2+ (fast)
C4H9OH2+ + H2O ⟶ C4H9OH + H3O+ (fast)
a) Write the rate law expected for this mechanism.
b) What is the overall balanced equation for the reaction?
c) What are the intermediates in the proposed mechanism?

19. Hydrogen and molecular iodine to produce hydrogen iodide:

H2(g) + I2(g) ⟶ 2HI(g)
A proposed mechanism for the reaction is:

Show that the reaction rate law is Rate= k [H2][I2]

NOTE: Step 1 is fast at equilibrium. Step 2 is slow.

20. It takes as little as 5 mL (1 tsp) of methanol to cause permanent blindness or death; and
unlike ethanol, methanol can be absorbed in toxic amounts by ingestion, inhalation of
vapor, or absorption through the skin. Nevertheless, methanol is present in a number of
common household products including antifreeze, windshield-washing fluid, and paint
remover.
One method that has been used to synthesize methanol is the combination of carbon
monoxide and hydrogen gases at 100°C:
CO(g) + 2H2(g) ⟶ CH3OH(g)
This reaction is catalyzed by a nickel compound.

a) Write the expression for the rate of this reaction in terms of [CO].
b) Write the expression for the rate of this reaction in terms of [H2] and in terms of
[CH3OH].

Given the following table of experimental data at 100°C.

Experiment [CO] (M) [H2] (M) Initial Rate (M/s)
1 5.60 11.2 0.952
2 5.60 22.4 0.952
3 11.2 11.2 1.90

c) Determine the initial rate of the reaction when the starting concentration of CO is
16.5 M.
d) Calculate the time required for the concentration of CO to be reduced from 16.5
M to 1.91 M.
e) Calculate t1/2 of the reaction.
f) Given that k is 3.0 s-1 at 200°C, calculate Ea of the reaction.
g) Use the calculated value of Ea to determine the value of k at 180°C.
CHEMICAL EQUILIBRIUM
1. Write the equilibrium expressions K and Kp for each of the following
gas-phase reactions.
a. N2 (g) + O2 (g) ⇌ 2NO(g)
b. N2O4 (g) ⇌ 2NO2 (g)
c. SiH4 (g) + 2Cl2 (g) ⇌ SiCl4 (g) + 2H2 (g)
d. 2PBr3 (g) + 3Cl2 (g) ⇌ 2PCl3 (g) + 3Br2 (g)

2. The following reactions have the indicated equilibrium constants at 100°C:

(1) 2NOBr(g) ⇌ 2NO(g) + Br2(g) Kc = 0.014
(2) Br2(g) + Cl2(g) ⇌ 2BrCl(g) Kc = 7.2
Determine the value of Kc for the following reactions at 100°C:
(a) 2NO(g) + Br2(g) ⇌ 2NOBr(g) (d) 2NOBr(g) + Cl2(g) ⇌ 2NO(g) + 2BrCl(g)
(b) 4NOBr(g) ⇌ 4NO(g) + 2Br2(g) (e) NO(g) + BrCl(g) ⇌ NOBr(g) + 1/2Cl2(g)
(c) NOBr(g) ⇌ NO(g) + 1/2Br2(g)

3. Phosgene is a potent chemical warfare agent that is now outlawed by international

agreement. It decomposes by the reaction
COCI2(g) ⇌ CO(g) + C12(g) Kc= 8.3 x 10-4 (360oC)
Calculate [CO], [CI2], and [COCI2] when each of the following amounts of phosgene
decomposes and reaches equilibrium in a 10.0-L flask:
(a) 5.00 mol of COCl2 (b) 0.100 mol of COCl2

4. Even at high T, the formation of nitric oxide is not favored:

N2(g) + 02(g) ⇌ 2NO(g) Kc = 4. 10 x 10-4 at 2000°C
What is [NO] when a mixture of 0.20 mol of N2(g) and 0.15 mol of O2(g) reach
equilibrium in a 1 .0-L container at 2000°C?

5. The equilibrium constant, Kc, for the reaction

N2O4(g) ⇌ 2NO2(g) is 4.63 x 10-3 at 25°C.
What is the value of Kp at this temperature?

6. The equilibrium constant, KP, for the reaction

N2O4(g) ⇌ 2NO2 (g)
is 0.113 at 298 K, which corresponds to a standard free-energy change of 5.4 kJ/mol. In a
certain experiment, the initial pressures are PN2O4 = 0.453 atm and PNO2 = 0.122 atm.
Calculate ΔG for the reaction at these pressures, and predict the direction in which the
reaction will proceed spontaneously to establish equilibrium.

7. Calculate the equilibrium constant, KP, for the following reaction at 25°C:
2H2O(l) ⇌ 2H2(g) + O2(g)
8. At 1100 K, Kp = 0.25 for the reaction
2SO2 (g) + O2 (g) ⇌ 2SO3 (g)
What is the value of Kc at this temperature?

9. Ammonium carbamate, NH4CO2NH2, decomposes as follows:

NH4CO2NH2(s) ⇌ 2NH3(g) + CO2(g)
Starting with only the solid, it is found that at 40°C the total gas pressure (NH3 and CO2)
is 0.363 atm. Calculate the equilibrium constant Kp.

10. Consider the following equilibrium process: PCl5(g) ⇌ PCl3(g) + Cl2(g) ΔH° = 92.5
kJ/mol Predict the direction of the shift in equilibrium when
a) the temperature is raised.
b) more chlorine gas is added to the reaction mixture.
c) some PCl3 is removed from the mixture.
d) the pressure on the gases is increased.
e) a catalyst is added to the reaction mixture.

11. The two most abundant atmospheric gases react to a tiny extent at 298 K in the presence
of a catalyst: N2(g) + O2(g) ⇌ 2NO(g) Kp = 4.35 x 10-31
(a) What are the equilibrium pressures of the three components when the
atmospheric partial pressures of O2 (0.210 atm) and of N2 (0.780 atm) are put into
an evacuated 1 .00-L flask at 298 K with catalyst?
(b) What is Ptotal in the container?
(c) Find Kc for this reaction at 298 K.