CML-101 Tutorial-1 (Chemical Kinetics)

1. Given the following data, determine the order of the reaction with respect to H2.
H2(g) + 2ICl(g) → I2(g) + 2HCl(g)

(a) one-half (b) second (c) first (d) third (e) three-halves
Answer: Note that order with respect to H2 is the question. Hence, we check where the
concentration/pressure of other reactant i.e. [ICl] (torr) is constant, and observe the rate and
pressure (in torr) of H2. It has been observed that, expt.-1 and expt.-3 has constant [ICl] value
in torr. However [H2] value decreases 5-fold and the rate (M/s) also decreases 5-fold, going
from expt.-1 to expt.-3. So the rate and [H2] value decreases linearly, hence it is first order
reaction with respect to H2.
2. A proposed mechanism for the following reaction is shown below. Identify the catalyst in
the reaction.
2H2O2(aq) → 2H2O(aq) + O2 in the presence of I-(aq)
Step 1: H2O2(aq) + I-(aq) → H2O(aq) + OI-(aq) (slow)
Step 2: H2O2(aq) + OI-(aq) → H2O(aq) + O2(g) + I-(aq) (fast)
(a) H2O2 (b) OI- (c) I- (d) H2O (e) O2
Answer: In the initial step (slow), I- is used as a catalyst reactant and in the second step it gets
reproduced (I-). Hence, I-(aq) is the catalyst in this reaction. Similarly, you can ask the students
to identify the intermediate (OI-(aq)).
3. The following data have been obtained for the decomposition of N2O5(g) at 67°C according
to the reaction 2N2O5(g) → 4NO2(g) + O2(g). Identify the order of the reaction with respect to
N2O5 and calculate the rate constant and the half-life of N2O5. Hint: It is not necessary to obtain
the result graphically, you may do a calculation by making estimates of the rates of change of
concentration.

Answer:
4. A number of reactions that take place on the surfaces of catalysts are zeroth order in the
reactant. One example is the decomposition of ammonia on hot tungsten. In an experiment, the
partial pressure of ammonia decreased from 21 kPa to 10 kPa in 770 s. (i) What is the rate
constant for the zeroth-order reaction? (ii) How long will it take for all the ammonia to be
consumed?
Answer:

5. Due to an excessive growth of bacteria in the lake water, with bacteria concentration 5.0 ×
10-7g/cm³, swimming in the lake has been prohibited. Swimming is only allowed when the
bacterial concentration reduces to 3.0 × 10-7 g/cm³. Based on the previous years data, the
bacterial death has been found to follow first-order kinetics with a death rate of 1.45 day-1, how
many days must the inhabitants wait until they can swim in the lake again?
Answer:
6. Consider a chemical reaction
A → products
that obeys the rate law
ⅆ[𝑨]
− = 𝒌[𝑨]𝒏
ⅆ𝒕
where n, the reaction order, can be any number except n = 1. Separate the concentration and
time variables and then integrate the resulting expression assuming the concentration of A is
[A]0 at time t = 0 and is [A] at time t to show that:
𝟏 𝟏 𝟏
(a) 𝒌𝒕 = ( − [𝑨]𝒏−𝟏) where n ≠ 1.
𝒏−𝟏 [𝑨]𝒏−𝟏 𝟎

(b) Use the above equation to derive the expression of half-life of a reaction, when n ≠ 1.
(c) Also, what happens to the expression derived in problem (b) when n = 2.
Answer:
7. Hydrogen peroxide, H2O2, decomposes in water by a first-order kinetic process. A 0.156-
mol dm-3 solution of H2O2 in water has an initial rate of 1.14 × 10-5 mol dm-3 s-1. Calculate the
rate constant for the decomposition reaction and the half- life of the decomposition reaction.
Answer:

8. You order a sample of Na3PO4, containing the radioisotope phosphorus-32 (𝑡1/2 = 14.3 days).
If the shipment is delayed in transit for two weeks, how much of the original activity will
remain when you receive the sample?
Answer:
9. Consider the schematic reaction .
a) If the reaction is one-half order with respect to [A], what is the integrated rate law expression
for this reaction?
b) What kind/type of plot would you construct to determine the rate constant k for the reaction?
c) What would be the half-life for this reaction? Will it depend on the initial concentration of
the reactant?
Answer:
10. The oxidation of NO to NO2, 2 NO(g) + O2(g) → 2 NO2(g), proceeds by the following
mechanism:
NO + NO → N2O2 (kₐ)
N2O2 → NO + NO (k'ₐ)
N2O2 + O2 → NO2 + NO2 (kb)
Verify that application of the steady-state approximation to the intermediate N2O2 results in
the rate law:
ⅆ[𝑵𝑶𝟐 ] 𝟐𝒌𝒂 𝒌𝒃 [𝑵𝑶]𝟐 [𝑶𝟐 ]
=
ⅆ𝒕 𝒌𝒂 ′ + 𝒌𝒃 [𝑶𝟐 ]
Answer:
 𝑘𝐴 𝑘𝐵
11. For the sequential reaction A → B → C, the rate constants are kA = 5 x 106 s-1
and kB = 3 x 106 s-1. Determine the time at which [B] is at a maximum.
Answer:
 𝒌𝒐𝒃𝒔
12. The rate law for the reaction described by: 2 H2(g) + 2 NO(g) → N2(g) + 2 H2O(g)
is given by:
ⅆ[𝐍𝟐 ]
= 𝒌obs [𝐇𝟐 ][𝐍𝐎]𝟐
ⅆ𝒕
Below are two proposed mechanisms:
Mechanism 1:
𝑘1
H2(g) + NO(g) + NO(g) → N2O(g) + H2O(g)
𝑘2
H2(g) + N2O(g) → N2(g) + H2O(g)
Mechanism 2:
NO(g) + NO(g) ⇌ N2O2(g) (Forward k1, Backward k-1)
𝑘2
H2(g) + N2O2(g) → N2O(g) + H2O(g)
𝑘3
H2(g) + N2O(g) → N2(g) + H2O(g)
(i) Under what conditions does mechanism 1 give the observed rate law? Express kobs in terms
of the rate constants for the individual steps of the mechanism. (ii) Under what conditions does
mechanism 2 give the observed rate law? Express kobs in terms of the rate constants for the
individual steps of the mechanism. (iii) Which of the mechanisms do you favour and why?
Answer:
 (iii)

13. The decomposition of ethane has the following mechanism:

𝑘1
C2 H6 → 2CH3
𝑘2
CH3 + C2 H6 → CH4 + C2 H5
𝑘3
C2 H5 → C2 H4 + H
𝑘4
H + C2 H6 → H2 + C2 H5
𝑘5
H + C2 H5 → C2 H6
(i) Write the expressions for:
ⅆ[𝐂𝟐 𝐇𝟔 ] ⅆ[𝐂𝐇𝟑 ] ⅆ[𝐂𝟐 𝐇𝟓 ] ⅆ[𝐇]
, , , .
ⅆ𝐭 ⅆ𝐭 ⅆ𝐭 ⅆ𝐭
(ii) Applying steady state approximation, show that:

ⅆ[𝐂𝟐 𝐇𝟔 ] 𝒌𝟏 𝒌𝟑 𝒌𝟒
− = [𝟐𝒌𝟏 + √ ] [𝐂𝟐 𝐇𝟔 ]
ⅆ𝐭 𝒌𝟓
Answer:
14. Consider the following sequential reaction scheme
𝑘𝐴 𝑘𝐼
A → I→ P
Assuming that only reactant A is present at t = 0, what is the expected time dependence of [P]
using the steady-state approximation?
Answer:
15. The decomposition of perbenzoic acid in water
2 C6H5CO3H(aq) ⇌ 2 C6H5CO2H(aq) + O2(g)
is proposed to occur by the following mechanism:
𝑘1
C6H5CO3H(aq) ⇌ C6H5CO3-(aq) + H⁺(aq)
𝑘−1
𝑘2
C6H5CO3H(aq) + C6H5CO3⁻(aq) → C6H5CO2H(aq) + C6H5CO2⁻(aq) + O2(g)
𝑘3
C6H5CO2⁻(aq) + H⁺(aq) → C6H5CO2H(aq)
Derive an expression for the rate of formation of O2 in terms of the reactant concentration and
[H⁺].
Answer:
16. The gas-phase decomposition of ethanoic acid at 1189 K proceeds by way of two parallel
reactions:
(i) CH3COOH → CH4 + CO2 𝒌𝟏 = 3.74 s-1
(ii) CH3COOH → CH2CO + H2O 𝒌𝟐 = 4.65 s-1
(a) What is the maximum theoretical yield of the ketene CH2CO at this temperature?
(b) Does the ratio of ketene to methane vary over time?
Answer:
17. The equilibrium constant in terms of the rate constants is given by the equation:
𝒌𝒂 𝒌𝒃
𝑲= / × / ×…
𝒌𝒂 𝒌𝒃

Show that this equation is an expression for the overall equilibrium constant in terms of the
rate constants for the intermediate steps of a reaction mechanism. Hint: Begin with a
mechanism containing three steps, and then argue that your expression may be generalized for
any number of steps.
Answer:
18. Show that if A reacts to form either B or C according to

then E, the observed activation energy for the disappearance of A, is given by

where, E1 is the activation energy for the first reaction and E2 is the activation energy for the
second reaction.
Answer:
19. SO2Cl2 decomposes following first order kinetics,
SO2Cl2(g) → SO2(g) + Cl2(g)
At 600 K the half-life for this process is 2.3 × 105 s. (i) What is the rate constant at this
temperature? (ii) At 320°C the half-life of this reaction changes to 3.2 × 104 s. What is the
activation energy required for this reaction?
Answer:
20. For the chemical reaction 2A(aq) ⇌ D(aq), with the forward and reverse rate constants
being 𝑘1 and 𝑘−1 respectively, derive the expression for the relaxation time in a temperature
jump experiment. Assume the forward reaction to be second order and the reverse reaction to
be first order.
Answer:
21. The thermal decomposition of ethylene oxide follows first order kinetics with a half-life of
363 minutes at 378.5°C. The activation energy of this reaction is 52 kcal/mol. Calculate the
time required to decompose 75% of ethylene oxide at 450°C.
Answer:

22. The Arrhenius parameters for the gas-phase decomposition of cyclobutane,

C4H8(g) → 2C2H4(g)
are A = 4.00 × 1015 s-1 and Ea = 261 kJmol-1. What is the half-life of cyclobutane at (i) 20°C,
(ii) 500°C?
Answer:
23. For the reaction: C2H5I + OH- → C2H5OH + I-, the rate constant was found to have a value
of 5.03 × 10-2 mol-1dm3s-1 at 289 K and 6.71 mol-1dm3s-1 at 333 K. What is the activation energy
of the reaction? What is the rate constant at 305 K?
Answer:
24. The reaction mechanism for renaturation of a double helix from its strands A and B is
thought to be,

where U is an unstable helix, and H is the stable form of the helix. The reaction between A and
B is first order in each species and the return of U to A + B is first order in U; the reaction of
U to H is first order in U. Deduce the rate law for the rate of formation of H in two ways: (i)
by assuming a pre-equilibrium and (ii) by assuming that the steady-state approximation can be
applied to U.
Answer:
25. Consider two products formed from reactant R in reactions for which: (a) product P1 is
thermodynamically more stable than product P2; and (b) the activation energy Ea for the
reaction leading to P2 is greater than that leading to P1. Derive an expression for the ratio
[P2]/[P1] when the reaction is under thermodynamic control. State your assumptions.
Answer:
26. The rate law for the reaction of para-hydrogen to ortho-hydrogen

is:

Show that the following mechanism is consistent with this rate law.
𝑘1
para-H2 ⇌ 2H(g) (fast equilibrium) (1)
𝑘−1
𝑘2
H(g) + para-H2(g) → ortho-H2(g) + H(g) (2)
Express kobs in terms of the rate constants for the individual steps of the reaction mechanism.
Answer:
For Q4 and Q7 , you may please mention the stoichiometric
coefficients of the reactants as 1.
Q4)

Q7)

𝑑
Q9) a) [A] = - k[A]1/2
𝑑𝑡

Please add a negative sign (which was missing).

Leads to an integrated rate law,
[A] = { [A]01/2 - (kt/2) } ½
b) slope = -k/2
c) t ½ = 1/k ( 2- 2) [A]01/2