CML101 CHEMICAL KINETICS

TUTORIAL PROBLEMS
1. Consider the following initial rate data for the reaction: 2 NO2(g) + F2(g) → 2 NO2F(g)
Run [NO2]0 /mol.dm-3 [F2]0 /mol.dm-3 v0 / mol.dm-3.s-1
1 1.15 1.15 6.12 x 10-4
2 1.72 1.15 1.36 x 10-3
3 1.15 2.30 1.22 x 10-3

where [NO2]0 and [F2]0 are the initial concentrations of NO2(g) and F2(g) and v0 is the initial rate. Determine
the reaction rate law and the value of the rate constant.

2. Consider the base-catalyzed reaction: OCl- (aq) + I- (aq) → OI- (aq) + Cl- (aq); Use the following initial-
rate data to determine the rate law and the corresponding rate constant for the reaction.
[OCl-] /mol.dm-3 [I-] /mol.dm-3 [OH-]0 /mol.dm-3 v0 / mol.dm-3.s-1
1.62 x 10-3 1.62 x 10-3 0.52 3.06 x 10-4
1.62 x 10-3 2.88 x 10-3 0.52 5.44 x 10-4
2.71 x 10-3 1.62 x 10-3 0.84 3.16 x 10-4
1.62 x 10-3 2.88 x 10-3 0.91 3.11 x 10-4

3. The rate law for the reaction described by N2O2 (g) → 2 NO (g) is first order in the concentration of N2O2
(g). Derive an expression for the time-dependent behaviour of [NO], the product concentration.
4. The reaction SO2Cl2 (g) → SO2 (g) + Cl2 (g) is first order and has a rate constant of 2.24 x 10-5 s-1 at 320
°C. Calculate the half-life of the reaction. What fraction of a sample of SO2Cl2 (g) remains after being
heated for 5 hrs at 320 °C? How long will a sample have to be heated at 320 °C to decompose 92% of the
initial amount present?
5. 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?
6. The rate of decomposition of acetaldehyde can be studied by measuring the pressure in a system at constant
volume and temperature. Express the rate of reaction in terms of the rate of change of the pressure. The
overall reaction is CH3CHO(g) → CH4(g) + CO(g).
7. The decomposition of acetaldehyde given in problem 6 is second order. Formulate the rate law in terms of
the total pressure of the system and integrate the result to express the pressure as a function of time.
8. The reaction A + B → P is found to be first order in both A and B. The reaction was carried out in a solution
that was initially 0.080 mol dm−3 in A and 0.060 mol dm−3 in B. After 1.0 h the concentration of B had
fallen to 0.030 mol dm−3. (i) Calculate the rate constant. (ii) What are the half-lives of the reactants?
[ ][ ]
9. The rate law 𝜐 = was established in a series of experiments. Identify the conditions under
[ ] ⁄
which (i) an order with respect to A, (ii) an order with respect to B, and (iii) an overall order, can be
assigned.
10. Derive the integrated form of a third-order rate law v = kr[A]2[B] in which the stoichiometry is 2A +
B → P and the reactants are initially present in (a) their stoichiometric proportions ([𝐵] = [𝐴] ); (b)
with B present initially in twice that amount ([B]0 = [A]0). Express your rate law in terms of [A]0, [B]0, and
x, where [A] = [A]0 − 2x.
11. The second-order rate constant for the reaction CH3COOC2H5 (aq) + OH− (aq) → CH3CO2− (aq) +
CH3CH2OH (aq) is 0.11 dm3 mol−1 s−1. What is the concentration of ester (CH3COOC2H5) after (i) 20 s,
(ii) 15 min when ethyl ethanoate is added to aqueous sodium hydroxide so that the initial concentrations
are [NaOH] = 0.060 mol dm−3 and [CH3COOC2H5] = 0.110 mol dm−3?
[ ]
12. Consider a reaction A → Products that obeys the rate law − = 𝑘[𝐴] , where n  1. (i) Derive the
integrated rate law assuming that the initial concentration of the reactant is [𝐴] at t = 0 and is equal to [A]
at time t. (ii) Use the rate law derived to write the expression for the half-life of a reaction of the order n.
(iii) Derive an expression for the time it takes for the concentration of a substance to fall to one-third the
initial value in an nth-order reaction.
13. 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?
14. The reaction cis-2-butene to trans-2-butene is first order in both directions. At 25 oC, the equilibrium
constant is 0.406 and the forward rate constant is 4.21×10-4 s-1. Starting with a sample of pure cis isomer
with [cis]o = 0.115 mol.dm-3, how long would it take for half the equilibrium amount of the trans isomer to
form?
15. The reaction A ⇄ B is first-order in both directions. (a) Derive an expression for the concentration of
A as a function of time when the initial molar concentrations of A and B are [A] 0 and [B]0. (b) What is the
final composition of the system?
16. The equilibrium constant for the reaction D+ + OD− ⇄ D2O is 4.08 x 1016 mol−1 dm3. The rate constant
for the reverse reaction (k-1) is independently found to be 2.52 x 10−6 s−1. What would the relaxation time
for a T-jump experiment be? The density of D2O is 1.04 g cm−3.
17. For the chemical reaction 2 A (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.
18. In a temperature-jump experiment to investigate the kinetics of an isomerization reaction that is first
order in both directions, the relaxation time was measured as 27.6 μs. The rate constant for the forward
reaction is known to be 12.4 ms–1. Calculate the rate constant for the reverse reaction.
19. Many reactions approximately double in rate for each 10 oC increase in temperature. For a reaction at
o
25 C, what is the Ea?
20. Suppose that in an industrial batch process a substance A produces the desired compound I that goes
on to decay to a worthless product C, each step of the reaction being first order. At what time will I be
present in greatest concentration? Calculate the maximum concentration of I.
21. Distinguish between reaction order and molecularity.
22. Using the steady state approximation, devise the rate law for the composition of N2O5:
2 N2O5 (g)  4 NO2(g) + O2(g)
On the basis of the following mechanism:
N2O5  NO2 + NO3 ka
NO2 + NO3  N2O5 ka `
NO2 + NO3  NO2 + O2 + NO kb
NO + N2O5  NO2 + NO2 + NO2 kc
23. A proposed mechanism for the reaction between H2 (g) and Br2 (g) is
Br2 ⇄ 2Br (forward: k1 and backward: k5)
Br + H2  HBr + H k2
H + Br2  HBr + Br k3
H + HBr  H2 + Br k4
Write expressions for d[HBr]/dt, d[H]/dt, and d[Br]/dt. Assuming that d[H]/dt = d[Br]/dt = 0, solve for
d[HBr]/dt in terms of [H2], [Br2], and [HBr]. If 1 >> (k4/k3){[HBr]/[Br2]}, what is the pseudo-order of the
reaction?

24. The decomposition of ozone 2 O3 (g)  3 O2 (g) occurs by the following mechanism:

𝑀 (𝑔) + 𝑂 (𝑔) ⇆ 𝑂 (𝑔) + 𝑂 (𝑔) + 𝑀 (𝑔) (forward: k1 and backward: k-1)

𝑂 (𝑔) + 𝑂 (𝑔) ⟶ 2𝑂 (𝑔) (rate constant k2)

where M is a molecule that can exchange energy with the reacting ozone molecule through a collision, but
does not react. Use this mechanism to derive the rate law for d[O3]/dt assuming that O(g) can be treated by
a steady state approximation(SSA)

25. Nitramide (O2NNH2) decomposes in water according to the chemical equation

𝒌𝒐𝒃𝒔
𝑶𝟐 𝑵𝑵𝑯𝟐 (𝒂𝒒) ⎯ 𝑵𝟐 𝑶(𝒈) + 𝑯𝟐 𝑶(𝒍)
[ ] [𝑶𝟐 𝑵𝑵𝑯𝟐 ]
With the experimental determined rate law being = 𝑘 [ ]
A proposed mechanism for the reaction is
𝑂 𝑁𝑁𝐻 (𝑎𝑞 ) ⇌ 𝑂 𝑁𝑁𝐻 (𝑎𝑞 ) + 𝐻 (𝑎𝑞 ) (𝑓𝑎𝑠𝑡 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚, 𝑘 , 𝑘 )
𝑂 𝑁𝑁𝐻 (𝑎𝑞 ) → 𝑁 𝑂(𝑔) + 𝑂𝐻 (𝑎𝑞) (slow)
𝐻 (𝑎𝑞) + 𝑂𝐻 (𝑎𝑞) → 𝐻 𝑂(𝑙) (fast)
Is this mechanism consistent with the observed rate law? If so, what is the relationship between kobs and
the rate constants for the individual steps of the mechanism?

26. Derive an equation for the steady-state rate of the sequence of reactions A ⇄ B ⇄ C ⇄ D, with [A]
maintained at a fixed value and the product D removed as soon as it is formed.
𝒌𝒐𝒃𝒔
27. The rate law for the reaction described by: 𝟐 𝑯𝟐 (𝒈) + 𝟐 𝑵𝑶(𝒈) ⎯ 𝑵𝟐 (𝒈) + 𝟐 𝑯𝟐 𝑶(𝒈) is given
[ ]
by = 𝑘 [𝐻 ][𝑁𝑂] . Below are two proposed mechanisms.

Mechanism 1
𝐻 (𝑔) + 𝑁𝑂(𝑔) + 𝑁𝑂(𝑔) → 𝑁 𝑂(𝑔) + 𝐻 𝑂(𝑔)
𝐻 (𝑔) + 𝑁 𝑂(𝑔) → 𝑁 (𝑔) + 𝐻 𝑂 (𝑔)

Mechanism 2
𝑁𝑂(𝑔) + 𝑁𝑂(𝑔) ⇌ 𝑁 𝑂 (𝑔) (Forward k1; backward k-1)
𝐻 (𝑔) + 𝑁 𝑂 (𝑔) → 𝑁 𝑂(𝑔) + 𝐻 𝑂(𝑔)
𝐻 (𝑔) + 𝑁 𝑂(𝑔) → 𝑁 (𝑔) + 𝐻 𝑂(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?
28. The following is a highly simplified mechanism for the decomposition of C3H8 :
𝐶 𝐻 → 𝐶𝐻 + 𝐶 𝐻
𝐶𝐻 + 𝐶 𝐻 → 𝐶𝐻 + 𝐶 𝐻
𝐶𝐻 → 𝐶 𝐻 + 𝐶𝐻
𝐶𝐻 + 𝐶𝐻 → 𝐶𝐻

Pick out the intermediates and formulate a steady state expression for the intermediates, where possible.
From these, find expressions for each steady state concentration, and then formulate the overall rate of
reaction in terms of the rate of production of CH4.

29. For the gas phase decomposition reaction (CH3)3COOC(CH3)3  2 CH3COCH3 + C2H6 , the
generally accepted mechanism is:

(𝐶𝐻 ) 𝐶𝑂𝑂(𝐶𝐻 ) → 2 (𝐶𝐻 ) 𝐶𝑂

(𝐶𝐻 ) 𝐶𝑂 → 𝐶𝐻 𝐶𝑂𝐶𝐻 + 𝐶𝐻
𝐶𝐻 + 𝐶𝐻 → 𝐶𝐻

Using the steady state assumption show that the reaction is first order throughout, even though it occurs in
three consecutive steps. Formulate the rate of reaction in terms of production of C2H6.

30. A proposed mechanism for the thermal decomposition of acetaldehyde (gas phase)
𝐶𝐻 𝐶𝐻𝑂 (𝑔) ⎯ 𝐶𝐻 (𝑔) + 𝐶𝑂(𝑔)

is
𝐶𝐻 𝐶𝐻𝑂 → 𝐶𝐻 + 𝐶𝐻𝑂
𝐶𝐻 + 𝐶𝐻 𝐶𝐻𝑂 → 𝐶𝐻 + 𝐶𝐻 𝐶𝑂
𝐶𝐻 𝐶𝑂 → 𝐶𝐻 + 𝐶𝑂
𝐶𝐻 + 𝐶𝐻 → 𝐶𝐻

(i) Determine the rate laws for CH4, CH3, and CH3CO.
(ii) Show that if you assume the steady-state approximation for the intermediate species, CH3 and
CH3CO, the rate law for methane formation is given by
⁄
𝑑[𝐶𝐻 ] 𝑘
= 𝑘 [𝐶𝐻 𝐶𝐻𝑂] ⁄
𝑑𝑡 𝑘
(iii) If the last step of the mechanism is replaced by 2 𝐶𝐻 𝐶𝐻𝑂 → 𝐶𝐻 𝐶𝑂𝐶𝑂𝐶𝐻 , apply the steady-state
approximation for the intermediate species, CH3 and CH3CO to show that the rate of formation of CO is
given by
⁄
𝑑[𝐶𝑂] 𝑘
= 𝑘 [𝐶𝐻 𝐶𝐻𝑂] ⁄
𝑑𝑡 𝑘
(iv) For parts (ii) and (iii), what are the overall activation energies Eobs given by in terms of the activation
energies of the individual reactions?
(v) Repeat part (iv) for Aobs, the measured Arrhenius pre-exponential factor for the overall reaction.

31. The chlorination of an organic molecule (M) to give P may proceed by the following mechanism: (i)
Cl2  2 Cl (ii) Cl + M  R (iii) R + Cl2  P + Cl (iv) Cl + Cl  Cl2 . (a) Setup the rate expressions for
intermediates. (b) Apply the steady state approximation to the intermediate species and obtain the rate
law.
32. The decomposition of ethane has the following mechanism:

[ ] [ ] [ ] [ ]
(i) Write the expressions for , , , .
(ii) Applying steady state approximation to the intermediates, show that