Tutorial Sheet 1

1. Consider the following initial data for the reaction

2NO2 (g) + F2 (g) → 2NO2F (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 X10-4
2 1.72 1.15 1.36 X10-3
3 1.15 2.30 1.22 X10-3
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.

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2. The rate law for the reaction described by
N2O2 (g) ) → 2NO (g)
is the first order in the concentration of N2O2 (g). Derive an expression for the time-dependent behavior of [NO], the
product concentration.

3. The reaction between carbon disulfide and ozone

CS2 (g) + 2O3 (g) →CO2 (g) + 2SO2 (g)
was studied using a large excess of CS2. The pressure of ozone as a function of time is given in the following table.
Is the reaction first order or second order with respect to ozone?

Time/s Ozone pressure/torr

_____________________________
0 1.76
30 1.04
60 0.79
120 0.52
180 0.37
240 0.29

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4. The rate constant K1 for the reaction described by

H+ (aq) + OH- (aq) H2O (l)

is 1.04 X 1011 dm3.mol-1.s-1. Calculate the half life of this reaction if the initial conditions are
(a) [H+]0 = [OH-]0 = 0.10 mol.dm-3
(b) [H+]0 = [OH-]0 = 1.0 X10-7 mol.dm-3

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5. Derive an integrated expression for a second-order rate law v = k[A][B] for a reaction of stoichiometry 2A + 3B →
P.

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 7 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 second order rate constant for the alkaline hydrolysis of ethyl formate in 85% ethanol (aqueous) at 29.86 0C is
4.53 L mol−1 s−1. (a) If the reactants are both present at 0.001 mol L−1, what will be the half-life of the reaction? (b)
If the concentration of one of the reactants is doubled and of the other is cut in half, how long will it take for half
the reactant present at the lower concentration to react?

9. The reaction A → B is nth order (where n = 1/2, 3/2, 2, 3 etc.) and goes to completion to the right. Derive the
expression for the half life in terms of k, n, and [A] 0.

10. A gas reaction 2A → B is second order in A and goes to completion in a reaction vessel of constant volume and
temperature with a half life of 1h. If the initial pressure of A is 1 bar, what are the partial pressures of A, of B, and
the total pressure at 1h, 2h, and at equilibrium? (p a = 0.5, pb = 0.25; 0.33, 0.33; 0, 0.5)

11. A first order reaction has a rate constant of 2.24 × 10 −5 s−1 at 3200C. Calculate the half-life of the reaction. What
fraction of the sample remains after being heated for 5 hrs at 320 0C? How long will a sample have to be heated at
3200C to decompose 92% of the initial amount present. (t1/2 = 3.09 × 104 s; 66.8%; 31.3h)

12. Predict how the total pressure varies during the reaction 2 ICl(g) + H 2(g) → I2(g) + 2 HCl(g) in a constant-volume
container. Assume that at the start of the reaction the partial pressures of the reactants are equal and that no products
are present.

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13. The rate of formation of C in the reaction 2 A + B → 2 C + 3 D is 2.7 mol dm−3s−1. State the reaction rate, and the
rates of formation or consumption of A, B, and D.

14. If the rate laws are expressed with (i) concentrations in moles per cubic decimetre, (ii) pressures in kilopascals,
what are the units of a second-order and of a third-order rate constant?

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15. The rate law v = (kr1[A][B])/(kr2 +kr3[B]1/2)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.

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16. The second-order rate constant for the reaction CH3COOC2H5(aq) + OH−(aq) → CH3CO2−(aq) + CH3CH2OH(aq) is
0.11 dm3mol−1s−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 −3and
[CH3COOC2H5] = 0.110 mol dm−3?

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17. Derive the integrated form of a third-order rate law v = kr[A]2[B] in which the stoichiometry is 2 A + B → P and the
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reactants are initially present in (a) their stoichiometric proportions ([𝐵]0 = [𝐴]0 ); (b) with B present initially in
2
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.

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18. The reaction cis-2-butene to trans-2-butene is first order in both directions. At 25°C, 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?

19. The equilibrium A ↔ B is first order in both directions. Derive an expression for the concentration of A as a
function of time when the initial molar concentrations of A and B are [A] o and [B]o. What is the final composition
of the system?

20. The equilibrium constant for the reaction D+ + OD− = D2O is 4.08 × 1016 mol−1 dm3. The rate constant for the
reverse reaction is independently found to be 2.52 × 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.

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21. 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.

22. Two radioactive nuclides decay by successive first-order processes: X 22.5d Y 33.0d Z (the quantities over
the arrows are the half-lives in days). Suppose that Y is an isotope that is required for medical applications. At what
time after X is first formed will Y be most abundant?

23. Many reactions approximately double in rate for each 10 C increase in temperature. For a reaction at 25 C, what is
the Ea?

24. The activation barrier for the hydrolysis of sucrose into glucose and fructose is 108 kJ/mol. If an enzyme increases
the rate of the hydrolysis reaction by a factor of 106, how much lower must the activation barrier be when the
sucrose is in the active site of enzyme. [Assume that the frequency factors for the catalyzed and uncatalyzed
reactions are identical and temperature is 25 ℃]

25. Consider parallel reactions where A forms P with rate constant k1 and A forms Q with rate constant k2. The
activation energies are 45.3 kJ/mol for 𝑘1 and 69.8 kJ/mol for𝑘2. If the rate constants are equal at 320 K, at what
temperature will 𝑘1/𝑘2 = 2?

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26. Consider the reaction mechanism

𝐴+𝐵 𝐶→𝑃

Write the expression for d[P]/ dt, the rate of product formation. Assume equilibrium is established in the first
reaction before any appreciable amount of product is formed, and show that d[P]/ dt = k 2K[A][B], where K is the
equilibrium constant for the first step.

27. The decomposition of ozone 2 O3 → 3 O2 (g) occurs by the reaction mechanism

M(g) + O3 (g) O2 (g) + O(g) + M(g)

𝐾2
O(g) + O3 (g) → 2 O2 (g)
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). (Ans: -1/2d[O3 ]/dt = k1k2[O3] 2 [M]/(k−1[O2][M] + k2[O3])

28. The rate law for the hydrolysis of ethyl acetate by aqueous sodium hydroxide at 298 K is k obs[OH−][CH3COOC2H5
]. The mechanism for the reaction is

CH3COOC2H5 + OH− CH3CO−(OH)OC2H5

𝐾2
CH3CO−(OH)OC2H5 → CH3COOH + CH3CH2O –
𝐾−3
CH3COOH + C2H5O – → CH3COO– + C2H5OH
Write the rates of formation of all the intermediate species? Under what conditions does this mechanism give the
observed rate law? For these conditions, express kobs in terms of the individual steps of the reaction mechanism.
𝐾 𝐾
(Ans: fast equilibrium for step 1; 2 1)
𝐾−1

29. A proposed mechanism for the reaction of nitramide in water is

O2NNH2 ⇋ O2NNH− + H+
O2NNH− → N2O + OH−
H+ + OH− → H2O
𝐾 [𝑂 𝑁𝑁𝐻 ]
The experimentally observed rate law for the reaction is 𝑜𝑏𝑠 2 + 2 . (a) What is the overall reaction? (b) What are
[𝐻]
the units of kobs? (c) Under what conditions is this mechanism consistent with the rate law? (d) Express kobs in terms
of the rate constants of the elementary reactions. (e) With this mechanism as an example explain the concept of rate
determining step.

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30. 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.

31. One suggested mechanism for the reaction

𝑆2 𝑂82− + 3𝐼 − → 2𝑆𝑂42− + 𝐼3−
is:
𝑆2 𝑂82− + 𝐼 − ⇋ 𝑆𝑂4 𝐼 − + 𝑆𝑂42− (rapid)
𝐾1
𝐼 − + 𝑆𝑂4 𝐼 − →
𝐼2 +𝑆𝑂42− (slow)
𝐾2
−
𝐼 + 𝐼2 → 𝐼3− (fast)
while another is:
𝐾1
𝑆2 𝑂82− + 𝐼 − → 𝑆2 𝑂8 𝐼 3− (slow)
𝐾2
𝑆2 𝑂8 𝐼 3− → 𝐼 + + 2𝑆𝑂42− (fast)
𝐾3
𝐼 − + 𝐼 + → 𝐼2 (fast)
𝐾4
𝐼 − + 𝐼2 → 𝐼3− (fast)
The reaction is first order both with respect to the persulfate and iodide ions. (i) Derive the rate laws for these two
mechanisms (ii) Discuss whether one can differentiate if the reaction proceeds according to either or both of these
mechanisms.

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