SCH4U8 Rates of Reaction & Mechanisms Practice Problems

1. In the reaction 𝐴 + 2𝐵 → 3𝐶 + 4𝐷, the initial concentration of 𝐴 was 0.0415 mol/L, and after
14.7 min the concentration of 𝐴 was 0.0206 mol/L. What is the average rate of consumption
in moles per litre per second of reactant 𝐵?
Time (s) Concentration (mol/L)
2. Calculate the average rate of a reaction, given the
following data: 60.0 5.00 x 10-2
85.0 3.25 x 10-2

3. For the reaction shown below, the average rate of formation of 𝐶𝑂!(#) is 5.50 x 10-4 mol/s.
' (
𝐵𝑟!(%&) + 𝐻𝐶𝑂𝑂𝐻(%&) → 2𝐵𝑟(%&) + 2𝐻(%&) + 𝐶𝑂!(#)
a) What minimum amount in moles of 𝐶𝑂!(#) is formed in 5.00 min?
b) How does this compare with the amount of 𝐵𝑟!(%&) that reacts in the same time?

4. The concentration of a reactant is 4.0 x 10-2 mol/L at t = 2.0 min. If the average rate of
consumption of the reactant from t = 1.5 min to t = 2.0 min was 0.045 mol/LŸs, what was the
concentration of this reactant at t = 1.5 min?

5. A zinc electrode is immersed in dilute sulfuric acid at 35.0oC and the following reaction
occurs:
𝑍𝑛()) + 𝐻! 𝑆𝑂*(%&) → 𝑍𝑛𝑆𝑂*(%&) + 𝐻!(#)
The volume of 𝐻!(#) present at t = 1.0 min is 30.0 mL and at t = 1.4 min is 42.0 mL. What is
the average rate of formation of 𝐻!(#) over this period of time measured in litres per second?

'
6. For the reaction shown below, the instantaneous rate of formation of 𝐵𝑟(%&) is 0.12 mol/LŸs
at t = 2.0 min.
' ' '
3𝐵𝑟𝑂(%&) → 𝐵𝑟𝑂+(%&) + 2𝐵𝑟(%&)
' '
What are the instantaneous rates of formation of 𝐵𝑟𝑂+(%&) and consumption of 𝐵𝑟𝑂(%&) ?

7. The data in the table below were obtained for the following reaction:
4𝐻𝐵𝑟(#) + 𝑂!(#) → 2𝐵𝑟!(#) + 2𝐻! 𝑂(#)
a) What is the average rate of
Time (s) [𝐻𝐵𝑟] (mol/L) [𝐵𝑟! ] (mol/L)
consumption of 𝐻𝐵𝑟(#) over 50.0 s?
0.00 0.42 0.00
b) What is the molar concentration of
50.0 0.26 ?
𝐵𝑟!(#) at t = 50.0s?

8. Consider the following reaction:

4𝑁𝐻+(#) + 5𝑂!(#) → 4𝑁𝑂(#) + 6𝐻! 𝑂(#)
Over a period of 1.80 min, the average rate of formation of 𝑁𝑂(#) is 1.04 mol/LŸs. What was
the amount of 𝑂!(#) consumed over this period of time?

9. A mass of 0.50 g of sodium metal reacts with water in 90.0 s.

2𝑁𝑎()) + 2𝐻! 𝑂(,) → 2𝑁𝑎𝑂𝐻(%&) + 𝐻!(#)
a) Express the rate of consumption of 𝑁𝑎()) in moles per second.
b) Calculate the rate at which 𝐻!(#) is generated in litres per second, at 30.0oC and
102.4 kPa. Assume that hydrogen is an ideal gas.
10. For the reaction shown below, the instantaneous change in concentration of 𝑁𝑂(#) is
1.4 mol/LŸs.
2𝑁𝑂(#) + 𝐶𝑙!(#) → 2𝑁𝑂𝐶𝑙(#)
What is the rate at which 𝐶𝑙!(#) is consumed and the rate at which 𝑁𝑂𝐶𝑙(#) is formed at this
time?

11. A reaction 𝐴 + 𝐵 → 𝐶 obeys the following rate law: 𝑟𝑎𝑡𝑒 = 𝑘[𝐵]! .

a) If [𝐴] is doubled, how will the rate change? Will the rate constant change? Explain.
b) What are the reaction orders for 𝐴 and 𝐵? What is the overall reaction order?
c) What are the units of the rate constant?

12. The decomposition of 𝑁! 𝑂- proceeds as follows:

2𝑁! 𝑂- → 4𝑁𝑂! + 𝑂!
The rate law is first order in 𝑁! 𝑂- . At 64oC the rate constant is 4.82 x 10-3 s-1.
a) Write the rate law for the reaction.
b) What is the rate of the reaction when [𝑁! 𝑂- ] = 0.0240 M?
c) What happens to the rate when the concentration of [𝑁! 𝑂- ] is doubled to 0.0480 M?

13. Consider the following reaction:

' '
𝐶𝐻+ 𝐵𝑟(%&) + 𝑂𝐻(%&) → 𝐶𝐻+ 𝑂𝐻(%&) + 𝐵𝑟(%&)
'
The rate law for this reaction is first order in 𝐶𝐻+ 𝐵𝑟(%&) and first order in 𝑂𝐻(%&) . When
'
[𝐶𝐻+ 𝐵𝑟] is 5.0 x 10 M and [𝑂𝐻 ] is 0.050 M, the reaction rate at 298 K is 0.0432 M/s.
-3

a) What is the value of the rate constant?

b) What are the units of the rate constant?
'
c) What would happen to the rate if the concentration of 𝑂𝐻(%&) were tripled?

14. The iodide ion reacts with hypochlorite ion (the active ingredient in chlorine bleaches) in the
following way:
𝑂𝐶𝑙 ' + 𝐼 ' → 𝑂𝐼 ' + 𝐶𝑙 '
This rapid reaction gives the following rate data:
[𝑂𝐶𝑙 ' ], M [𝐼 ' ], M Rate, M/s
-3 -3
1.5 x 10 1.5 x 10 1.36 x 10-4
-3 -3
3.0 x 10 1.5 x 10 2.72 x 10-4
1.5 x 10-3 3.0 x 10-3 2.72 x 10-4
a) Write the rate law for this reaction.
b) Calculate the rate constant.
c) Calculate the rate when [𝑂𝐶𝑙 ' ] = 2.0 x 10-3 M and [𝐼 ' ] = 5.0 x 10-4 M.

15. The following data were measured for the reaction 𝐵𝐹+(#) + 𝑁𝐻+(#) → 𝐹+ 𝐵𝑁𝐻+(#) :
Experiment [𝐵𝐹+ ] (M) [𝑁𝐻+ ] (M) Initial Rate, (M/s)
1 0.250 0.250 0.2130
2 0.250 0.125 0.1065
3 0.200 0.100 0.0682
4 0.350 0.100 0.1193
5 0.175 0.100 0.0596
a) What is the rate law for the reaction?
b) What is the overall order of the reaction?
c) What is the value of the rate constant for the reaction?
d) What is the rate when [𝐵𝐹+ ] = 0.100 M and [𝑁𝐻+ ] = 0.500 M?
16. Consider the gas-phase reaction between nitric oxide and bromine at 273oC:
2𝑁𝑂(#) + 𝐵𝑟!(#) → 2𝑁𝑂𝐵𝑟(#)
The following data for the initial rate of appearance of 𝑁𝑂𝐵𝑟(#) were obtained:
Experiment [𝑁𝑂] (M) [𝐵𝑟! ] (M) Initial Rate (M/s)
1 0.10 0.20 24
2 0.25 0.20 150
3 0.10 0.50 60
4 0.35 0.50 735
a) Determine the rate law.
b) Calculate the average value for the rate constant for the appearance of 𝑁𝑂𝐵𝑟(#) from the
four data sets.
c) How is the rate of appearance of 𝑁𝑂𝐵𝑟(#) related to the rate of disappearance of 𝐵𝑟! ?
d) What is the rate of disappearance of 𝐵𝑟! when [𝑁𝑂] = 0.075 M and [𝐵𝑟! ] = 0.25 M?

17. a) Define the following symbols that are encountered in rate equations: [𝐴]. , 𝑡//! , [𝐴]1 , 𝑘.
b) What quantity, when graphed versus time, will yield a straight line for a first-order
reaction?

18. a) The gas-phase decomposition 𝑆𝑂! 𝐶𝑙!(#) → 𝑆𝑂!(#) + 𝐶𝑙!(#) is first-order in 𝑆𝑂! 𝐶𝑙!(#) . At
600 K the half-life for this process is 2.3 x 105 s. What is the rate constant at this
temperature?
b) At 320oC the rate constant is 2.2 x 10-5 s-1. What is the half-life at this temperature?

19. As described in the question above, the decomposition of 𝑆𝑂! 𝐶𝑙!(#) is a first-order process.
The rate constant for the decomposition at 660 K is 4.5 x 10-2 s-1.
a) If we begin with an initial 𝑆𝑂! 𝐶𝑙!(#) pressure of 375 torr, what is the pressure of this
substance after 65 s?
b) At what time will the pressure of 𝑆𝑂! 𝐶𝑙!(#) decline to one-tenth of its initial value?

20. The gas-phase decomposition 2𝑁𝑂!(#) → 2𝑁𝑂(#) + 𝑂!(#) is studied at 383oC, giving the
following data:
Time (s) [𝑁𝑂! ] (M) a) Is the reaction first-order or second-order with respect to
0.0 0.100 the concentration of 𝑁𝑂!(#) ?
5.0 0.017 b) What is the value of the rate constant?
10.0 0.0090
15.0 0.0062
20.0 0.0047

21. Complete the following potential energy diagram by adding the following labels: (i) an
appropriate label for the x-axis and y-axis (ii) 𝐸%(234) (iii) 𝐸%(567) (iv) ∆𝐻589 .
a) Is the forward reaction endothermic or exothermic?
b) Which has the higher potential energy; the reactants or the products?
22. Consider the following reaction:
𝐴𝐵 + 𝐶 → 𝐴𝐶 + 𝐵 ∆𝐻589 = +65 𝑘𝐽, 𝐸%(567) = +34 𝑘𝐽
Draw and label a potential energy diagram for this reaction. Calculate and label 𝐸%(234) .

23. Consider the reaction below:

𝐶 + 𝐶 → 𝐶𝐷 𝐸%(234) = +61 𝑘𝐽, 𝐸%(567) = +150 𝑘𝐽
Draw and label a potential energy diagram for this reaction. Calculate and label ∆𝐻589 .

24. In the upper atmosphere, oxygen exists as 𝑂!(#) , as ozone, 𝑂+(#) , and as individual oxygen
atoms, 𝑂(#) . Ozone and atomic oxygen react to form two molecules of oxygen gas. The
enthalpy change is -392 kJ and the activation energy is +19.0 kJ. Draw and label a potential
energy diagram. Include a value for 𝐸%(567) .

25. For a reaction, on an arbitrary scale, the potential energies are as follows: activated
complex, +112 kJ; reactants, +36 kJ; products, +78 kJ.
a) Determine the activation energy and the enthalpy change for the reaction.
b) Draw a labeled potential energy diagram for the reaction, indicating the relative energies
of the reactants, products, and the activated complex.

26. Refer to the molar enthalpies of combustion for hydrocarbons included with the
Thermochemistry Practice Problems.
a) Write a balanced thermochemical equation for the combustion of methane gas, 𝐶𝐻*(#) .
b) Draw a potential energy diagram that would reasonably represent this combustion
reaction. Indicate the ∆𝐻:;<= and a molecular structure that could represent an activated
complex in this reaction.

27. When steam is passed over hot iron, a reaction occurs as shown below.
3𝐹𝑒()) + 4𝐻! 𝑂(#) ⇄ 𝐹𝑒+ 𝑂*()) + 4𝐻!(#) ∆𝐻589 = −151.2 𝑘𝐽
The activation energy for the reverse reaction, 𝐸%(567) , is +200.7 kJ.
a) Calculate the activation energy for the forward reaction.
b) Draw a labeled potential energy diagram showing the enthalpy change, and the
activation energies for the forward and reverse reactions.

28. The decomposition of dinitrogen tetroxide, 𝑁! 𝑂*(#) , to nitrogen dioxide, 𝑁𝑂!(#) , is a

reversible reaction. The activation energy for the decomposition reaction is +58.6 kJ.
𝑁! 𝑂*(#) + 55.3 𝑘𝐽 ⇄ 2𝑁𝑂!(#)
Draw a potential energy diagram for the reaction showing appropriate labels for both axes,
𝐸%(234) , 𝐸%(567) , and ∆𝐻589 .

29. What is 𝐸%(234) for the reaction represented below that has 𝐸%(567) of +235 kJ?
𝐴 + 2𝐶𝐷 + 85 𝑘𝐽 → 𝐺

30. a) What is meant by the term elementary reaction?

b) What is the difference between a unimolecular and a bimolecular elementary reaction?
c) What is a reaction mechanism?
31. What is the molecularity of each of the following elementary reactions? Write a rate law for
each.
a) 𝐶𝑙!(#) → 2𝐶𝑙(#)
' '
b) 𝑂𝐶𝑙(#) + 𝐻! 𝑂(#) → 𝐻𝑂𝐶𝑙(#) + 𝑂𝐻(#)
c) 𝑁𝑂(#) + 𝐶𝑙!(#) → 𝑁𝑂𝐶𝑙!(#)

32. a) Based on the following reaction profile, how many

intermediates are formed in the reaction 𝐴 → 𝐷?
b) How many transition states are there?
c) Which step is the fastest?
d) Is the reaction 𝐴 → 𝐷 exothermic or endothermic?

33. The following mechanism has been proposed for the gas-
phase reaction of 𝐻!(#) with 𝐼𝐶𝑙(#) :
𝐻!(#) + 𝐼𝐶𝑙(#) → 𝐻𝐼(#) + 𝐻𝐶𝑙(#)
𝐻𝐼(#) + 𝐼𝐶𝑙(#) → 𝐼!(#) + 𝐻𝐶𝑙(#)
a) Write the balanced equation for the overall reaction.
b) Identify any intermediates in the mechanism.
c) Write the rate laws for each elementary reaction in the mechanism.
d) If the first step is slow and the second one is fast, what rate law do you expect to be
observed for the overall reaction?

34. The following mechanism has been proposed for the gas-phase reaction of chloroform
(𝐶𝐻𝐶𝑙+(#) ) and chlorine:
(1) 𝐶𝑙!(#) ⇄ 2𝐶𝑙(#) (fast)
(2) 𝐶𝑙(#) + 𝐶𝐻𝐶𝑙+(#) → 𝐻𝐶𝑙(#) + 𝐶𝐶𝑙+(#) (slow)
(3) 𝐶𝑙(#) + 𝐶𝐶𝑙+(#) → 𝐶𝐶𝑙*(#) (fast)
a) What is the overall reaction?
b) What are the intermediates in the mechanism?
c) What is the molecularity of each of the elementary reactions?
d) What is the rate-determining step?
e) What is the rate law predicted by this mechanism? [Hint: The overall reaction order is
not an integer.]

35. The oxidation of 𝑆𝑂!(#) to 𝑆𝑂+(#) is catalyzed by 𝑁𝑂!(#) . The reaction proceeds as follows:
𝑁𝑂!(#) + 𝑆𝑂!(#) → 𝑁𝑂(#) + 𝑆𝑂+(#)
2𝑁𝑂(#) + 𝑂!(#) → 2𝑁𝑂!(#)
a) Show that the two reactions can be summed to give the overall oxidation of 𝑆𝑂!(#) to
𝑆𝑂+(#) . [Hint: The top reaction must be multiplied by a factor so the 𝑁𝑂(#) and 𝑁𝑂!(#)
cancel out.]
b) Why do we consider 𝑁𝑂!(#) a catalyst and not an intermediate in this reaction?
 Answers
1. 4.72 x 10-5 mol/L!s 20. a) The graph of 1/[NO2] vs. t is linear;
2. 7 x 10-4 mol/L!s second order.
3. a) 0.165 mol b) 10 M-1s-1
b) 0.165 mol Br2(aq) 21. y-axis: potential energy;
4. 1.4 mol/L x-axis: reaction progress;
5. 5.0 x 10-4 L/s Ea(fwd): between reactants & transition state;
6. rate of formation of BrO3- = 0.060 mol/L!s; Ea(rev): between products & transition state;
rate of consumption of BrO- = 0.18 mol/L!s ΔHrxn: between reactants & products
7. a) 0.0030 mol/L!s a) endothermic
b) 0.075 mol/L b) products
8. 1.40 x 102 mol 22. Ea(fwd) = +99 kJ
9. a) 2.42 x 10-4 mol/s 23. ΔHrxn = -89 kJ
b) 2.98 x 10-3 L/s 24. Ea(rev) = +411 kJ
10. 0.70 mol/L!s Cl2 consumption; 25. a) Ea = +76 kJ; ΔHrxn = +42 kJ
1.4 mol/L!s NOCl production 26. a) CH4(g) + 2O2(g) " CO2(g) + 2H2O(l) + 891 kJ
11. a) If [A] doubles, there is no change in the rate or 27. a) +49.5 kJ
the rate constant. The overall rate is unchanged 28. Ea(rev) = +3.3 kJ
because [A] does not appear in the rate law; rate 29. +320 kJ
constants only change with temperature. 30. a) A process that occurs in a single event.
b) Zero order in A; second order in B; second b) unimolecular – one reactant particle;
order overall. bimolecular – two reactant particles.
c) M-1s-1 c) A series of steps that describe how a reaction
12. a) rate = k[N2O5] proceeds.
b) 1.16 x 10-4 M/s 31. a) unimolecular; rate = k[Cl2]
c) Reaction rate doubles. b) bimolecular; rate = k[OCl-][H2O]
13. a) & b) 1.7 x 102 M-1s-1 c) bimolecular; rate = k[NO][Cl2]
c) Reaction rate triples. 32. a) two – B & C
14. a) rate = k[OCl-][I-] b) three
b) 60 M-1s-1 c) C " D
c) 6.0 x 10-5 M/s d) endothermic
15. a) rate = k[BF3][NH3] 33. a) H2(g) + 2ICl(g) " I2(g) + 2HCl(g)
b) second order b) HI(g)
c) 3.41 M-1s-1 c) first step: rate = k[H2][ICl];
d) 0.170 M/s second step: rate = k[HI][ICl]
16. a) rate = k[NO]2[Br2] d) rate = k[H2][ICl]
b) 1.2 x 104 M-2s-1 34. a) Cl2(g) + CHCl3(g) " HCl(g) + CCl4(g)
! ∆[!"#$] ∆[!" ]
!
c) =!− b) Cl(g) & CCl3(g)
! ∆! ∆!
d) 8.4 M/s c) unimolecular; bimolecular; bimolecular
17. a) [A]0 is reactant concentration at time zero d) step 2 (slow step)
(initial concentration); t1/2 is the half-life (time e) rate = k[CHCl3][Cl2]1/2
taken to reduce [A]0 by half); [A]t is reactant 35. a) Multiply the coefficients in the first step by 2
concentration at time t; k is the rate constant and sum.
for a particular reaction. b) It is a catalyst because it is first consumed and
b) ln[A] vs. t then produced. Intermediates are produced
18. a) 3.0 x 10-6 s-1 and then consumed.
b) 3.2 x 104 s
19. a) 20 torr
b) 51 s