Topics : Chemical Kinetics

Part A: Reaction Rates and Factors that Affect Reaction Rates

1. Acid hydrolysis of 1-iodobutane to produce butanol as follow: CH3CH2CH2CH2I + H2O  CH3CH2CH2CH2OH + HI

A graph of concentration of 1-iodobutane against time was plotted as shown below. From the graph, determine

(a) the initial rate [C4H9I,], mol L-1

(b) the rate at 300 s and 600 s
(c) the average rate in the first 500s
0.11

0.1

0.09

0.08

0.07

0.06

0.05

0.04

0.03

0.02

0.01

0
0 100 200 300 400 500 600 700 800 900

Time (s)
2. Hydrogen peroxide, H2O2 decomposes into oxygen and water according to the equation below.
2H2O2(l)  2H2O(l) + O2(g)

The graph shows the concentration of H2O2

as a function of time.
[H2O2], mol L-1

From the graph, determine 0.011

(a)the initial rate
(b) the instantaneous rate of disappearance
0.01
of H2O2 at 300s
(c) the instantaneous rate of formation of O2
at 300 s 0.009
(d) the average rate of the reaction between
150 s to 500 s 0.008

0.007

0.006

0.005

0.004

0.003

0.002

0.001

0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
Time (s)
3. Graph below shows the volume of carbon dioxide gas collected when a fixed mass of marble chips reacted with an excess of dilute
hydrochloric acid at constant temperature.

CaCO3(s) + 2HCl(aq)  CaCl2(aq) + H2O(g) + CO2(g)

The rate of this reaction can be studied by measuring the time it takes for a given volume of CO2 to be collected.

W
Volume of CO2/cm3

Time/s
(a) State and explain what happened to the rate of this reaction at point W
(b) Explain why the reaction rate is increased if the chips of marble are reduced in size.
(c) On the axes above, sketch a curve to show how the volume of CO2 would change with time if the reaction were repeated under the
same conditions but in the presence of catalyst.

4. Consider the following reaction

2CU2+(aq) + 6CN-(aq)  2[Cu(CN)2]-(aq) + (CN)2(aq)

(a) Express the rate of reaction in terms of the four species in the equation.
(b) At a particular moment, the rate of formation of [Cu(CN)2]- is 5.60 x 10-2 mol L-1 s-1. What is the rate express in terms of CN- and (CN)2
5. Dinitrogen pentoxide decomposes according to the equation

2N2O5(g)  4NO2(g) + O2(g)

At a particular instance, the rate of disappearance of N2O5 is 1.65 x 10-3 mol L-1 s-1. Calculate is the rate of formation of NO2 and O2 at that
instance.

6. The reaction taking place in the Haber process is

N2(g) + 3H2(g)  2NH3(g)

(a) Write the expression for the rate of the reaction with respect to each of the reactants and products
(b) At a particular moment, when N2 is decreasing at a rate 1.5 x 10-3 mol L-1 s-1, how fast is the NH3 is increasing?

Part B: The Rate Law and the Order of Reaction

1. The initial rate of the reaction between A and B was measured in a series of experiments and the following rate equation was deduced.

Rate = k[A][B]2

Expt Initial [A], Initial [B] Initial rate,

mol L-1 mol L-1 mol L-1 s-1
1 0.020 1.2 x 10-4
0.020
2 0.040
0.040
3 0.040 2.4 x 10-4

4 0.030
0.060
5 7.2 x 10-4
 0.040

(a) Using the data for experiment 1, calculate a value for the rate constant k and state its unit.
(b) Complete the table for the reaction between A and B

2. The initial rate of reaction between ester and aqueous sodium hydroxide was measured in a series of experiments at a constant
temperature. The data obtained are shown below.

Expt Initial [OH-] Initial [ester] Initial rate,

mol L-1 mol L-1 mol L-1 s-1
0.040 0.030 4.0 x 10-4
1
0.040 0.045 6.0 x 10-4
2
0.060 0.045 9.0 x 10-4
3
0.120 0.060
4

(a) Determine the order of reaction with respect to ester and the order of reaction with respect to OH-.
(b) Determine the rate constant k and state its unit.
(c) Determine the initial rate in experiment 4.
3. The reaction of thiosulfate ion with acid follows the equation

S2O32-(aq) + 2H+(aq)  S(s) + SO2(g) + H2O(l)

The following data were collected for the above reaction

Expt Initial [S2O32-] mol Initial [H+] mol Initial rate , mol
L-1 L-1 L-1 s-1
0.10 0.60 0.04224
1
0.10 0.40 0.04224
2
0.05 0.40 0.02112
3
0.025 0.40 0.01056
4

(a) Determine the rate law for the reaction.

(b) Determine the value of the rate constant with it correct units.

4. The reaction of nitric oxide with hydrogen at 128oC is given below.

2NO(g) + 2H2(g)  N2(g) + 2H2O(g)

Three experiments were carried out separately and the following data are collected.

Experiment [NO]/ mol dm-3 [H2]/ mol dm-3 Initial rate/ mol dm-3 s-1
1 1.0 x 10-2 2.0 x 10-3 5.0 x 10-5
2 1.0 x 10-2 4.0 x 10-3 1.0 x 10-4
3 2.0 x 10-2 8.0 x 10-3 8.0 x 10-4

(a) Determine the order of reaction with respect to H2 and NO.

 (b) Write the rate equation for the reaction.
(c) Calculate the rate constant, k

5. The reaction between peroxodisulfate and iodide follows the equation

2I-(aq) + S2O82-(aq)  I2(aq) + 2SO42-(aq)

The reaction rates were studies at 25oC. The following results were obtained

Expt [S2O82-] [I-] Initial rate

mol L-1 mol L-1 mol L-1 s-1
1 0.080 12.5 x 10-6
0.040
2 0.040 6.25 x 10-6
0.040
3 0.060 7.03 x 10-6
0.030
4 0.080 6.25 x 10-6
0.020

(a) Determine the rate law

(b) Calculate the value of the rate constant with it correct units
6. Consider the following reaction:

A + B  product

The reaction is first order with respect to A and second order with respect to B

(a) Write the rate equation for the reaction.

(b) The initial rate of reaction at certain temperature for the above reaction is x mol L-1 s-1. What will the new rate (in terms of x) be if the
concentration of A is double and the concentration of B halved?

7. Consider the following reaction:

BrO3- + 6H+ + 5Br-  3Br2 + 3H2O

A kinetic of the above reaction was studied and it was found that, doubling the concentration of BrO3- and Br- the rate of reaction increased
by a factor of 1 and 2 respectively. However, the rate of reaction is independent on the concentration of H+.

(a) Write the rate equation for the reaction and what is the overall order of reaction?
(b) Explain the effects on the reaction rate and rate constant when [BrO3-] is decreased by 3 times and [Br-] is tripled.

8. Indicate the order of reaction consistent with each observation.

(a) A plot of concentration of the reactant versus time yields a straight line.
(b) The reaction has a half life that is independent of initial concentration.
(c) A plot of the inverse of the concentration versus time yields a straight line.
(d) A plot of the natural log of the concentration of the reactant versus time yields a straight line.
(e) The half life of the reactant gets longer as the initial concentration is decreased.
9. The elimination of alcohols is facilitated by acid as shown as below

C2H5OH(l) + H+(aq)  C2H4(g) + H3O+(aq)

Concentration versus time data were collected for this reaction, and a plot of [C2H5OH] versus time resulted in a straight line with a slope
value of -4.00 x 10-5 mol L-1 s-1.

(a) Determine the rate law, the integrated rate law and the value of the rate constant for this reaction.
(b) If the initial concentration of C2H5OH was 1.25 x 10-2 mol/L, calculate the half life for this reaction.
(c) How much time is required for all of the 1.25 x 10-2 mol/L to be eliminated by acid?

10. The following reaction was monitored as a function of time:

A  B + C

A plot of ln[A] versus time yields a straight line with slope -0.0045 s-1.

(a) What is the value of the rate constant for this reaction at this temperature.
(b) Write the rate law for the reaction.
(c) What is the half-life?
(d) If the initial concentration of A is 0.250 M, what is the concentration after 225s?

11. The decomposition of XY is second order and has rate constant of 7.02 x 10-3 L mol-1 s-1 at a certain temperature.

(a) What is the half-life for this reaction at an initial concentration of 0.100 M?
(b) How long will it take for the concentration of XY to decrease to 12.5% of its initial concentration when the initial concentration is 0.100
M?
(c) If the initial concentration of XY is 0.050 M, what is the concentration of XY after 50s?
12. The data below show the concentration of cyclobutane (C4H8) versus time for the reaction:

C4H8  2C2H4

Time (s) [C4H8] mol/L

0 1.000
10 0.894
20 0.799
30 0.714
40 0.638
50 0.571
60 0.510
70 0.456
80 0.408
90 0.364
100 0.326

Determine the order of the reaction and the value of the rate constant. What is the rate of reaction when [C4H8] is 0.25 M
13. The data below show the concentration of N2O5 versus time for the reaction

N2O5(g)  NO3(g) + NO2(g)

Determine the order of the reaction and the value of the rate constant. Predict the concentration of N2O5 at 250s

Time (s) [N2O5], mol/L

0 1.000
25 0.822
50 0.677
75 0.557
100 0.458
125 0.377
150 0.310
175 0.255
200 0.210
14. Decomposition of HI(g) at 508oC is 2HI(g)  H2(g) + I2(g)
The molar concentration of HI was
measured at interval time (s) and the Concentration of HI (M) vs Time (s)
graph of concentration against time for
decomposition HI at 508oC is shown
below. 0.11

(a) Based on the graph, determine the 0.1

order of reaction with respect to HI
and write the rate equation for the 0.09
decomposition.
(b) Determine the rate constant, k for 0.08
the decomposition of HI

Concentration of HI (M)
0.07

0.06

0.05

0.04

0.03

0.02

0.01

0
0 50 100 150 200 250 300 350 400 450

Time (S) of Reaction

15. The graph below shows the decomposition of sulfuryl chloride (SO2Cl2) at certain temperature.
SO2Cl2(g) 
SO2(g) + Cl2(g)
(a) Determine the Concentration of SO2Cl2 (M) vs Time (s) order of
reaction with respect to
SO2Cl2 and write 0.11 the rate
equation
(b) Determine the rate 0.1 constant, k

0.09

0.08

0.07

0.06

0.05
Concentration SO2Cl2 (M)

0.04

0.03

0.02

0.01

0
0 100 200 300 400 500 600 700 800 900 1000 1100 1200
Time (s)
16. 2-methyl-2-bromopropane undergoes hydrolysis to produce 2-methyl-2-butanol as shown in the equation below
C4H9Cl + OH-  C4H9OH + Cl-
The graph of concentration of C4H9Cl and OH- against time for this reaction was plotted on the same scale. Based on the graph determine
the order of reaction with respect to C4H9Cl and the order of reaction with respect to OH-. Write the rate equation for this hydrolysis
 0.25
[C4H9Cl] and [OH-]

C4H9Cl
0.2

OH-
Time(s)

0.15

0.1

0.05

0
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210
17. The reaction between NO and H2 is 2NO + 2H2  N2 + 2H2O
Determine the order of reaction with respect to NO and order of reaction with respect to H2 and write the rate equation

0.11

0.1

0.09

Part C: The
0.08 Collision
Theory
[NO] and [H2]

0.07

0.06

0.05

H2
0.04
H2
0.03
NO
0.02
NO

0.01

0
0 10 20 30 40 50 60 70 80 90 100 110 120
Time(s)
18. State two conditions for an effective collision to occur between reactant molecules to form products

19. Consider the reaction 2SO2(g) + 2NO2(g)  2SO3(g) + 2NO(g). Draw the transition state and explain why it cannot be isolated as
independent chemical species.

20. Explain why some reactions occur at room temperature while others occur at higher temperature?

21. Explain based on the collision theory, how the rate of reaction is affected by the following factor

(a) Increase the partial pressure of reactant.

(b) Increase the temperature of the reaction.
(c) Increase the concentration of reactant

Part D: The Effect of Temperature on Reaction Kinetics

22. The decomposition of N2O into N2 and O2 follows second order. At certain temperature, T, the frequency factor, A is 5.0 x 1011 L mol-1 s-1
Ea -29000 K
and is equal to e T . Determine the activation energy of this reaction.
RT

23. The rate constant, k for certain reaction at 35oC is 4.50 x 10-2 s-1. Determine the rate constant at 50oC. Explain why the rate constants are
not the same at different temperatures.

24. In term of reaction kinetics, explain the effect of temperature on the rate of reaction. Sketch a Maxwell-Boltzmann distribution curves by
labelling the high and low temperature to support your explanation.

25. The rate constant for the decomposition of N2O5 is studied at different temperature

2N2O5(g)  2N2O4(g) + O2(g)

The data as shown below

Temperature / K Rate constant, k / s-1

283 3.83 x 10-6
 293 1.71 x 10-5
303 6.94 x 10-5
313 2.57 x 10-4
323 8.78 x 10-4

Plot a suitable graph and determine

(a) The activation energy
(b) The frequency factor, A

26. The decomposition of NO2 into NO and O2 is second order. The rate constant of the decomposition is studied at different temperature. The
following data were collected from the reaction.

Temperature / oC Rate constant, k / mol-1 L s-1

400 7.8
410 10
420 14
430 18
440 24

Plot a suitable graph and determine

(a) The activation energy
(b) The rate constant at 425oC

Part E: The Effect of Catalyst on Reaction Kinetics

27. In term of reaction kinetics, explain why the addition of catalyst speeds up a chemical reaction. Sketch a Maxwell-Boltzmann distribution
curves by labelling with and without catalyst to support your answer.

28. Does the order of reaction for certain chemical reaction change after the addition of catalyst? Explain why

29. Does the yield of product for certain chemical reaction increase after the addition of catalyst? Explain why

30. Does the overall stoichiometry increase for certain chemical reaction after the addition of catalyst?

31. Does the enthalpy change of the reaction change after the addition of catalyst?
Part F: Reaction Mechanism

32. A two-step mechanism is proposed for the decomposition of nitrosyl chloride, NO2Cl at 50oC. In the decomposition, the rate constant, k1 is
smaller than k2
k1
Step 1 NO2Cl(g)  NO2(g) + Cl(g)

k2
Step 2 Cl(g) + NO2Cl(g)  NO2(g) + Cl2(g)

(a) Write the overall equation for the reaction

(b) Identify the intermediate in the reaction
(c) Write the rate law for the reaction above. Explain your answer.

33. The energy profile for V  Y reaction is shown below

Potential energy

V
W
X
Y

Reaction progress
(a) Determine the number of elementary steps involved in this reaction
(b) Identify the intermediates involved in this reaction.
(c) Identify the rate-determining step and write the rate law