Exercise 1 Oxidation of Oxalic Acid by Permanganate Ions

Permanganate ions (MnO 4 ) react with oxalic acid (H2C2O4) in an acidic medium according to the following
equation:
2 MnO 4 (aq) + 5 H2C2O4(aq) + 6 H3O+(aq) → 2 Mn2+(aq) + 10 CO2(g) + 14 H2O(l)

where (MnO 4 ) is the only colored species in this reactional medium.

1. Kinetic Factors
In order to study the effect of some kinetic factors on the rate of the above reaction, the three following
mixtures are prepared. (Potassium permanganate solution is added to each mixture at t = 0).
Mixture (A) Mixture (B) Mixture (C)
-1
H2C2O4 : C1 = 0.01 mol.L V1 = 20 mL V1 = 20 mL V1 = 20 mL
H2SO4 concentrated V2 = 10 mL V2 = 10 mL V2 = 10 mL
Distilled water 0 60 mL 0
Temperature θ 20 ºC 20 ºC 40 º C
KMnO4 : C3 = 5.0x10-3 mol.L-1 V3 = 10 mL V3 = 10 mL V3 = 10 mL
Δt Δt (A) = 140 s Δt (B) = 190 s Δt (C) = 22 s
Δt is the time needed to obtain the decolorization of the mixture.
1.1. Interpret the decolorization of the solution at the end of the reaction.
1.2. With reference to the results obtained in the above table:
1.2.1. Indicate, by comparing the initial state of mixtures, the kinetic factor studied in:
(A) and (B) on one hand;
(A) and (C) on the other hand.
1.2.2. Deduce the effect of each factor on the rate of the reaction.
1.2.3. Specify the most convenient experimental condition that should be provided to perform the
titration between oxalic acid solution of concentration C1 and acidified potassium
permanganate of concentration C3.

2. Study of Mixture (B)

The two following mixtures are prepared at the same temperature θ = 20 ºC:

Mixture (B) Mixture (D)

H2C2O4 : C1 = 0.01 mol.L-1 V1 = 20 mL V1 = 20 mL
H2SO4 concentrated V2 = 10 mL V2 = 10 mL
Distilled water 60 mL 60 mL
Temperature θ 20 ºC 20 ºC
KMnO4 : C3 = 5.0x10-3 mol.L-1 V3 = 10 mL V3 = 10 mL
- Some grains of
manganese (II) sulfate
Δt Δt (B) = 190 s Δt (D) = 50 s

The permanganate solution and the grains of manganese II sulfate are introduced at t = 0.

2.1. Deduce from this study the role of Mn2+ ions in mixture (D). Calculate the initial concentration of
each : [MnO 4 ] 0 and [H2C2O4] 0 in mixture (B). Deduce the concentration of Mn2+ ions at t = 190 s.

Exercise 2 Kinetic of the polymerization reaction of ethyne

At a temperature T = 500K, and in the presence of Nickel as catalyst, ethye gas C2H2, is transformed into
benzene gas molecule C6H6 according to the following equation:
3C2H2  C6H6

1
 1. Kinetic study of the reaction
In order to study the kinetic of this transformation, 3x10-3 mol of ethyne is introduced into a vessel of
constant volume V maintained at constant temperature 500K. As the reaction proceeds, the
concentration of ethyne left over time is determined. The results are given in the table of document 1.
t (sec) 0 100 200 280 320 360 480
[C2H2] x 10-3 mol.L-1 3 2 1.5 1.3 1.2 1.1 0.789
Document 1

1.1. Recopy and complete the following table, in terms of x, the number of moles of benzene formed at
instant t:
C2H2 C6H6
t=0
t

1.2. Show that the number of moes of C2H2 at instant t is given by the relation:
𝑛𝑡 (𝐶2 𝐻2 ) = 3(10−3 − 𝑛𝑡 (𝐶6 𝐻6 ))
1.3. Plot the curve [C2H2]= f(t) in the time interval [0 – 360]. Take the scale:1cm – 50s and
1cm – 0.5x10-3mol.L-1
1.4. Determine graphically the half life time of this reaction.
1.5. Specify whether the instant of time t =480s is sufficient for the total polymerization of ethyne.
1.6. The rate of disappearance of C2H2 at 200s is 5x10-6 mol.L-1.s-1.
1.6.1. Calculate the rate of the reaction at t = 200s.
1.6.2. Choose, by justifying, from the below propositions the correct one about the initial rate ro
of disappearance of C2H2:
a. ro= 5x10-6 mol.L-1.s-1 b. ro > 5x10-6 mol.L-1.s-1 c. ro < 5x10-6 mol.L-1.s-1
1.6.3. Compare the rate of disappearance of C2H2 to the rate of appearance of C6H6 at instant t.

2. Influence of the kinetic factors

Three experiments A, B and C are performed to plot the curve [C2H2]= g(t) by changing in each case
one of the following experimental conditions:
[C6H6] x 10 -3 mol.L-1 I
a. without catalyst.
b. At a higher temperature. II
c. Starting with a greater amount of C2H2. Initial experiment

The three curves are plotted I, II and III as shown in III

document 2.
Attribute to each experiment the corresponding curve. time (s)
Justify.

Exercise 3 Oxidation Reaction of Iodide Ions

The oxidation of potassium iodide (KI) by sodium peroxydisulfate (Na2S2O8) is represented by the following
equation:
2I-(aq) + S2O82-(aq)  I2(aq) + 2SO42-(aq)
Given: Molar mass in g.mol-1: M(KI) = 166g.mol-1

1. Preparation of solution (S)

The label on a bottle containing potassium iodide solution (So) shows the following indications: % by mass of
KI: Po = 45%
A sample of solution (So) is diluted and a new solution (S) of P = 1.75% by mass of KI is obtained.
 1.1. Show that the concentration of solution (So) and solution (S) are Co = 8.46mol.L-1 and C = 0.33mol.L-1
respectively.
Given: The density of KI solution is d = 3.12g/cm3.
1.2. Choose, by justifying, from the table of document 1 the convenient kit needed to perform the dilution
process
Kit A Kit B Kit C Kit D
1000mL volumetric flask 500mL volumetric flask 500mL volumetric flask 100mL volumetric flask
20mL volumetric pipet 20 volumetric pipet 20mL graduated pipet 10mL volumetric pipet
Document 1

2. Kinetic study

Experiment 1:
A mixture (A) is prepared where 100mL of
potassium iodide solution (S) of concentration C =
n(I-) x10-2 mol
3.5
0.33mol.L-1 is oxidized with 100mL of sodium 3
peroxydisulfate solution of concentration C1 = 2.5
0.10mol.L-1 at 25 oC. 2
1.5
The progress of the reaction is studied by
1
determining the remained amount of I- through a
0.5
titration of iodine formed during same intervals of
0
time. The kinetic curve n(I-) versus time is plotted
0 20 40 60 80 100
as given in the graph of document 2 time (min)
Document 2
2.1. Determine if the initial mixture is
stoichiometry or not
2.2. To what limit the concentration of I2 tends at the end of the reaction.
2.3. Choose the correct answer. Justify using the graph. Then deduce the kinetic factor responsible of this
variation of rate.
a) ro(I-) < r20(I-) b) ro(I-) = r20(I-) c) ro(I-) > r20(I-) d) ro(I-) ≥ r20(I-)
2.4. Calculate the concentration of I- at the half life time of the reaction.
2.5. The final time tf needed by the reaction to be over is 180min.
Indicate graphically the value of half-life time. Compare it with the half final time. Indicate by
justifying the reason that can explain the result of comparison.

3. Kinetic factors

The experiment 1 is repeated with a single modification. The reaction is performed at 10 oC.

3.1. Specify whether the concentration of I2 is changed at

3.1.1. the end time of the reaction.
3.1.2. the instant of time t = 40min.
3.2. Compare while justifying the concentration of I – at t = 40min in the first experiment to the
concentration of I – in the new experiment at T = 10 oC at the same instant t = 40min.

Exercise 4 Kinetic Study of The Oxidation of Magnesium Metal

Magnesium is a metal that reacts with an aqueous solution of hydrochloric acid (H3O+,Cl-) according to the
following equation
Mg + 2 H3O+  Mg2+ + H2 + 2H2O

* This exercise aims to study the kinetic of the above reaction

* Given: molar mass in g.mol-1: Mg – 24 ; HCl – 36.5
* Density of HCl solution is 1.02g/mL

1. Preparation of Hydrochloric Acid Solution

Hydrochloric acid solution (S) of concentration C = 0.4 mol.L-1 is prepared from another concentrated solution
(So) of concentration Co .
Consider Po be the percentage of HCl in solution (So).
Document 1 shows the two sets of material that are available in the laboratory.

Set Available HCl solution (So) Volumetric flask Graduated pipette

Set a 50 mL 5 mL
Co (mol.L-1); Po = 17.9 %
Set b 100 mL 10 mL
Document 1
1.1. Show that the concentration Co of HCl is 5 mol.L-1.
1.2. Explain, if each one of the two sets is convenient to perform the above dilution. Taking into
consideration that one take out of the initial solution is allowed.

2. Preliminary Study of the Reaction:

First Experiment:
At a temperature of 25 oC, add 0.24 g strip of magnesium metal into a closed flask containing a volume V = 100
ml of hydrochloric acid solution of concentration C = 0.4 mol/l (The volume V of the solution doesn't change)

2.1. Specify whether the initial mixture is stoichiometry or not.

2.2. Determine the concentration of Mg2+ ions at the end of the reaction.
2.3. Show that, at each instant of time t, the relation between [H3O+] in mol.L-1 and the [Mg2+] expressed in
mol.L-1:
[𝐻3 𝑂+ ]𝑡1 = [𝐻3 𝑂+ ]𝑜 − 10𝑛𝑜 (𝑀𝑔)
2
2.4. Deduce, at the half life time of the reaction, that the [H3O+]t1/2 = 0.3mol.L-1

3. Kinetic study:

The released volume of hydrogen gas, at different instants permit to determine the concentration of Mg2+ ions.
The results obtained are shown in the following table of Document 1

t (min) 12 25 35 55 70 90 110 135

[Mg ] x10-3 mol.L-1
2+
17 33.6 48.3 62 73.8 82.8 90 94

3.1. Plot the curve [Mg2+] = f (t). Take the following scale:
Abscissa: 1cm for 20min and ordinate: 1 cm for 8 ×10-3 mol/l
3.2. Determine the half life time of the reaction
3.3. At instant t= 160 min, the concentration of H3O+ is 0.2mol.L-1. Verify if this time represents the end of
the reaction.

4. Effect of some kinetic factors:

Consider the three Experiments described below have the same experimental conditions as in the First
Experiment with only one modification in each experiment

Second Experiment: The initial concentration of H3O+ ions is 0.5 mol/l

Third Experiment: It takes place at a temperature different than 25oC
Fourth experiment: The reaction takes place in the presence of finely divided particles of magnesium metal

4.1. Answer by true or false. Justify

a. Rate ( 1st experiment) = Rate ( 2nd experiment).
 b. [Mg2+ ]max (in 1st experiment) < [Mg2+]max (in 2nd experiment)

4.2. The concentration of [Mg2+] in the third experiment at the instant 35 min is greater than [Mg2+] in the
first experiment
Specify whether the temperature in the third experiment is greater or smaller than 25oC.

4.3. Choose the correct answer. Justify.

a. Half life time t1/2 : t1/2 (1st experiment) > t1/2 (4th experiment)
b. Half life time t1/2 : t1/2 (1st experiment) = t1/2 (4th experiment)
c. Half life time t1/2 : t1/2 (1st experiment) < t1/2 (4th experiment)