‫الخاصة‬2020 ‫دورة العام‬ ‫امتحانات الشهادة الثانوية العامة‬ ‫وزارة التربية والتعليم العالي‬

2020 ‫ أيلول‬28 ‫اإلثنين‬ ‫ علوم الحياة‬:‫فرع‬ ‫المديرية العامة للتربية‬

‫دائرة االمتحانات الرسمية‬
:‫االسم‬ ‫مسابقة في مادة الكيمياء‬
:‫الرقم‬ ‫ ساعتان‬:‫المدة‬

This Exam Includes Three Exercises. It Is Inscribed on Four Pages Numbered from 1 to 4.
The Use of A Non-programmable Calculator Is Allowed.

Answer the Three Following Exercises:

Exercise 1 (6 points) Study of a Slow Reaction

Hydrogen peroxide (H2O2) oxidizes iodide ions (I −) in acidic medium in a slow reaction which takes place
according to the following equation:
− +
2 I(aq) + H2O2 (aq) + 2 H(aq) ⟶ I2 (aq) + 2 H2 O (l)

The aim of this exercise is to study the kinetic of this reaction.

1. Preparation of a Hydrogen Peroxide (H2O2) Solution (S1)
Available is a hydrogen peroxide solution (So) of concentration Co = 2.7 mol.L-1. It is required to prepare a
hydrogen peroxide solution (S1) of concentration C1 = 0.1 mol.L-1.
Choose, from the document-1, the most suitable set of glassware to realize this dilution. Justify.

Set A Set B Set C

Volumetric flask of 100 mL Volumetric flask of 100 mL Volumetric flask of 100 mL
Volumetric pipet of 10 mL Graduated pipet of 10 mL Graduated cylinder of 10 mL
Beaker of 50 mL Beaker of 50 mL Beaker of 50 mL
Document-1

2. Preliminary Study
In a beaker, one mixes:
- A volume V1 = 18 mL of potassium iodide solution (K++ I −) of concentration C1 = 0.1 mol.L-1
- A volume V2 = 9 mL of sulfuric acid solution H2SO4 of concentration C2 = 1 mol.L-1.
At instant t = 0 s, a volume V3 = 3 mL of hydrogen peroxide solution H2O2 of concentration
C3 = 0.1 mol.L -1 is added to the beaker.
In this mixture, sulfuric acid is in excess.

2.1.Calculate the initial concentrations of iodide ions [I − ]o and hydrogen peroxide [H2O2]o in the
reaction mixture.
2.2.Show that hydrogen peroxide H2O2 is the limiting reactant.
3. Kinetic Study
By an appropriate method, the concentration of iodine [I 2] at different instants is determined. The results are
grouped in the table of document-2.

t (s) 100 200 300 400 500 600 650

[I2] (10-3 mol.L-1) 3.85 5.9 7.5 8.6 9.4 9.85 10
Document-2

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 3.1. Plot the curve representing the variation of the concentration of iodine as a function of time
[I2] = f (t) in the interval of time [0 - 650 s].
Take the scales: In abscissa: 1 cm for 50 s ;
In ordinates: 1 cm for 1×10-3 mol.L-1.
3.2.Show that t= 650s represents the end time of reaction.
3.3.Determine graphically the half-life time of reaction t1/2.
3.4.Justify the following statements:
3.4.1.The initial rate of formation of I2 is greater than its rate of formation at t = 300 s.
3.4.2.The concentration of iodide ions at t ½ is [I-]1/2 = 50×10-3 mol.L-1.
3.5.From the curves of document-3, specify the one that corresponds to the variation of the
concentration of iodide ions as a function of time [I-] = g (t).

[I-] [I-]
(10-3 mol.L-1) (10-3mol.L-1)
70 70

60 60

50 50

40 40

30 30

20 20

10 10
t (s) t(s)
0 0
0 100 200 300 400 500 600 700 0 100 200 300 400 500 600 700
Curve a Curve b
Document-3

Exercise 2 (7points) Amylic Alcohol

Amylic alcohol is extracted from potatoes; it is a saturated noncyclic chain alcohol.

The aim of this exercise is to study an esterification reaction of the amylic alcohol.

Given: Molar mass in g.mol -1: M (H) = 1; M (C) = 12 and M (O) = 16

1. Identification of Amylic Alcohol

The analysis of a sample of amylic alcohol (A) of molecular formula (CxHyO) gives the mass composition
represented in document-1:

% H = 13.64% %C = 68.18% %O = 18.18%

Document-1

1.1. Show that the molecular formula of amylic alcohol (A) is C5H12O.
1.2. The mild oxidation of amylic alcohol (A) by an excess of a potassium permanganate solution an
acidic medium, gives an organic compound (C). When the compound (C) is dissolved in water, a
solution of a pH clearly less than 7 is obtained. Specify whether this test allows identifying the class
of alcohol (A).
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 1.3. Write the four possible condensed structural formulas for the alcohol (A).
1.4. Amylic alcohol (A) is a chiral molecule.
1.4.1. Justify that this alcohol is the 2-methyl-1-butanol.
1.4.2. Represent, according to Cram, the two enantiomers of this alcohol.

2. Preparation of an Ester (E)

In order to synthesize an ester (E), an equimolar mixture of amylic alcohol (A) and the compound (C) is
heated to reflux in presence of few drops of concentrated sulfuric acid.
2.1. Write, using condensed structural formulas, the equation of this esterification reaction.
2.2. Give the systematic name of the ester (E).
2.3. State two characteristics for this reaction.
(𝐘)𝟐
2.4. Given the following relation: KC = (𝟏−𝐘)𝟐 , where KC represents the equilibrium constant of the
esterification reaction and Y is the corresponding yield. Calculate the yield of this esterification
reaction knowing that KC = 4.
2.5. Consider the two following propositions:
2.5.1. Replacing compound (C) by its chlorinated derivative increases the yield of the esterification
reaction.
2.5.2. Replacing the equimolar mixture of alcohol (A) and compound (C) by a non-equimolar
mixture does not affect the yield of the esterification reaction.
In the case the proposition is correct, justify. In the case, the proposition is false, correct it.

Exercise 3 (7 points) Nitrogen Content in "Ammonitrate"

Ammonium nitrate, of formula NH4NO3, is mainly used as a nitrogen fertilizer under the name
"ammonitrate".

The aim of this exercise is to study the acid-base character of ammonium ion (NH4+) and then to determine
the nitrogen content of "ammonitrate" sample.

Given
- Molar masses of nitrogen: M(N) = 14 g.mol-1.
- This study is realized at 25 oC.
- pH-range of color change of Phenolphthalein: colorless 8.2 – 10 pink
- Nitrate ion (NO3− ) is a chemical species with no acid-base character.

1. Acid-base Character of Ammonium Ion (N𝐇𝟒+ )

Available is a solution (S) of ammonium nitrate (NH 4+ + NO− -2 -1
3 ) of concentration C = 1.0×10 mol.L . The
pH of the solution (S) is pH(S) = 5.6

1.1. Show that the ammonium ion (NH4+) is a weak acid.

1.2. Write the equation of the reaction of ammonium ion with water knowing that the acid-base pairs
involved are NH4+/NH3 and H3O+/H2O.
1.3. Determine the degree of dissociation α of NH4+ ion in water.
1.4. The solution (S) is diluted 10 times. We obtain a solution (S1). Let α1 be the degree of dissociation
of NH4+ in this solution. Choose from the following, the corresponding value of α1. Justify.

a) 2×10-4 b) 2.5×10-4 c) 8×10-4

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2. Titration of an Ammonium Nitrate Solution (Sʹ)

A mass m= 6.0 g of "ammonitrate" sample is used to prepare a solution (Sʹ) of ammonium nitrate of volume
V = 250.0 mL.
A volume Va = 10.0 mL of this solution is taken and introduced into a beaker. Then few drops of an
appropriate colored indicator are added. A sodium hydroxide solution (Na + + HO−) of concentration
Cb = 0.20 mol.L-1 is gradually added into the beaker.
Equivalence is reached after the addition of a volume VbE = 14.6 mL of sodium hydroxide solution.

The equation of the titration reaction is: NH4++ HO− → NH3 + H2O

2.1. Answer by true or false the following three propositions. Justify.

2.1.1. The sodium hydroxide solution is added using a graduated cylinder.
2.1.2. Phenolphthalein is an appropriate indicator for this titration.
2.1.3. NH4+/ NH3 and HO− / H2O are the two acid-base pairs involved in this titration.
2.2. Determine the molar concentration of ammonium nitrate in solution (Sʹ).
2.3. Verify that the mass of nitrogen (N) in the "ammonitrate" sample is m(N)=2.04 g.
2.4. Deduce the mass percentage of nitrogen in the sample studied.

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