‫مالحظات عامة‬

‫‪ -١‬النماذج المطروحة تراعي التقليصات في المنهج التي حصلت خالل العام الدراسي الحالي‬

‫‪ -٢‬النماذج المطروحة تراعي قرارات المركز التربوي من ناحية وقت المسابقة وعدد األسئلة‬

‫‪ -٣‬لإلستفادة ُي َفضّل حل المسابقة أولا ومن ثم الذهاب لإلطالع على الباريم‬

‫والعالمة التي ممكن أن تنالها على هذا النموذج‬

‫‪ -٤‬لإلستفادة ُي َفضّل أثناء حل المسابقة اللتزام بالوقت المحدد لها‬

‫‪ -٥‬ليس من الضروري أن العالمة التي يمكن أن تنالها على هذا النموذج هي تلك التي ستحصل‬
‫عليها في المتحان الرسمي‬

‫‪ -٦‬ل داعي للتوتر في حال عدم تمكنك من عدم حل بعض األسئلة‪ .‬يمكن‬
‫مراجعة الباريم ومعرفة طريقة اإلجابة‬

‫‪ -٧‬يجري العمل على تنزيل أكثر من نموذج في معظم المواد‪ .‬لذلك راجع‬
‫المنصة للتأكد من تنزيل نماذج اضافية‬

‫‪ -٨‬هذه النماذج خاصة بالمشتركين بمنصة شاطر‪ .‬لذلك يُمنع نشرها وتداولها تحت طائلة المسؤولية‬
 2 ‫نموذج‬ ‫العامة‬
ّ ‫شهادة الثّانويّة‬
ّ ‫امتحانات ال‬
‫ علوم الحياة‬:‫الفرع‬

‫مسابقة في مادة الكيمياء‬

‫ ساعة ونصف‬:‫المدة‬

This exam is composed of three exercises prescribed on 4 pages. The use of non-programmable
calculator is allowed. Answer the following three exercises.

Exercise-1- ( 7 points ) Kinetic of the oxidation of 2- propanol

2-propanol is a colorless, flammable chemical compound with a strong odor.

The purpose of this exercise is to study the kinetic of the above reaction.
During the experiment, the temperature T is kept constant.

1. Preliminary study.

 2-propanol is oxidized by hydrogen chromate ions (HCrO4 –) in acidic medium according to the
following equation: 2 HCrO4 - + 3 C3H8O + 8 H+ 2 Cr3+ + 3 (A) + 8 H2O
 A solution of 2-propanol of initial concentration C1 = 0.8×10-2 mol.L-1 are oxidized by hydrogen
chromate ions (HCrO4-) of initial concentration C2 = 1.08×10-3 mol.L-1 in acidic medium.
 The volume of solution is constant during the reaction.
Document-1-

Referring to document-1-:
1.1. Specify the family of (A). Write its condensed structural formula.
1.2. Identify the limiting reactant.

2. Kinetic study.

To study the kinetic of the oxidation reaction, 8 bulbs are prepared with same initial reactional
mixture. At different times the concentration of hydrogen dichromate ion is calculated and the
results are given in the table of document-2-.

Time (min) 10 20 30 40 50 60 80
[HCrO4-] ×10-3 mol.L-1 0.851 0.671 0.529 0.417 0.329 0.259 0.161
Document-2-

2.1. Verify whether the time t= 80 min represents the end of reaction time.
2.2. Plot the curve [HCrO4-] = f(t) in the interval of time [0 ;80 min].
Scale: x-axis: 1 cm for 10 min ; y-axis : 1 cm for 0.1×10-3 mol.L-1
2.3. Explain, graphically, the variation of the rate of disappearance of HCrO4- ions
with time. Deduce the kinetic factor responsible for this variation.
2.4. Determine the half-life time of the reaction t½.
 2.5. The experiment is repeated at temperature T ' < T. Choose, with justification, the
correct answer:
2.5.1. [HCrO4-] remaining at 80 min at T ' is :
i- less than that at T ii- greater than that at T iii- equal to that at T
2.5.2. [Cr3+] formed at end of reaction :
i- remains constant ii- decreases iii- increases

Exercise-2- (6 points) Titration of hydrogen iodide solution

The purpose of this exercise is to verify the percentage by mass of hydrogen iodide (HI) in a
commercial product.

On the label of a bottle of commercial hydrogen iodide solution, we read the following information:
Molar mass of HI : M(HI) = 128 g.mol-1 ; density of solution : ρ = 1.7 g.mL-1
Percentage by mass of HI in solution: p = 57 % .
Document-1-

Given: The study is performed at 25°C .

Ionic product of water Kw =10-14

1. Preparation of HI solution (S).

1.1. Referring to document-1-, show that the concentration of the commercial solution
(S0) of HI is C0 = 7.57 mol.L-1.
1.2. Solution (S0) is diluted 100 times in order to prepare a solution (S) .

Volumetric flask: 250 mL , 500 mL, 1000 mL. Beaker: 150 mL, 250 mL
Volumetric pipet: 5 mL , 15 mL, 25 mL Graduated cylinder: 20 mL, 50 mL
Document-2-
Choose, from document-2- , the appropriate glassware needed for the preparation
of solution (S).
1.3. The pH of solution (S) is equal to 1.12 .
Verify whether HI is a strong acid.

2. Titration of HI solution.
Into a beaker, introduce a volume Va = 15 mL of solution (S) of HI (H3O+(aq)+I-(aq)) and a certain
volume of distilled water to immerse properly the pH-meter electrode. A sodium hydroxide
solution NaOH (Na+(aq) + HO-(aq)) of molar concentration Cb = 6 ×10-2 mol.L-1 is added
progressively. Equivalence is reached after addition of a volume Vb.E = 18.7 mL.

2.1. Write the equation of titration.

2.2. Based on chemical species present in the beaker at equivalence, specify the point that
represents the equivalence point:
A (Vb.E =18.7 mL ; pHE = 8.3) ; B (Vb.E=18.7 mL ; pHE = 7) ; C (Vb.E= 18.7 mL ; pHE = 5.8)
2.3. Determine the concentration of solution (S). Deduce that of (S0).
2.4. Calculate the percentage by mass of HI in solution (S0). Is it in accordance with that
on the label, knowing that the percentage error allowed is < 5%?
 2.5. Choose the correct answer. Justify without calculation.
2.5.1. The pH of solution after addition of 10 mL of NaOH is equal to:
i- 1.68 ii- 7 iii- 12.1
2.5.2. NaOH solution is replaced by KOH solution of same concentration, Vb.E :
i- increases ii- decreases iii- remains constant

Exercise 3 ( 7 points) Synthesis of an ester

Esters give to many fruits, flowers, and some conserved foods their characteristics odor and taste.
An ester (E) is prepared from the reaction of a saturated non-cyclic monoalcohol (A) and a
saturated non-cyclic monocarboxylic acid (B). Document-1- shows the condensed structural
formula of the ester (E).
 The yield of an equimolar mixture of acid and alcohol
is 67% for a primary alcohol and 60% for a secondary
alcohol.
 M(ester) = 144 g.mol-1.
 Density of (B): ρ = 0.95 g.mL-1
Document-1-  Molar mass of (B) : M(B) = 88 g.mol-1
Document-2-

Given: molar masses in g.mol-1 : M(C) = 12 ; M(H) = 1 ; M(O) = 16

1. Study of esterification reaction.

0.3 mol of (A) and 27.8 mL of (B) are heated to reflux for 40 min in the presence of few mL
of concentrated sulfuric acid solution. The mass of ester (E) at 40 min is equal to 24 g.

1.1. Write the equation of esterification reaction, using condensed structural formulas.
Give the systematic name of (A), (B) and (E).
1.2. Indicate the purpose of reflux heating.
1.3. Show that the initial mixture is equimolar.
1.4. Specify whether equilibrium is reached at t = 40 min, knowing that the equilibrium
constant of reaction is KC = 2.3.

2. Yield of reaction.

Reacting mixture Percentage yield (Y) at equilibrium

Experiment -1- 0.3 mol of (A) + 0.3 mol of (B) Y1

Experiment -2- 0.3 mol of (A) + 0.3 mol of (B) Y2

+ 0.2 mol of water
Document- 3 -

2.1. Referring to document-2-, deduce the percentage yield of experiment -1- (Y1).
2.2. Referring to document -3- and experiment-2-:
2.2.1. Determine the percentage yield (Y2) of the reaction knowing that number of mol
of water formed at equilibrium is 0.348 mol .
 2.2.2. Compare Y1 and Y2 .
2.2.3. Why the glassware used in the preparation of ester should be dry?
2.3. The acid (B) is replaced by its chlorinated derivative (C) in the preparation of (E).
2.3.1. What is the advantage of using (C) instead of (B) in the preparation of ester (E)?
2.3.2. Identify (C). Circle and name its functional group.
2.3.3. Write the equation of preparation of (E) from (C), using condensed structural
formulas.
Exercise 1 (7 points)
Q Expected answers Note
1.1 The condensed structural formula of 2-propanol is CH3-CHOH-CH3 (0.25) . It is a 1
secondary alcohol(0,25) (functional carbon attached to 2 alkyl groups). Then its
oxidation leads to the formation of a ketone .Therefore (A) is a ketone(0.25) .Its
condensed structural formula is CH3-CO-CH3 (0.25)
1.2 R( C3H8O) = ( C3H8 O) initial = C1 𝑉 = 0.8×10−2 V = 2.67 ×10-3V (0.25)
3 3 3
- ( HCrO4 − ) initial C2 𝑉 1.08×10−3 V
R( HCrO4 ) = = = = 5.4 ×10-4V = 0.54×10-3V(0.25) 0.75
2 2 2
Since the volume of solution is constant
then R( C3H8O) > R( HCrO4 - ) therefore HCrO4 – is the limiting reactant.(0.25)
2.1 Since HCrO4 – is the limiting reactant then at the end of reaction its concentration is
equal to zero.(0,25) 0.75
From table in document-2- : [HCrO4 - ]t=80min = 0.161×10-3 mol.L-1 ≠ 0 (0.25)
Then the time t= 80min does not represent the end of reaction time(0.25)
2.2.

2.3 The negative slope of the tangent to the curve at point of abscissa t which is equal
to the rate of disappearance of HCrO4 - ions , decreases with time(0. 5) . Then the 1
rate of disappearance of HCrO4 – ions decreases with time. (0.25)
This variation is due to the decrease in the concentration of reactants HCrO4 – and
C3H8O.Then the concentration of reactants HCrO4 – and C3H8O is the kinetic factor
responsible for this variation.(0.25)
2.4 Half-life time is the time needed for half of the initial amount of HCrO4 – ions to
disappear (to be consumed). (0.25) 1
[HCrO4 − ]𝑖𝑛𝑖𝑡𝑖𝑎𝑙 1.08×10−3
[HCrO4 - ]t1/2 = = = 0.54 ×10-3 mol.L-1 (0.25)
2 2
From curve : t ½ = 29 min. (0.25) (t½ should appear on the curve) (0.25)
2.5.1 Temperature is a kinetic factor. As temperature decreases, the rate of disappearance
of HCrO4 – ions decreases. (0.25) 1
At each instant t : [HCrO4-]reacted at T’ < [HCrO4-]reacted at T (0.25)
Then [HCrO4-] rem at T’ > [HCrO4-] rem at T (0.25) . therefore (iii). (0.25)

2.5.2 Since the initial amount of reactants is the same then number of mol of Cr3+ ions 0.5
does not change.
In the same volume of solution, [Cr3+] remains constant(0.25) . Then (i)(0.25)
Exercise 2 (6 points)
Q Expected answers Note
1.1 mass of (HI) (n×M)of HI C(S0)×M(HI)
p= ×100 = (ρ×V)of ×100 = ×100 ⟹ (0. 5)
mass of solution solution ρ(solution) 0.75
ρ(solution)× p 1700×57
C0 = = = 7.57 mol.L-1 (0.25)
M(HI)×100 128×100

1.2 Volumetric flask ( 500 mL) (0.25) ; volumetric pipet ( 5 mL) (0.25) 0.5

1.3 During dilution the number of mol of solute (HI) is conserved

C
n(HI)in (S0)=n(HI)in(S) ⟹ CV=C0V0 ⟹ dilution factor = 0 ⟹
C
C0 7.57 -2 -1
C(S)= = = 7.57×10 mol.L (0.5) 0.75
100 100

̶ log(C)= ̶ log(7.57×10-2) = 1.12 and pH= 1.12

Since pH = ̶ log(C) then HI is a strong acid (0.25)
2.1 H3O +(aq) + HO - (aq) → 2 H2O(l) 0. 5
2.2. The species present at equivalence are : Na+ and I- (spectator ions) and H2O (of pH=7
at 25°C) . then the solution is neutral . (0.25) 0.5
Therefore B (Vb.E=18.7 mL ; pHE = 7) (0.25)
2.3 At equivalence and according to S.R:
n (H3O +) (present initially in beaker) = n (HO –)(added from buret to reach equivalence) 1
CaVa = CbVb.E (0. 5) with Cb = 6×10-2 mol.L-1, Vb.E = 18.7 mL and Va=15 mL
Then Ca = 0.0748 mol.L-1 (0.25)
Therefore : C(S0) = 100 × Ca = 100 × 0.0748 = 7.48 mol.L-1 (0.25)

2.4 Percentage by mass of NaOH (p) :

C(S0)×M(HI)×100 7.48×128×100
p(HI ) = = = 56.32% (0.25) 0.5
ρ(solution) 1700
|theoretical value− experimentalvalue| 57−56.32
% error = ×100 = ×100 = 1.19 % < 5%
theoretical value 57

Then it is in accordance with the given value (57 %). (0.25)

2.5.1 Vb (added) =10 mL < Vb.E = 18.7 mL ⟹ H3O+ is the limiting reactant (0.25)
⟹ the solution at end of reaction is acidic ⟹ pH < 7 ⟹ pH = 1.68 (0.25) 0. 75
Then (i) (0.25)
2.5.2 NaOH and KOH are strong bases of same concentration
⇒ same quantity of HO-. (0.25)
At equivalence and according to S.R : 0.75
n (H3O +) (present initially in beaker) = n (HO –)( added from buret to reach equivalence)
But n(H3O +)initial is constant ⇒ CbVb.E is constant.
Since Cb is the same then Vb.E is the same. (0.25)
Therefore (iii) (0.25)
Exercise 3 (7 points)
Q Expected answers Note
1.1

(0.75)
(A): 2-methylpropanoic acid (0.25) 1.5
(B) : 2-butanol (0.25)
(E) : 1-methylpropyl-2-methyl propanoate (0.25)

1.2 Reflux heating : increase the rate of reaction without losing any of reactants or products
by returning them back to the medium. 0.25

1.3 m(B) ρ(B)×V(B) 0.95×27.8

n(B) = = = = 0.3 mol (0.25)
M(B) M(B) 88 0.5
n(A)0= n(B)0 then the mixture is equimolar (0.25)
1.4
Ester Water Acid Alcohol
Initial state (t=0) 0.3 0.3 0 0
At t=40 min 0.3 - x 0.3 - x x x
0.133 0.133 0.167 0.167
m(E) 24 1
n(ester) = = = 0.167 mol (0.25)
M(E) 144
n (ester)t n (water)t
[ester][water] × n(ester)×n(water) (0.167)(0.167)
v v
Q=
[acid][alcohol]
= n (alcohol)t n (acid)t = = = 1.25 (0.5)
× n(acid)×n(alcohol) (0.133)(0.133)
v v

Q = 1.25 < KC =2.3 then not at equilibrium (0.25)

2.1 Since (A) is secondary alcohol (functional carbon attached to two alkyl groups ) then
0.25
Y1 = 60%
2.2.1
Acid Alcohol Ester Water
Initial state (t=0) 0.3 0.3 0 0.2
Equilibrium state 0.3 - x 0.3 - x x 0.2+x
0.152 0.152 0.148 0.348
n(ester)experimental
Y2 = ×100 (0.25) with n(ester)experimental = 0.148 mol (0.25)
n(ester)theoretical

Assume the reaction is complete : 1.25

n(acid)initial 0.3
R(acid) = = = 0.3 R(acid) = R(alcohol)
1 1
n(alcohol)initial 0.3
R(alcohol) = = = 0.3 ⇒ the mixture is stoichiometric.
1 1
n(acid)reacted n(ester)formed
Acc to S.R : = ⇒ n(ester)theoretical = 0.3 mol(0. 5) ⇒
1 1
0.148
Y2 = ×100 = 49.3% (0.25)
0.3
2.2.2 Y2 < Y1 0.25
2.2.3 Glassware should be dry since presence of water favors hydrolysis reaction of ester
0.25
2.3.1 It will make the reaction complete and more rapid than esterification 0.25
2.3.2
Acyl chloride group

(3× 0.25) 1
2-methyl propanoyl chloride(0.25)
2.3.3

0.5