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‫اعداد االستاذ علي حسن بكري‬

‫واالستاذة زينب الحسن‬

‫‪Page 1 / 9‬‬
This Exam Includes Three Exercises. It Is Inscribed on 4 Pages Numbered From 1 to 4. The Use of A
Non-programmable Calculator is Allowed.
Answer the three following Exercises:

Exercise 1 (7 points) Formaldehyde Adhesive

Formaldehyde (CH2O) is an adhesive that belongs to the family of glue called thermosets.
In order to harden when it cures objects, formaldehyde is used with a hardener: ammonium chloride (NH4Cl).
The balanced equation of the complete reaction that takes place is:
4 NH4+ (aq) + 6 CH2O(aq) → 4 H3O+(aq) + (CH2)6N4 (aq) + 2 H2O(L)
Hardening occurs at low pH values due to H3O+ ions produced during the reaction.
Given:
• molar masses in g.mol-1 of NH4Cl = 53.5 and CH2O = 30
• formaldehyde resin requires acidic condition of pH usually set around 4 to be cured.
• Ammonium chloride (NH4Cl) is an ionic compound very soluble in water, the dissociation
𝐻2 𝑂
+ −
equation of this compound is: NH4Cl(s) → 𝑁𝐻4(𝑎𝑞) +𝐶𝑙(𝑎𝑞)

1. Preliminary Study of the Reaction

An initial reaction mixture is prepared by mixing a mass m1 = 5.35 mg of NH4Cl and a mass m2 = 12.5 mg
of CH2O at T = 20oC. The total volume of the reaction mixture is maintained at V= 1L.
1.1.Calculate the initial number of moles of each reactant.
1.2.Deduce the limiting reactant.
1.3.Specify whether, at the end of the reaction, the pH value in the reaction medium agrees with the required
condition for formaldehyde resin to be cured.
1.4.Show that, at any time t, the concentration of CH2O in mol.L-1, [CH2O]t , is related to the pH of the solution
by the following relation:
𝟑
[CH2O]t = 4.16 × 10-4 -
𝟐 ×𝟏𝟎𝒑𝑯

2. Kinetic Study of the Reaction

A study of the kinetics of this reaction is done. A reaction mixture is prepared at 20oC, and the concentration
of H3O+ ions is measured over time. The obtained results are grouped in the table of document-1.

Time (min) 0 1 2 3 4 5 6 7 8 … 𝑡∞
+
[H3O ] × 10 mol.L 0
-5 -1 3 5 6.5 7.5 8.2 8.8 9.2 9.5 … 10
Document-1

2.1.Plot the curve representing the variation in the concentration of H3O+ ions as a function of time:
[H3O+] = f (t) in the time interval [0 – 8 min].
Take the following scales: Abscissa: 1cm for 1 min; Ordinate: 1 cm for 1 × 10-5 mol.L-1.
2.2.Deduce graphically the variation of rate of formation of H3O+ ions as time passes.
2.3.Indicate the kinetic factor responsible for this evolution of rate over time.
Page 2 / 9
2.4.Determine the half-life time, t1/2.
2.5.The rate of formation of H3O+ at t =4 min: r(H3O+)4 = 8.36 × 10-6 mol.L-1.min -1.
Choose from the following values the one that represents the rate of disappearance of CH2O at t= 4 min.
a) 8.3× 10-6 mol.L-1.min -1 c) 12.54× 10-6 mol.L-1.min -1.
b) - 8.3× 10-6 mol.L-1.min -1 d) - 12.54× 10-6 mol.L-1.min -1.

2.6.The experiment realized above is repeated, but with one modification: the temperature of the reaction is
maintained at T’ > 20oC.
- Trace, on the same graph of question 2.1, the shape of the curve representing the variation of the
concentration of (H3O+) as a function of time: [H3O] = g (t) in the interval of time [0 – 8 min]. Justify.
Exercise 2 (6.5 points) Industrial Importance of Ethanol
Ethanol is a chemical compound of great industrial and commercial importance. It is used in a wide variety of
chemical reactions.
1.Ethanol and Catalyst

Document-1 represents two possible reactions of ethanol.

𝑨𝒍𝟐 𝑶𝟑/𝟑𝟎𝟎𝟎 𝑪 𝑪𝒖/𝟑𝟎𝟎𝟎 𝑪
Reaction (R2)….. (𝑫) + 𝑯𝟐 𝑶 ← Ethanol→ (𝑩) + H2 …. Reaction (R1)
Document-1

1.1. Indicate the property of catalyst illustrated in document-1.

1.2. Write the equation of the reaction (R1), using the condensed structural formulas of the organic
compounds.
1.3. The reaction (R1) is a mild oxidation. Justify.

2.Ethanol and Synthesis of an Ester

The ester, noted E, whose condensed structural formula

is represented in document-2, makes it possible to
obtain an aroma of red fruits which can be used to
intensify the taste of a beer.
To obtain ester E, a volume of carboxylic acid (A) 𝑉acide = 43,0 𝑚𝐿 is refluxed with a volume of an alcohol (B)
𝑉alcool = 20,0 𝑚𝐿 (3,4 x10-1mol) , in the presence of sulfuric acid. We obtain, after separation, rinsing and
drying, a n(E) = 0,23 𝑚𝑜𝑙 of ester E.
The equation of the esterification reaction, written in the general case with R and R' representing carbon chains,
is as follows:
R—COOH + R’—OH ⇄ R—COO—R’ + H2O
Carboxylic acide Alcohol Ester water

Given :
• density 𝜌 (in g⋅mL-1) at 25 °C of carboxylic aicd (A) is 0,93 and its molar mass is 116 g.mol-1

2.1. Give the name of each compound (A) and (E).

2.2. The compound 2-Methylpentanoic acid is an isomer of carboxylic acid (A).
2.2.1.Write the condensed structural formula of this isomer.
Page 3 / 9
 2.2.2.ONLY LS : Verify that the molecule of this isomer is chiral.
2.3.State the importance of reflux heating.
2.4.Show that the initial quantity of substance of
the acid (A) is 3.4 x 10-1 mol.
2.5.Determine the percentage of esterification of
the acid (B) at the end of the evolution of the
system.
2.6.Different experiments have been implemented
in order to observe the impact of the rise in
temperature, the presence of a catalyst or an
excess of one of the reactants during an
esterification reaction. The results are grouped
in document-3:
Refering to document-3
2.6.1 Choose the characteristics of this
esterification reaction.
Slow, fast, total, limited, exothermic, athermic
and endothermic.
2.6.2 Indicate and justify two ways to increase
the rate of the reaction. Document -3
2.6.3 Specify how to increase the yield of the reaction.

Exercise 3 (6.5 points) A Household Product

Destop® is a concentrated basic solution of sodium hydroxide used to unclog clogged pipes. The mass
percentage of sodium hydroxide in the commercial solution can be 10%, 20%, etc. .
Given :
- The titration is carried out at 25 ºC.
- Molar mass of sodium hydroxide: M (NaOH) = 40 g.mol-1.
- The value of ionic product of water at 25oC is Kw = 10-14

1. Behavior of Sodium Hydroxide in Water

In the laboratory, we have a bottle containing a solution of sodium hydroxide (Na++HO-) denoted (S) with a
molar concentration Cb = 3.16 x 10-2 mol.L-1.
The pH pf solution (S) is pH(S) = 12.5
1.1. Calculate the molar concentration of hydroxide ions, [HO-] in the solution.
1.2.Prove that sodium hydroxide is a strong base.
1.3.What will be the pH of the solution after diluting it 10 times?

2. Dilution of the Commercial Solution.

The commercial solution having too high a concentration is diluted. 500 mL of a solution (S') of concentration
C1 are prepared, by diluting 100 times a volume Vo of the solution of ˝ Destop˝.
Choose, with justification, from document-1, the most precise set to prepare the solution (S’).

Page 4 / 9
 Set (a) Set (b) Set (c)
- 50 mLbeaker - 50 mLbeaker - 50 mLbeaker
- 500 mL erlenmeyer flask - 500 mL volumetric flask - 500 mL volumetric flask
- 5 mL volumetric pipet - 5 mL volumetric pipet - 5 mL graduated pipet
Document-1

3. pH- metric Titration of Solution (S’)

- A volume Vb = 20 mL of solution (S’) is introduced into a beaker and distilled water is added for
suitable immersion of the combined electrode of the pH meter.
- The pH-metric titration of the solution (S) is carried out with a hydrochloric acid solution of
concentration Ca = 7.2x10-2 mol.L-1.
- The volume of hydrochloric acid poured to achieve equivalence is determined graphically, its value is:
VaE = 168 mL.
3.1.The titration of this household product ˝ Destop˝ is carried out after dilution. Give two reasons for this
dilution.
3.2.Write the equation of titration reaction.
3.3.Determine the concentration of the solution (S') in sodium hydroxide.
3.4.Deduce the mass percentage of the solution ˝ Destop˝ in sodium hydroxide, knowing that its density is
μ = 1,22 g.mL-1.
3.5.For each of the following statements, justify the correct one and correct the false one.
3.5.1 Addition of distilled water for proper immersion of the combination electrode of the pH meter,
increases the initial pH value of the solution (S’).
3.5.2 The pH of the final solution after adding a large excess of hydrochloric acid, tends towards pH = 0.
3.5.3 The pH of the reaction mixture corresponding to VaE is 7.

Page 5 / 9
Part Exercise 1 (7 points) Formaldehyde Adhesive
Mark
of Q Answer
𝑚 5.35×10−3
Initial number of moles of NH4Cl: n(NH4Cl)o = 𝑀 = = 0.1× 10−3 𝑚𝑜𝑙
53.5
1.1 𝑚 12.5 ×10−3
1
Initial number of moles of CH2O: n(CH2O)o= 𝑀 = = 0.4167 × 10−3 𝑚𝑜𝑙
30
𝑛1
R(NH4+ ) = = 2.5 × 10−5
4
𝑛
1.2 R(CH2O) = 62 = 6.94 × 10−5 0,75
R(NH4+ ) < R(CH2O) then NH4+ is the limiting reactant
formaldehyde resin requires acidic condition of pH usually set around 4 to be cured
By stoichiometric ratios:
𝑛(𝐻3 𝑂 + )∞ 𝑛(𝑁𝐻4+ )𝑜
= then 𝑛(𝐻3 𝑂+ )∞ = 0.1× 10−3 𝑚𝑜𝑙
4 4
1.3 𝑛(𝐻3 𝑂 + )∞ 0.1×10−3 𝑚𝑜𝑙 1
[𝐻3 𝑂+ ]∞ = = = 0.1× 10−3 𝑚𝑜𝑙.L-1
𝑉 1
pH = -log [𝐻3 𝑂+ ]∞ = 4
 Yes, at the end of the reaction, the pH value in the reaction medium agrees with the
required condition for formaldehyde resin to be cured.
At any time during the reaction:
𝑛(𝐻3 𝑂 + )𝑝 (𝑡) 𝑛(𝐶𝐻2 𝑂)𝑟𝑒𝑎 (𝑡) 3 × 𝑛(𝐻3 𝑂 + )𝑝 (𝑡)
By S.R: = then 𝑛(𝐶𝐻2 𝑂)𝑟𝑒𝑎 (𝑡) =
4 6 4
n (CH2O) rem (t) = n (CH2O)o - n (CH2O)rea (t)
3 × 𝑛(𝐻3 𝑂 + )𝑝 (𝑡)
n (CH2O) rem (t) = n (CH2O)o -
1.4 2 0,5
3 ×[𝐻3 𝑂 + ]𝑝 (𝑡)
divide by Vsolution: [CH2O] rem (t) = [CH2O]o - 2
3 ×10−𝑝𝐻
[CH2O] rem (t) = [CH2O]o - 2
𝟑
[CH2O]t = 4.16 × 10-4 - 𝟐 ×𝟏𝟎𝒑𝑯

2.1 0,75

The rate of formation of a product (H3O+) at an instant t is the slope of the tangent to the
2.2 curve at that instant (t). 0.5
Graphically we notice that: ( Slope)t=0 >( Slope)t=3> ( Slope)t=6
Page 6 / 9
 Then r(H3O+)t=0 > r(H3O+)t= 3 > r(H3O+)t=6
Then as time passes rate decreases
2.3 Kinetic factor: concentration of reactants, as [Reactants] decreases, rate decreases. 0.25
Half life time: t ½ is the time needed for the concentration of H3O+ to reach half its
maximum value.
2.4 0.75
[H3O+]t1/2 = [H3O+]∞/2 = 5 × 10−5 mol.L-1
Graphically it corresponds to t ½ = 2 min
𝑟(𝐻3 𝑂 + )(𝑡) 𝑟(𝐶𝐻2 𝑂) (𝑡) 6 × 𝑟(𝐻3 𝑂 + )(𝑡)
2.5 = then 𝑟(𝐶𝐻2 𝑂) (4) = = 12.54 × 10−6 mol.L-1.min-1 0.5
4 6 4
The answer is (C).

2.6 1

In both experiments, the initial concentrations of the reactants is the same, the only
difference is the temperature:
Temp (in 1)< Temp (in 2)
Temperature is a kinetic factor, as temperature increases, rate of reaction increases,
Then H3O+ is formed faster in the new experiment than experiment1.
At any time: [H3O+]t (in 1) < [H3O+]t (in 2) until infinity:

Part Exercise 2 (6,5 points) Industrial Importance of Ethanol Mark

of Q Correction
Starting from the same reactant, which is ethanol, the products of a reaction can be
1.1 0,5
different, depending on the catalyst used. Then a catalyst is characterized by its selectivity.
𝑪𝒖/𝟑𝟎𝟎𝟎 𝑪
1.2 𝑪𝑯𝟑‫→ 𝑯𝑶 𝟐𝑯𝑪ــــ‬ 𝑪𝑯𝟑‫ 𝑶𝑯𝑪ــــ‬+ H2 0,5
1.3 It is mild oxidation, because the carbon chain is preserved during oxidation. 0.5

2.1 0,25

This molecule is chiral, because the carbon atom no2 is an asymmetric atom, it is linked to
2.2 0,5
4 different groups of atoms : -H , -COOH, -CH3 and –CH2CH2CH3
Heating under reflux speeds up the reaction without losing reaction components by
2.3 0,5
condensing their vapors and returning them to the reaction medium.
𝜌 = 0,930 𝑔.𝑚𝐿-1, 𝑀 = 116 𝑔.𝑚𝑜𝑙-1 ; 𝑉 = 43,0 𝑚𝐿
2.4 m(A) 𝜌(𝐴)𝑥𝑉(𝐴) 0,93𝑥43 0,5
n= = = = 3,4𝑥10−1 𝑚𝑜𝑙
M(A) 𝑀 116
2.5 n(acide) esterified = n (ester) form = = 0,23 𝑚𝑜𝑙 0,75
Page 7 / 9
 n(acide) esterified 0,23
% of esterification =  100 =  100 = 67,65%
n(acide) initial 0,34
Slow, limited and athermic.

Note explanation is not required in this part since verb “choose” does not require
justification, but we will explain for more understanding.
2.6.1 Temperature is a kinetic factor, as temperature changes , α at ∞ is always 0.67, it has no 0,75
effect on Kc, the reaction is athermal.
From the analysis of the document the conversion rate of the esterification α is still 0.67
(equimolar mixture), the reaction is limited. at ∞
The reaction needs 20 min to finish, it is a slow reaction.
One can increase the reaction rate by changing the temperature (kinetic factor) and by
using a catalyst.
By comparing the two graphs (b) and (d), we observe that the graph (b) has a horizontal
tangent, so the equilibrium is reached. The graph (b) has no horizontal tangent therefore it
2.6.2 1
does not reach equilibrium, and hence the catalyst increases the rate of reaction.
By comparing the two graphs (d ) and ( e) , we see that the graph ( d) where the
temperature is 700C is faster than the graph ( e) where the temperature is 200C
Then the temperature is a factor that accelerates the kinetic reaction.
The graphs (a) and (b) corresponds to experiments at the same temperature (70°C) and in
the presence of a catalyst, but the initial amounts of reactants are different for the acid
(unequal to the alcohol). The quantity of ester formed is greater for the experiment that
2.6.3 corresponds to graph (a) than that to the experiment that corresponds to graph )b). 0,75
So, the introduction of an initial non equimolar mixture promotes the reaction in the
direction of formation of the ester and thus increases the yield of esterification more than
67%.

Part Exercise 3 (6,5 points) A Household Product

Mark
of Q Solution
1.1 Molar concentration of OH is [OH ] = 10𝑝𝐻−𝑝𝐾𝑤 = 1012.5−14 = 0.0316 𝑚𝑜𝑙. 𝐿−1
- -
0.5
1.2 In this solution Cb = [OH-] , then it is strong base. 0.5
Diluting a strong base 10 times decreases it spH by 1 unit. So its pH will be 11.5 after 10
1.3 0.5
times dilution
Upon dilution, numbe rof moles of dissolved solute is conserved :
𝑛(𝑁𝑎𝑂𝐻)𝑡𝑎𝑘𝑒𝑛 𝑏𝑦 𝑝𝑖𝑝𝑒𝑡 = 𝑛(𝑁𝑎𝑂𝐻)𝑖𝑛 𝑡ℎ𝑒 𝑝𝑟𝑒𝑝𝑎𝑟𝑒𝑑 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝐶𝑜 𝑉𝑜 = 𝐶𝑆′ 𝑉𝑆′
2 V 500 0.75
Dilution factor = 100 = , so V0 = = 5 mL.
V0 100
So the most precise set is set (b).
If the titration is carried out before dilution, we will need a big volume from the burette to
3.1 0.5
reach equivalence point. This leads to loss of time, materials, and accuracy
3.2 The equation of the titration reaction is : H3O+ + HO – → 2 H2O 0.5
At equivalence point :
n (OH – ) dans 20 mL de (S) = n (H3O+) dans 16,8 mL de la solution acide.
3.3 CbVb = CaVaE 1
𝐶 𝑉
Cb = 𝑎𝑉𝑏𝑎𝐸
Page 8 / 9
 7,2  10 −2  16,8  10 −3
C(S) = −3
≈ 6,05x10-2 mol.L-1.
20  10
𝑚 (𝑁𝑎𝑂𝐻)
%𝑚 (𝑁𝑎𝑂𝐻) = × 100
𝑚(𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛)
(𝑛×𝑀 )𝑁𝑎𝑂𝐻
%𝑚 (𝑁𝑎𝑂𝐻) = (𝜌×𝑉) × 100
𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝐶𝑜 ×𝑀𝑁𝑎𝑂𝐻
%𝑚 (𝑁𝑎𝑂𝐻) = × 100
𝜌𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
3.4 𝐶𝑆′ ×100 ×𝑀𝑁𝑎𝑂𝐻 0,75
%𝑚 (𝑁𝑎𝑂𝐻)= × 100
𝜌𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
6.02 ×10−2 ×100 ×40
%𝑚 (𝑁𝑎𝑂𝐻)= × 100
1.22×103
%𝑚 (𝑁𝑎𝑂𝐻) = 19.8%
pH = pKw + LogCb
Addition of water for proper immersion of pH- meter electrodes decreases the concentration
3.5.1 0.5
of the basic solution initially present in the beaker and thus decreases the pH of the solution
False
The pH of the solution after adding of large excess of acidic solution from burette
3.5.2. tends toward the pH = -log Ca = -log7.2x10-2 = 1.14 0.5
False
At equivalence, the species in the solution are: spectator ions Na+ and Cl –and H2O which
3.5.3 gives a pHE = 7. 0.5
True

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