ENSTI-Annaba-CPST-2nd year Solutions chemistry (2024/2025)

Tutorial 2. Acid-Base Equilibria

Exercise 1. (Definitions of acid and base)

Consider the following substances:
𝐻𝐶𝑙𝑂4, 𝐶𝑁 −, 𝑁𝑎+, 𝐻2 𝑆, 𝐾𝑂𝐻, 𝐻𝐶𝑂3 −, 𝑆𝑂4 2−, 𝐻2 𝑂, 𝑁𝑂3 −
1. Write possible reaction equation(s) for each substance in aqueous medium.
𝐻𝐶𝑙𝑂4 (Perchloric acid) : 𝐻𝐶𝑙𝑂4 + 𝐻2 𝑂 → 𝐻3 𝑂 + + 𝐶𝑙𝑂4 −
𝐶𝑁 − (Cyanide ion) : 𝐶𝑁 − + 𝐻2 𝑂 ⇌ 𝐻𝐶𝑁 + 𝐻𝑂 −
𝑁𝑎+ (Sodium ion) : cannot participate in acid-base reactions
𝐻2 𝑆 (Hydrogen sulfide) : 𝐻2 𝑆 + 𝐻2 𝑂 ⇌ 𝐻3 𝑂+ + 𝐻𝑆 −
KOH (Potassium hydroxide) : 𝐾𝑂𝐻 → 𝐾 + + 𝐻𝑂−
𝐻𝐶𝑂3 − (Bicarbonate ion) : 𝐻𝐶𝑂3 − + 𝐻2 𝑂 ⇌ 𝐻2 𝐶𝑂3 + 𝐻𝑂 −
2−
𝐻𝐶𝑂3 − + 𝐻2 𝑂 ⇌ 𝐻3 𝑂+ + 𝐶𝑂3
 𝑆𝑂4 2− (Sulfate ion) : 𝑆𝑂4 2− + 𝐻2 𝑂 ⇌ 𝐻𝑆𝑂4 − + 𝐻𝑂 −
 𝐻2 𝑂 (Water) : 2𝐻2 𝑂 ⇌ 𝐻3 𝑂+ + 𝐻𝑂 −
 𝑁𝑂3 − (Nitrate ion) : cannot participate in acid-base reactions

2. Identify which substances act as the Bronsted–Lowry acids and which act as Bronsted–
Lowry bases. Determine which are strong and which are weak.
To identify whether a substance acts as a Brønsted–Lowry acid or base, acids are defined as substances
that donate an 𝐻 + , while bases are substances that accept an 𝐻 + .
Strong acids or bases, completely ionize, do not have a 𝑝𝐾𝑎 value (in exercise data), while weak acids
and bases establish an equilibrium and can be described using 𝑝𝐾𝑎 values of their pair (acid/base).
Acids Bases
Strong acids Weak acids Strong bases Weak bases
−
𝐻𝐶𝑙𝑂4 𝐻2 𝑆, 𝐻𝐶𝑂3 , 𝐻2 𝑂 𝐾𝑂𝐻 *(Arrhenius base) 𝐶𝑁 𝑆𝑂4 2−, 𝐻𝐶𝑂3 − , 𝐻2 𝑂
−

3. Determine which substances are amphoteric.

𝐻𝐶𝑂3 − and 𝐻2 𝑂 are amphoteric substances, they act as both an acid and a base.

4. Which substances act as spectator ions?

𝑁𝑎+ and 𝑁𝑂3 − are spectator ions. They are derived from the ionization of strong electrolyte like
(𝑁𝑎𝐶𝑙, 𝑁𝑎𝑂𝐻) and (𝐻𝑁𝑂3 , 𝐻𝑁𝑂3 ) respectively. Furthermore, they cannot participate in the chemical
reaction occurring in a solution and do not take part in any acid-base equilibria or 𝑝𝐾𝑎 /𝑝𝐾𝑏 pairs. Their
presence does not affect the 𝑝𝐻 or the equilibrium of the acid-base reactions occurring in the solution.

5. Rank the substances according to their 𝑝𝐾𝑎 values. Identify the most acidic and the most
basic substances.
The most basic substance is 𝐶𝑁 −, and the most acidic substance is 𝐻2 𝑆.

Dr. A. AMIRA 1/5

ENSTI-Annaba-CPST-2nd year Solutions chemistry (2024/2025)

Exercise 2. (Strong acid)

Perchloric acid (𝐻𝐶𝑙𝑂4) is used in industry for electropolishing and etching of various metals.
In the laboratory, a chemist has prepared two solutions (A&B) of this acid.
Solution A: 200 𝑚𝐿 of distilled water is added to 100𝜇𝐿 of 0.02 𝑀 solution of perchloric acid.
Solution B: the solution A is diluted 1:200 with distilled water.
1. Calculate the concentration of each solution.
Solution A:
𝐶𝐴,1 𝑉𝐴,1 0.02 × 100 𝜇𝐿
𝐶𝐴,1 𝑉𝐴,1 = 𝐶𝐴,2 𝑉𝐴,2 ⇒ 𝐶𝐴,2 = = ≈ 10−5 𝑀
𝑉𝐴,2 (200 × 103 + 100)𝜇𝐿
Solution B:
(1:200) means, to each 1 𝑚𝐿 of the solution A is added 199 𝑚𝐿 of water to obtain a final volume of
200 𝑚𝐿. This means the solution A has been diluted by a factor 𝑓 of 200.
𝐶𝐴 10−5
𝑓= ⇒ 𝐶𝐵 = ≈ 5 × 10−8 𝑀
𝐶𝐵 200
2. Calculate the 𝑝𝐻 of the prepared solutions.
When the perchloric acid is dissolved in water, two equilibria produce hydronium ions:
𝐻𝐶𝑙𝑂4 + 𝐻2 𝑂 → 𝐻3 𝑂+ + 𝐶𝑙𝑂4 −
2𝐻2 𝑂 ⇌ 𝐻3 𝑂 + + 𝐻𝑂− 𝐾𝑤 = [𝐻3 𝑂+ ][𝑂𝐻 − ]
Solution A: 𝐶𝐴,2 = 10−5 𝑀 > 3 × 10−7 𝑀 ⇒ The autoprotolysis of water is negligible.
𝑝𝐻 = −𝑙𝑜𝑔 𝐶𝐴,2 = − 𝑙𝑜𝑔( 10−5 ) = 5 < 6.5
Solution B: 𝐶𝐵 = 5 × 10−8 𝑀 < 3 × 10−7 𝑀 ⇒ The autoprotolysis of water is considerable.
MB: 𝐶𝐵 = [𝐶𝑙𝑂4 − ]
CB: [𝐻3 𝑂 + ] = [𝐶𝑙𝑂4 − ] + [𝐻𝑂− ]
𝐾
Substituting [𝐶𝑙𝑂4 − ] for 𝐶𝐵 and [𝐻𝑂− ] = [𝐻 𝑤+] in CB yields:
3𝑂
𝐾𝑤
[𝐻3 𝑂+ ] = 𝐶𝐵 +
[𝐻3 𝑂+ ]
Which rearranges to: [𝐻3 𝑂 + ]2 − 𝐶𝐵 [𝐻3 𝑂+ ] − 𝐾𝑒 = 0
1
Therefore, 𝑝𝐻 = −𝑙𝑜𝑔 [ (𝐶𝐵 + √𝐶𝐵 2 + 4𝐾𝑤 )] = − 𝑙𝑜𝑔( 1.28 × 10−7 ) = 6.89 > 6.5
2

3. Calculate the concentration of all species present in each of the above solutions.
Solution A: [𝐻3 𝑂 + ] = [𝐶𝑙𝑂4 − ] = 10−5 𝑀.
𝐾𝑤 10−14
[𝐻𝑂 − ] = = = 10−9 𝑀
[𝐻3 𝑂+ ] 10−5
Solution B: [𝐻3 𝑂 + ] = 1.28 × 10−7 , [𝐶𝑙𝑂4 − ] = 5 × 10−8 𝑀.
𝐾𝑤 10−14
[𝐻𝑂 − ] = = = 7.81 × 10−8 𝑀.
[𝐻3 𝑂+ ] 1.28 × 10−7

Exercise 3. (Weak acid)

Acetic acid (𝐶𝐻3 𝐶𝑂𝑂𝐻) is often used as an acidulant and preservative in food. Worldwide, its
most common use has been as vinegar.
 Complete the table below by calculating the missing information for each acetic acid solution,
knowing that its 𝑝𝐾𝑎 = 4.75.
Acetic acid solution A B C
−3
𝐶 (𝑀) 0.044 𝑀 10 10−6
Ionization percent (𝛼) 2% 12.4% 94.93%
𝑝𝐻 3.05 3.90 6

Dr. A. AMIRA 2/5

ENSTI-Annaba-CPST-2nd year Solutions chemistry (2024/2025)

When the acetic acid is dissolved in water, two equilibria produce hydronium ions:
[𝐻3 𝑂+ ][𝐶𝐻3 𝐶𝑂𝑂− ]
𝐶𝐻3 𝐶𝑂𝑂𝐻(𝑎𝑞) + 𝐻2 𝑂(𝑙) ⇌ 𝐻3 𝑂 + (𝑎𝑞) + 𝐶𝐻3 𝐶𝑂𝑂 − (𝑎𝑞) 𝐾𝑎 = [𝐶𝐻3 𝐶𝑂𝑂𝐻]
2𝐻2 𝑂 ⇌ 𝐻3 𝑂 + + 𝐻𝑂− 𝐾𝑤 = [𝐻3 𝑂 + ][𝑂𝐻 −]

 Solution A: Supposing APN

𝐶𝐻3 𝐶𝑂𝑂𝐻(𝑎𝑞) + 𝐻2 𝑂(𝑙) ⇌ 𝐻3 𝑂+ (𝑎𝑞) + 𝐶𝐻3 𝐶𝑂𝑂− (𝑎𝑞)
I C excess 0 0
Eq 𝐶 − 𝐶𝛼 excess 𝐶𝛼 𝐶𝛼
The degree of dissociation of acetic acid is 𝛼 = 2% = 0.02 < 0.1 ⇒ this acid is slightly dissociated
([𝐶𝐻3 𝐶𝑂𝑂𝐻] ≥ 10 [𝐶𝐻3 𝐶𝑂𝑂− ]), for this 𝐶𝛼 can be neglected front of C.
The expression of dissociation constant can be written as :
(𝐶𝛼)(𝐶𝛼) (𝐶𝛼)2
𝐾𝑎 = (𝐶−𝐶𝛼)
= = 𝐶𝛼 2 (only in the case of APN)
𝐶
𝐾𝑎 10−𝑝𝐾𝑎 10−4.75
𝐶= 2 = = = 0.044 𝑀
𝛼 (0.02)2 (0.02)2
The 𝑝𝐻 of the solution is calculated according to the formula:
1
𝑝𝐻 = (𝑝𝐾𝑎 − 𝑙𝑜𝑔𝐶𝑎 ) = 3.05 < 6.5 𝑎𝑛𝑑 < 𝑝𝐾𝑎 − 1
2
 Solution B:

Let's locate the dissociation equilibrium of this acid;

𝑝𝐾𝑎 − 𝑝𝐶𝑎 = 4.75 + 𝑙𝑜𝑔(10−3 ) = −1 < 1.75 < 2 ⇒ Acid Moderately Dissociated (AMD).
In the case of APN: [𝐻3 𝑂 + ]2 + 𝐾𝑎 [𝐻3 𝑂+ ] − 𝐾𝑎 𝐶𝑎 = 0
1
𝑝𝐻 = −𝑙𝑜𝑔 [ (−𝐾𝑎 + √𝐾𝑎 2 + 4𝐾𝑎 𝐶𝑎 )] = 𝑝𝐻 = −𝑙𝑜𝑔 (1.24 × 10−4 ) = 3.90 < 6.5
2
The degree of dissociation α in terms of concentrations is:
[𝐶𝐻3 𝐶𝑂𝑂− ] [𝐻3 𝑂 + ] 1.24 × 10−4
𝛼= = = = 0.124 (12.4%), 10% < 12.4% < 90%
𝐶0 𝐶0 10−3
 Solution C:

𝑝𝐻 = 6 > 6.5 (𝐴𝑃𝑁) 𝑎𝑛𝑑 > 𝑝𝐾𝑎 + 1 ⇒ The acid is totally dissociated (ATD).
[𝐻3 𝑂 + ] = 10−𝑝𝐻 = 10−6 𝑀
The degree of dissociation can be also calculated from the constant of dissociation.
(𝐶𝛼)(𝐶𝛼) 𝐶𝛼 2
𝐾𝑎 = =
(𝐶 − 𝐶𝛼) 1 − 𝛼
𝐶𝛼 2 + 𝐾𝑎 𝛼 − 𝐾𝑎 = 0 ⇔ (10−6 )𝛼 2 + (10−4.75 )𝛼 − (10−4.75 ) = 0
The resolution of the equation gives: 𝛼 = 0.9493 (94,93% > 90%)
Exercise 4. (Strong monobase and dibase)
I. Potassium hydroxide (𝐾𝑂𝐻) is used in alkaline batteries, which are used to power many
devices including remote controllers.
1. What is the 𝑝𝐻 of a 10−4 𝑀 𝐾𝑂𝐻 solution.
When 𝐾𝑂𝐻 is dissolved in water, two equilibria produce hydroxide ions:
𝐾𝑂𝐻 → 𝐾 + + 𝐻𝑂−
2𝐻2 𝑂 ⇌ 𝐻3 𝑂 + + 𝐻𝑂− 𝐾𝑤 = [𝐻3 𝑂+ ][𝑂𝐻 − ]
𝐾𝑂𝐻 is a strong base that completely dissociates in water.
For a 10−4 𝑀 𝐾𝑂𝐻 solution, the concentration of hydroxide ions [𝐻𝑂− ]= 10−4 𝑀 > 3 × 10−7 𝑀.
⇒ The autoprotolysis of water is negligible.
𝑝𝐻 = 14 + 𝑙𝑜𝑔 𝐶𝐾𝑂𝐻 = 14 + 𝑙𝑜𝑔( 10−4 ) = 10 > 7.5
Dr. A. AMIRA 3/5
ENSTI-Annaba-CPST-2nd year Solutions chemistry (2024/2025)

2. What is the amount of potassium hydroxide should be added to one liter of pure water to
change the 𝑝𝐻 by 0.2 units?
To change the 𝑝𝐻 of pure water, which has a 𝑝𝐻 of 7, by 0.2 units, the final 𝑝𝐻 will be 7.2. In this case
the autoprotolysis of water is considerable (𝑝𝐻 < 7.5).
MB: 𝐶𝑏 = [𝐾 + ]
CB: [𝐻3 𝑂 + ] + [𝐾 + ] = [𝑂𝐻 − ]
𝐾
Substituting [𝐾 + ] for 𝐶𝑏 and [𝑂𝐻 − ] = [𝐻 𝑤+] in CB yields:
3𝑂
𝐾𝑤
[𝐻3 𝑂+ ] + 𝐶𝑏 =
[𝐻3 𝑂 + ]
2
𝐾 −[𝐻 𝑂+ ]2 10−14 −(10−7.2 )
Therefore, 𝐶𝑏 = 𝑤[𝐻 3+] = = 9.54 × 10−8 M < 3 × 10−7 𝑀
3𝑂 10−7.2
𝑛 𝑚𝐾𝑂𝐻
𝐶𝑏 = = ⇒ 𝑚𝐾𝑂𝐻 = 𝐶𝑏 × 𝑀𝐾𝑂𝐻 × 𝑉 = 9.53 × 10−8 × 56.11 × 1 = 5.35 × 10−6 𝑔
𝑉 𝑀𝐾𝑂𝐻 𝑉
The amount of potassium hydroxide to be added to one liter of pure water to change the 𝑝𝐻 by 0.2 units
is 5.35 𝜇𝑔.

II. Magnesium hydroxide 𝑀𝑔(𝑂𝐻)2 is used in cosmetic and personal care products as
neutralizing agent to control 𝑝𝐻 levels and protect the skin from damage caused by highly
acidic chemicals.
A chemist prepared a solution by dissolving 7.3 𝑚𝑔 of magnesium hydroxide in 250 𝑐𝑚3 of
distilled water, and then measured its 𝑝𝐻 at 25°𝐶. It was found to be 11.
 Is the magnesium hydroxide a strong base?

Calculating the concentration of the solution:

𝑚𝑀𝑔(𝑂𝐻)2 7.3
𝐶𝑏 = = = 5 × 10−4 𝑀
𝑀𝑀𝑔(𝑂𝐻)2 𝑉 58.33 × 0.25
Supposing 𝑀𝑔(𝑂𝐻)₂ is a strong base that completely dissociates in water.
𝑀𝑔(𝑂𝐻)₂ → 𝑀𝑔2+ + 2𝐻𝑂 −
2𝐻2 𝑂 ⇌ 𝐻3 𝑂 + + 𝐻𝑂−
Each mole of 𝑀𝑔(𝑂𝐻)₂ produces 2 hydroxide ions,
Therefore, the concentration of hydroxide ions produced is: [𝐻𝑂− ] = 2 × (5 × 10−4 ) = 10−3 𝑀
> 3 × 10−7 𝑀 (𝐴𝑃𝑁)
The 𝑝𝐻 of the solution is calculated according to the formula:
𝑝𝐻 = 14 + 𝑙𝑜𝑔[𝐻𝑂− ] = 11 > 7.5
Therefore, yes the magnesium hydroxide is a strong base.

Exercise 5. (Weak base)

Ammonia (𝑁𝐻3 ) is used in wastewater treatment as well as in the leather, rubber, paper, food
and beverage industries.
The percentage of protonated ammonia molecules in a 10−3 𝑀 solution is 11.82%.
1. How is the base protonated?
When ammonia is dissolved in water, there are two equilibria in the medium:
[𝑁𝐻4 + ][𝐻𝑂− ]
𝑁𝐻3 (𝑎𝑞) + 𝐻2 𝑂(𝑙) ⇌ 𝑁𝐻4 + (𝑎𝑞) + 𝐻𝑂 − (𝑎𝑞) 𝐾𝑏 = [𝑁𝐻3 ]
2𝐻2 𝑂 ⇌ 𝐻3 𝑂+ + 𝐻𝑂 − 𝐾𝑤 = [𝐻3 𝑂 ][𝑂𝐻 − ]
+

The percentage of ionization (protonation degree) is 11.82%; 10% < 𝛼 < 90%. Therefore, the
base is moderately protonated (BMP).

2. Calculate the molar concentrations of the different species present in the solution?
+
The present species in solution are: 𝑁𝐻3 , 𝑁𝐻4 + , 𝐻𝑂− and 𝐻3 𝑂 .

Dr. A. AMIRA 4/5

ENSTI-Annaba-CPST-2nd year Solutions chemistry (2024/2025)

Supposing APN; we can write the extent of the reaction as function of 𝛼; in the ICE table below:
𝑁𝐻3 (𝑎𝑞) + 𝐻2 𝑂(𝑙) ⇌ 𝑁𝐻4 + (𝑎𝑞) + 𝐻𝑂− (𝑎𝑞)
I C excess 0 0
Eq 𝐶 − 𝐶𝛼 excess 𝐶𝛼 𝐶𝛼
−4
[ 𝑁𝐻4 + ] = [𝐻𝑂 − ] = 𝐶𝑏 𝛼 = 1.18 × 10 𝑀
[𝑁𝐻3 ] = 𝐶𝑏 − 𝐶𝑏 𝛼 = 8.81 × 10 −4
𝑀
𝐾𝑤
[𝐻3 𝑂+ ] = [ = 8.46 × 10−11 𝑀
𝑂𝐻 − ]
3. Deduce the 𝑝𝐾𝑎 and 𝑝𝐾𝑏 of the couple (𝑁𝐻4 +/𝑁𝐻3 ).
[𝑁𝐻4 + ][𝐻𝑂−]
𝐾𝑏 = = 1.58 × 10−5 ⇒ 𝑝𝐾𝑏 = 4.8
[𝑁𝐻3 ]
𝑝𝐾𝑎 + 𝑝𝐾𝑏 = 14 ⇒ 𝑝𝐾𝑎 = 9.2

4. Calculate the 𝑝𝐻 of the solution.

𝑝𝐻 = −𝑙𝑜𝑔[𝐻3 𝑂 + ] = 10.07
𝑝𝐾𝑎 − 1 < 𝑝𝐻 < 𝑝𝐾𝑎 + 1 (BMP)

Dr. A. AMIRA 5/5