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

Exercise 6. (Salt solutions)

Calculate the 𝑝𝐻 for each salt solution below:
1. 0.25𝑀 solution of 𝐶𝑎𝐶𝑙2 .
𝐻2 𝑂
𝐶𝑎𝐶𝑙2 (𝑠) → 𝐶𝑎2+ (𝑎𝑞) + 2𝐶𝑙− (𝑎𝑞)
I C 0 0
F 0 C 2C
2𝐻2 𝑂 (𝑙) ⇌ 𝐻3 𝑂 + (𝑎𝑞) + 𝐻𝑂− (𝑎𝑞)……….𝐾𝑤 = 10−14
Species present in solution are 𝐶𝑎2+ , 𝐶𝑙− , 𝐻3 𝑂 + , HO− and 𝐻2 𝑂.
𝐾𝑤 = [𝐻3 𝑂 + ]𝑤 [𝐻𝑂− ]𝑤 = 10−14
[𝐶𝑙− ]
(𝑀𝐵): 𝐶𝑠𝑎𝑙𝑡 = [𝐶𝑎2+ ] =
2
(𝐶𝐵): [𝐻3 𝑂 + ]𝑤 + 2[𝐶𝑎2+ ] = [𝑂𝐻 − ]𝑤 + [𝐶𝑙 − ]
We deduce : [𝐻3 𝑂 + ]𝑤 = [𝑂𝐻 − ]𝑤 = 10−7 ⇒ 𝒑𝑯 = 𝟕 (𝑛𝑒𝑢𝑡𝑟𝑎𝑙 𝑚𝑒𝑑𝑖𝑢𝑚)

2. 0.5𝑀 solution of 𝐾𝐻𝑆𝑂4 .

𝐻2 𝑂
𝐾𝐻𝑆𝑂4 (𝑠) → 𝐾 + (𝑎𝑞) + 𝐻𝑆𝑂4 − (𝑎𝑞)
I C 0 0
F 0 C C
2𝐻2 𝑂 (𝑙) ⇌ 𝐻3 𝑂 + (𝑎𝑞) + 𝐻𝑂− (𝑎𝑞)……….𝐾𝑤 = 10−14
The solution will be acidic because the conjugate acid (𝑯𝑺𝑶𝟒 − ) can hydrolyze, increasing hydronium
ions.
𝐻𝑆𝑂4 − (𝑎𝑞) + 𝐻2 𝑂(𝑙) ⇌ 𝐻3 𝑂 + (𝑎𝑞) + 𝑆𝑂4 2− (𝑎𝑞) 𝐾𝑎 = 10−1.92 < 1 ⇒ 𝐶𝑅𝑃
I C excess 0 0
F C−𝒙 excess 𝒙 𝒙
Species present in solution are 𝐾 + , 𝐻𝑆𝑂4 − , 𝑆𝑂4 2− , 𝐻3 𝑂 + , 𝐻𝑂− and 𝐻2 𝑂.
[𝐻3 𝑂+ ][𝑆𝑂4 2−]
𝐾𝑤 = [𝐻3 𝑂 + ][𝐻𝑂− ]𝑤 = 10−14 , 𝐾𝑎 = [𝐻𝑆𝑂4 − ]
− 2−
(𝑀𝐵): 𝐶𝑠𝑎𝑙𝑡 = [𝐾 + ]
= [𝐻𝑆𝑂4 ] + [𝑆𝑂4 ]
+
(𝐶𝐵): [𝐾 ] + [𝐻3 𝑂 ] = [𝐻𝑆𝑂4 − ] + 2[𝑆𝑂4 2− ] + [𝑂𝐻 − ]𝑤
+

Let’s locate the dissociation equilibrium of the acid applying (𝑝𝐾a − 𝑝𝐶𝑎 );
(𝑝𝐾a − 𝑝𝐶𝑎 ) = 1.92 + log(0.5) = −1 < 1.61 < 2 ⇒ 𝑚𝑜𝑑𝑒𝑟𝑎𝑡𝑒𝑙𝑦 𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑒𝑑 𝑎𝑐𝑖𝑑 [𝐻𝑆𝑂4 − ] ≈ [𝑆𝑂4 2− ]
Supposing APN; and making (𝐶𝐵 − 𝑀𝐵), it gives:
(𝐶𝐵): [𝐻3 𝑂 + ] = [𝑆𝑂4 2− ]
(𝑀𝐵): [𝐻𝑆𝑂4 − ] = 𝐶𝑠𝑎𝑙𝑡 − [𝑆𝑂4 2− ] = 𝐶𝑠𝑎𝑙𝑡 − [𝐻3 𝑂 + ]

Replacing [𝐻𝑆𝑂4 − ] and [𝑆𝑂4 2− ] in 𝐾𝑎 , the result is:

[𝐻3 𝑂 + ]2
𝐾𝑎 =
𝐶𝑠𝑎𝑙𝑡 − [𝐻3 𝑂 + ]
We can also deduce the same formula from the ICE table:
𝑥2
𝐾𝑎 = (𝐴𝑃𝑁)
𝐶𝑠𝑎𝑙𝑡 − 𝑥
[𝐻3 𝑂 + ]2 + 𝐾𝑎 [𝐻3 𝑂+ ] − 𝐾𝑎 𝐶𝑠𝑎𝑙𝑡 = 0
[𝐻3 𝑂 + ] = 0.07𝑀 ⟹ 𝒑𝑯 = 𝟏. 𝟏𝟓 < 6.5 (𝐴𝑃𝑁 𝑣𝑒𝑟𝑖𝑓𝑖𝑒𝑑)
3. 0.05𝑀 solution of 𝐶𝑎𝐶𝑂3 .
𝐻2 𝑂
𝐶𝑎𝐶𝑂3 (𝑠) → 𝐶𝑎2+ (𝑎𝑞 ) + 𝐶𝑂3 2−(𝑎𝑞)
I C 0 0
F 0 C C
2𝐻2 𝑂 (𝑙) ⇌ 𝐻3 𝑂 + (𝑎𝑞) + 𝐻𝑂− (𝑎𝑞)…….…….𝐾𝑤 = 10−14

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The solution will be basic because the conjugate dibase (𝐶𝑂3 2− ) can hydrolyze, increasing hydroxide
ions.
𝐾
𝐶𝑂3 2− (𝑎𝑞) + 𝐻2 𝑂 (𝑙) ⇌ 𝐻𝐶𝑂3 − (𝑎𝑞) +𝐻𝑂− (𝑎𝑞) … … … … … … … . . 𝐾𝑏,2 = 𝑤 = 10−3.68
𝐾𝑎,2
− 𝐾𝑤
𝐻𝐶𝑂3 (𝑎𝑞) + 𝐻2 𝑂 (𝑙) ⇌ 𝐻2 𝐶𝑂3 (𝑎𝑞) + 𝐻𝑂 − (𝑎𝑞) … … … … . … . . 𝐾𝑏,1 = = 10−7.62
𝐾𝑎,1
𝑝𝐾𝑎,2 − 𝑝𝐾𝑎,1 = 10.32 − 6.38 = 3.94 > 2 ⇒ Only the first basicity (lowest 𝑝𝐾𝑏 , ℎ𝑖𝑔ℎ𝑒𝑠𝑡 𝑝𝐾𝑎 ) is taken
into account, and the calculation is carried out as for a monoprotic base.

𝐶𝑂3 2− (𝑎𝑞) + 𝐻2 𝑂(𝑙) ⇌ 𝐻𝐶𝑂3 − (𝑎𝑞) + 𝐻𝑂− (𝑎𝑞) 𝐾𝑏,2 = 10−3.68 < 1 ⇒ 𝐶𝑅𝑃
I C excess 0 0
F C−𝒙 excess 𝒙 𝒙
Species present in solution are 𝐶𝑎2+ , 𝐶𝑂3 2− , 𝐻𝐶𝑂3 − , 𝐻3 𝑂 + , 𝐻𝑂− and 𝐻2 𝑂.
[𝐻𝑂− ][𝐻𝐶𝑂3 − ]
𝐾𝑤 = [𝐻3 𝑂 + ]𝑤 [𝐻𝑂− ]= 10−14 , 𝐾𝑏,2 = 2−
[𝐶𝑂3 ]
(𝑀𝐵): 𝐶𝑠𝑎𝑙𝑡 = [𝐶𝑎2+ ] = [𝐶𝑂3 2− ] + [𝐻𝐶𝑂3 − ]
(𝐶𝐵): 2[𝐶𝑎2+ ] + [𝐻3 𝑂+ ] = 2[𝐶𝑂3 2− ] + [𝐻𝐶𝑂3 − ] + [𝐻𝑂− ]
𝑤
Supposing APN, and making (𝐶𝐵 − 2𝑀𝐵), it gives: [𝐻𝐶𝑂3 − ] = [𝐻𝑂− ]

Let’s locate the dissociation equilibrium applying (𝑝𝐾b,2 − 𝑝𝐶𝑏 );

(𝑝𝐾𝑏,2 − 𝑝𝐶𝑏 ) = 10.32 + log(0.05) = 9.01 > 2 ⇒ 𝑠𝑙𝑖𝑔ℎ𝑡𝑙𝑦 𝑝𝑟𝑜𝑡𝑜𝑛𝑎𝑡𝑒𝑑 𝑏𝑎𝑠𝑒 [𝐶𝑂3 2− ] ≥ 10[𝐻𝐶𝑂3 − ]
([𝐻𝐶𝑂3 − ] are neglected in front of [𝐶𝑂3 2− ])
(𝑀𝐵): 𝐶𝑠𝑎𝑙𝑡 = [𝐶𝑂3 2− ]
Replacing [𝐶𝑂3 2− ] and [𝐻𝐶𝑂3 − ] in 𝐾𝑏,2 , the result is:
[𝐻𝑂 − ]2
𝐾𝑏,2 =
𝐶𝑠𝑎𝑙𝑡
We can also deduce the same formula from the ICE table:
𝑥2
𝐾𝑎 = (𝐴𝑃𝑁)
𝐶𝑠𝑎𝑙𝑡
[𝐻𝑂− ] = √𝐾𝑏,2 𝐶𝑠𝑎𝑙𝑡 = √10−3.68 × 0.05 = 3.23 × 10−3 𝑀 ⟹ 𝑝𝐻 = 14 + log(3.2 × 10−3 ) = 𝟏𝟏. 𝟓 > 7.5
(𝐴𝑃𝑁 𝑣𝑒𝑟𝑖𝑓𝑖𝑒𝑑)

4. 0.1𝑀 solution of 𝑁𝑎𝐻𝐶𝑂3 .

𝐻2 𝑂
𝑁𝑎𝐻𝐶𝑂3 (𝑠) → 𝑁𝑎+ (𝑎𝑞) + 𝐻𝐶𝑂3 − (𝑎𝑞)
I C 0 0
F 0 C C
2𝐻2 𝑂 (𝑙) ⇌ 𝐻3 𝑂 + (𝑎𝑞) + 𝐻𝑂− (𝑎𝑞)…….…….𝐾𝑤 = 10−14
The solution (𝐻𝐶𝑂3 − ) is an ampholyte, it can hydrolyze, and gives hydronium and
hydroxide ions.
𝐻𝐶𝑂3 − (𝑎𝑞 ) + 𝐻2 𝑂 (𝑙) ⇌ 𝐶𝑂3 2− (𝑎𝑞) +𝐻3 𝑂 +(𝑎𝑞) … … … … … . . 𝐾𝑎,2 = 10−10.32
𝐻𝐶𝑂3 − (𝑎𝑞 ) + 𝐻2 𝑂 (𝑙 ) ⇌ 𝐻2 𝐶𝑂3 (𝑎𝑞 ) + 𝐻𝑂 −(𝑎𝑞 ) … … … … . … . . 𝐾𝑏,1 = 10−7.62
𝐾𝑏,1 > 𝐾𝑎,2 ⇒ 𝑏𝑎𝑠𝑖𝑐 𝑚𝑒𝑑𝑖𝑢𝑚
𝐻𝐶𝑂3 −(𝑎𝑞 ) + 𝐻𝐶𝑂3 − (𝑎𝑞 ) ⇌ 𝐶𝑂3 2− (𝑎𝑞 ) + 𝐻2 𝐶𝑂3 (𝑎𝑞 ) … 𝐾 = 10−3.94 < 1 ⇒ 𝐸𝑃𝑅
𝐻𝐶𝑂3 − (𝑎𝑞 ) + 𝐻𝐶𝑂3 − (𝑎𝑞 ) ⇌ 𝐶𝑂3 2− (𝑎𝑞 ) + 𝐻2 𝐶𝑂3 (𝑎𝑞 )
I C C 0 0
Eq 𝐶−𝑥 𝐶−𝑥 𝑥 𝑥
Replacing the concentrations in the product of constants to find the pH;
[𝐻3 𝑂 + ][𝐻𝐶𝑂3 − ] [𝐻3 𝑂 + ][𝐶𝑂3 2− ]
𝐾𝑎,1 × 𝐾𝑎,2 = × = [𝐻3 𝑂+ ]2
[𝐻2 𝐶𝑂3 ] [𝐻𝐶𝑂3 − ]
1
𝑝𝐻 = − log √𝐾𝑎,1 × 𝐾𝑎,2 = (𝑝𝐾𝑎,1 + 𝑝𝐾𝑎,2 ) = 𝟖. 𝟑𝟓
2

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5. 0.01𝑀 solution of (𝑁𝐻4 )3 𝑃𝑂4 . Acceptor of

pKa
Donor of
𝐻2 𝑂 + 3−
(𝑁𝐻4 )3 𝑃𝑂4 (𝑠) → 3𝑁𝐻4 (𝑎𝑞 ) + 𝑃𝑂4 (𝑎𝑞) (Base) (Acid)

I C 0 0
F 0 3C C
2𝐻2 𝑂 (𝑙) ⇌ 𝐻3 𝑂 + (𝑎𝑞) + 𝐻𝑂− (𝑎𝑞)…….…….𝐾𝑤 = 10−14

𝑁𝐻4 + 𝑎𝑛𝑑 𝑃𝑂4 3− , and 𝐻2 𝑂 are initially present in the solution.

The gamma rule (I) is used to find the preponderant reaction;
𝑃𝑂4 3− (𝑎𝑞 ) + 𝑁𝐻4 + (𝑎𝑞 ) ⇌ 𝑁𝐻3 (𝑎𝑞 ) + 𝐻𝑃𝑂4 2− (𝑎𝑞) 𝐾 = 1012.37−9.25 = 103.12
𝐾 > 103 ⇒ 𝑄𝑃𝑅
I 0.01 0.03 0 0
Eq →0 0.02 0.01 0.01

We need to find the new equivalent solution;

The present species now are, 𝑁𝐻4 + (0.02𝑀), 𝑁𝐻3 (0.01𝑀) and 𝐻𝑃𝑂4 2− (0.01𝑀). (I)
The gamma rule (II) is used again to find the new preponderant reaction.
𝑁𝐻3 (𝑎𝑞 ) + 𝑁𝐻4 + (𝑎𝑞 ) ⇌ 𝑁𝐻3 (𝑎𝑞 ) + 𝑁𝐻4 +𝑎𝑞) 𝐾 = 1 ⇒ 𝐸𝑃𝑅 (𝑡ℎ𝑒 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛𝑠 𝑎𝑟𝑒 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡𝑠)

The Henderson-Hasselbalch equation is used for calculating the 𝑝𝐻.

[𝑁𝐻3 ] 0.01
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 + = 9.25 + 𝑙𝑜𝑔 0.02 = 𝟖. 𝟗𝟒
[𝑁𝐻4 ]

6. 0.01𝑀 solution of (𝑁𝐻4 )2 𝐻𝑃𝑂4 .

𝐻2 𝑂
(𝑁𝐻4 )2 𝐻𝑃𝑂4 (𝑠) → 2𝑁𝐻4 + (𝑎𝑞 ) + 𝐻𝑃𝑂4 2− (𝑎𝑞)
I C 0 0
F 0 2C C
2𝐻2 𝑂 (𝑙) ⇌ 𝐻3 𝑂 + (𝑎𝑞) + 𝐻𝑂− (𝑎𝑞)…….…….𝐾𝑤 = 10−14
𝑁𝐻4 + 𝑎𝑛𝑑 𝐻𝑃𝑂4 2− and 𝐻2 𝑂 are initially present in the solution.
The gamma rule (III) is used to find the preponderant reaction;
𝐻𝑃𝑂4 2− (𝑎𝑞 ) + 𝑁𝐻4 + (𝑎𝑞 ) ⇌ 𝑁𝐻3 (𝑎𝑞 ) + 𝐻2 𝑃𝑂4 −(𝑎𝑞) 𝐾 = 107.25−9.25 = 103.12 < 1 ⇒ 𝐶𝑃𝑅 (II)
I 0.01 0.02 0 0
F 0.01 − 𝑥 0.02 − 𝑥 𝑥 𝑥

Let's locate the dissociation equilibrium of 𝑁𝐻4 + (𝑎𝑐𝑖𝑑) 𝑎𝑛𝑑 𝐻𝑃𝑂4 2− (𝑏𝑎𝑠𝑒);
𝑝𝐾𝑎 − 𝑝𝐶𝑎 = 9.25 + 𝑙𝑜𝑔(0.01) = 7.25 > 2
⇒ 𝑠𝑙𝑖𝑔ℎ𝑡𝑙𝑦 𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑒𝑑 𝑎𝑐𝑖𝑑 [𝑁𝐻4 + ] ≥ 10[𝑁𝐻3 ]
𝑝𝐾𝑏 − 𝑝𝐶𝑏 = (14 − 7.20) + 𝑙𝑜𝑔(0.01) = 4.8 > 2
⇒ 𝑠𝑙𝑖𝑔ℎ𝑡𝑙𝑦 𝑝𝑟𝑜𝑡𝑜𝑛𝑎𝑡𝑒𝑑 𝑏𝑎𝑠𝑒 [𝐻𝑃𝑂4 2− ] ≥ 10[𝐻2 𝑃𝑂4 − ]

Therefore, we can write the concentrations of different species as follow:

[𝑁𝐻4 + ] ≈ 0.02𝑀, [𝐻𝑃𝑂4 2− ] ≈ 0.01𝑀, [𝑁𝐻3 ] = [𝐻2 𝑃𝑂4 − ] = 𝑥
Replacing them in the product of constants to find the 𝑝𝐻;
[𝐻3 𝑂 + ][𝑁𝐻3 ] [𝐻3 𝑂+ ][𝐻𝑃𝑂4 𝟐− ] [𝐻3 𝑂+ ]2
𝐾𝑎,1 × 𝐾𝑎,2 = × =
[𝑁𝐻4 + ] [𝐻𝟐 𝑃𝑂4 − ] 2
1 1
𝑝𝐻 = − log √2 × 𝐾𝑎,1 × 𝐾𝑎,2 = (𝑝𝐾𝑎,1 + 𝑝𝐾𝑎,2 ) − 𝑙𝑜𝑔2 = 𝟖. 𝟎𝟕
2 2
(III)

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Exercise 7. (Mixtures)
Determine the 𝑝𝐻 of the following mixture:
𝑴 − 𝟏: 𝐻𝐶𝑙 (12.5 𝑚𝐿, 4 × 10−2 𝑀) + 𝐶𝐻3 𝐶𝑂𝑂𝐻 (12.5 𝑚𝐿, 7 × 10−2 𝑀) + 25 𝑚𝐿 𝐻2 𝑂.
𝐻𝐶𝑙(𝑎𝑞) + 𝐻2 𝑂 (𝑙) → 𝐻3 𝑂 + (𝑎𝑞) + 𝐶𝑙 − (𝑎𝑞)
𝐶𝐻3 𝐶𝑂𝑂𝐻(𝑎𝑞) + 𝐻2 𝑂(𝑙) ⇌ 𝐶𝐻3 𝐶𝑂𝑂− (𝑎𝑞) + 𝐻3 𝑂 + (𝑎𝑞) … … … 𝐾𝑎 = 10−4.8
2𝐻2 𝑂 (𝑙) ⇌ 𝐻3 𝑂 + (𝑎𝑞) + 𝐻𝑂− (𝑎𝑞)…….…….𝐾𝑤 = 10−14
The species present initially in solution are:
𝐻3 𝑂 + , 𝐶𝑙− (𝑠𝑝𝑒𝑐𝑡𝑎𝑡𝑜𝑟 𝑖𝑜𝑛), 𝐶𝐻3 𝐶𝑂𝑂𝐻 and 𝐻2 𝑂.
Let’s calculate the concentration of these species in the mixture:
𝐶𝐻 𝑂+,𝑖 × 𝑉𝐻3 𝑂+,𝑖 0.04 × 12.5
𝐶𝐻3 𝑂+,𝑚 = 3 = = 10−2 𝑀
𝑉𝑡𝑜𝑡 50
𝐶𝐴𝑐𝑂𝐻,𝑖 × 𝑉𝐴𝑐𝑂𝐻,𝑖 0.07 × 12.5
𝐶𝐴𝑐𝑂𝐻,𝑚 = = = 1.75 × 10−2 𝑀
𝑉𝑡𝑜𝑡 50

Method 1. Let’s compare the concentrations of hydronium ions provided from each acid in the mixture.
Let’s locate the dissociation equilibrium of weak acid applying (𝑝𝐾a − 𝑝𝐶𝑎 );
(𝑝𝐾𝑎 − 𝑝𝐶𝑎 ) = 4.8 + log(1.75 × 10−2 ) = 3.04 > 2 ⇒ 𝑠𝑙𝑖𝑔ℎ𝑡𝑙𝑦 𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑒𝑑 𝑎𝑐𝑖𝑑 [𝐴𝑐𝑂𝐻] ≥ 10[𝐴𝑐𝑂− ]

𝐶𝐻3 𝐶𝑂𝑂𝐻(𝑎𝑞 ) + 𝐻2 𝑂(𝑙 ) ⇌ 𝐶𝐻3 𝐶𝑂𝑂− (𝑎𝑞 ) + 𝐻3 𝑂+ (𝑎𝑞 ) 𝐾𝑎 = 10−4.8 < 1 ⇒ 𝐶𝑅𝑃
I C excess 0 0
F C−𝒙 excess 𝒙 𝒙

𝑥2
Supposing APN: 𝐾𝑎 = ⇒ 𝑥 = [𝐻3 𝑂 + ] = √𝐾𝑎 × 𝐶𝐴𝑐𝑂𝐻,𝑚 = √10−4.8 × 1.75 × 10−2 = 5.26 × 10−4 𝑀
𝐶
[𝐻3 𝑂+ ]𝐻𝐶𝑙,𝑚 10−2
= = 19 ⇒ [𝐻3 𝑂 + ]𝐴𝑐𝑂𝐻,𝑚 𝑖𝑠 𝑛𝑒𝑔𝑙𝑒𝑐𝑡𝑒𝑑 in front of [𝐻3 𝑂+ ]𝐻𝐶𝑙,𝑚 .
[𝐻3 𝑂+] 𝐴𝑐𝑂𝐻,𝑚 5.26×10−4

The calculation of 𝑝𝐻 is carried out as for a strong acid: [𝐻3 𝑂+ ]𝐻𝐶𝑙,𝑚 > 3 × 10−7 𝑀 ⇒ 𝐴𝑃𝑁

𝑝𝐻 = −𝑙𝑜𝑔(10−2 ) = 𝟐 < 6.5 (𝐴𝑃𝑁 verified)

Method 2.
𝐶𝐻3 𝐶𝑂𝑂𝐻(𝑎𝑞 ) + 𝐻2 𝑂(𝑙 ) ⇌ 𝐶𝐻3 𝐶𝑂𝑂− (𝑎𝑞 ) + 𝐻3 𝑂+ (𝑎𝑞 ) 𝐾𝑎 = 10−4.8 < 1 ⇒ 𝐶𝑅𝑃
I 1.75 × 10−2 excess 0 0.01
F 1.75 × 10−2 − 𝑥 excess 𝑥 𝑥 + 0.01
Supposing APN;
[𝐻3 𝑂+ ][𝐶𝐻3 𝐶𝑂𝑂 − ] 𝑥(𝑥 + 0.01)
𝐾𝑎 = = = 10−𝟒.𝟖 ⇒ 𝑥 = 2.76 × 10−5 𝑀 ≪ 0.01𝑀
[𝐶𝐻3 𝐶𝑂𝑂𝐻] 1.75 × 10−2 − 𝑥

[𝐻3 𝑂+ ] ≈ 0.01𝑀 ⇒ 𝒑𝑯 = 𝟐

𝑴 − 𝟐: 𝑴 − 𝟏 + 𝑁𝑎𝑂𝐻( 13.8 𝑚𝐿, 10−1 𝑀).

𝐻2 𝑂
𝑁𝑎𝑂𝐻(𝑎𝑞) → 𝑁𝑎+ (𝑎𝑞) + 𝐻𝑂 − (𝑎𝑞)
Let’s calculate the concentration of these species in the mixture:
𝐶𝐻 𝑂+,𝑖 × 𝑉𝐻3 𝑂+,𝑖 0.04 × 12.5
𝐶𝐻3 𝑂+,𝑚 = 3 = = 7.83 × 10−3 𝑀
𝑉𝑡𝑜𝑡 63.8
𝐶𝐴𝑐𝑂𝐻,𝑖 × 𝑉𝐴𝑐𝑂𝐻,𝑖 0.07 × 12.5
𝐶𝐴𝑐𝑂𝐻,𝑚 = = = 1.37 × 10−2 𝑀
𝑉𝑡𝑜𝑡 63.8
𝐶𝐻𝑂− ,𝑖 × 𝑉𝐻𝑂− ,𝑖 0.1 × 13.8
𝐶𝐻𝑂−,𝑚 = = = 2.16 × 10−2 𝑀
𝑉𝑡𝑜𝑡 63.8

𝐻3 𝑂 + , 𝐻𝑂− , 𝐶𝐻3 𝐶𝑂𝑂𝐻, 𝑁𝑎+ , 𝐶𝑙 − (𝑠𝑝𝑒𝑐𝑡𝑎𝑡𝑜𝑟 𝑖𝑜𝑛𝑠) and 𝐻2 𝑂.

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The gamma rule (I) is used to find the preponderant reaction;

𝐻𝑂 − (𝑎𝑞 ) + 𝐻3 𝑂+ (𝑎𝑞 ) ⇌ 2𝐻2 𝑂(𝑙) 𝐾 = 1014 > 103 ⇒ 𝑄𝑃𝑅
I 2.16 × 10 −2
7.83 × 10 −3
excess
Eq 1.37 × 10−3
→0 excess

We need to find the new equivalent solution;

The gamma rule (II) is used again to find the new preponderant reaction.
𝐻𝑂 − (𝑎𝑞) + 𝐶𝐻3 𝐶𝑂𝑂𝐻(𝑎𝑞) ⇌ 𝐶𝐻3 𝐶𝑂𝑂− (𝑎𝑞) + 𝐻2 𝑂(𝑙) 𝐾 = 1014 > 103 ⇒ 𝑄𝑃𝑅
(I)
I 1.37 × 10 −2
1.37 × 10 −2
0 excess
Eq →0 →0 1.37 × 10−2 excess

The 𝐶𝐻3 𝐶𝑂𝑂−is the only species that has remained in solution, it reacts according to the
reaction:
𝐶𝐻3 𝐶𝑂𝑂− (𝑎𝑞 ) + 𝐻2 𝑂(𝑙 ) ⇌ 𝐻𝑂− (𝑎𝑞 ) + 𝐶𝐻3 𝐶𝑂𝑂𝐻(𝑎𝑞 ) 𝐾 = 10−9.2 < 1 ⇒ 𝐶𝑃𝑅
Let’s locate the dissociation equilibrium applying (𝑝𝐾b − 𝑝𝐶𝑏 );
(𝑝𝐾𝑏,2 − 𝑝𝐶𝑏 ) = (14 − 4.8) + log(1.37 × 10−2 ) = 7.33 > 2
⇒ 𝑠𝑙𝑖𝑔ℎ𝑡𝑙𝑦 𝑝𝑟𝑜𝑡𝑜𝑛𝑎𝑡𝑒𝑑 𝑏𝑎𝑠𝑒
1 1
Supposing APN : 𝑝𝐻 = 7 + 2 (𝑝𝐾𝑎 + 𝑙𝑜𝑔𝐶𝑏 ) = 7 + 2 (4,8 + log(1.37 × 10−2 )) = 𝟖, 𝟒𝟔 > 7.5 (II)
(𝐴𝑃𝑁 verified)

𝑴 − 𝟑: 𝐶𝐻3 𝐶𝑂𝑂𝐻 (10 𝑚𝐿, 0.1 𝑀) + 𝑁𝑎𝑁𝑂2 (6 𝑚𝐿, 0.1 𝑀).

𝐶𝐻3 𝐶𝑂𝑂𝐻(𝑎𝑞) + 𝐻2 𝑂(𝑙) ⇌ 𝐶𝐻3 𝐶𝑂𝑂− (𝑎𝑞) + 𝐻3 𝑂 + (𝑎𝑞) … … … 𝐾𝑎 = 10−4.8

𝐻2 𝑂
𝑁𝑎𝑁𝑂2 (𝑠) → 𝑁𝑎+ (𝑎𝑞) + 𝑁𝑂2− (𝑎𝑞)
2𝐻2 𝑂 (𝑙) ⇌ 𝐻3 𝑂 + (𝑎𝑞) + 𝐻𝑂− (𝑎𝑞)…….…….𝐾𝑤 = 10−14
The species present initially in solution are:
𝐶𝐻3 𝐶𝑂𝑂𝐻, 𝑁𝑎 + (𝑠𝑝𝑒𝑐𝑡𝑎𝑡𝑜𝑟 𝑖𝑜𝑛), 𝑁𝑂2− , and 𝐻2 𝑂.
Let’s calculate the concentration of species in the mixture:
𝐶𝑁𝑂2−,𝑖 × 𝑉𝑁𝑂2− ,𝑖 0.1 × 6
𝐶𝑁𝑂2− ,𝑚 = = = 3.75 × 10−2 𝑀
𝑉𝑡𝑜𝑡 16
𝐶𝐴𝑐𝑂𝐻,𝑖 × 𝑉𝐴𝑐𝑂𝐻,𝑖 0.1 × 10
𝐶𝐴𝑐𝑂𝐻,𝑚 = = = 6.25 × 10−2 𝑀
𝑉𝑡𝑜𝑡 16
The gamma rule is used to find the preponderant reaction;
𝑁𝑂2− (𝑎𝑞) + 𝐶𝐻3 𝐶𝑂𝑂𝐻(𝑎𝑞) ⇌ 𝐶𝐻3 𝐶𝑂𝑂 − (𝑎𝑞) + 𝐻𝑁𝑂2 (𝑎𝑞) 𝐾 = 10−1.6 < 1 ⇒ 𝐶𝑃𝑅
I 3.75 × 10 −2
6.25 × 10 0−2
0
Eq (3.75 × 10 − 𝑥) (6.25 × 10 − 𝑥)
−2 −2
𝑥 𝑥
Let’s locate the equilibrium of 𝑁𝑂2− and 𝐶𝐻3 𝐶𝑂𝑂𝐻 by applying 𝑝𝐾 − 𝑝𝐶:
𝑁𝑂2− : 𝑝𝐾𝑏 − 𝑝𝐶𝑏 = (14 − 3.2) + log(3.75 × 10−2 ) = 9.32 > 2 ⇒ 𝑆𝑃𝐵 ⇒ 𝑥 𝑖𝑠 𝑛𝑒𝑔𝑙𝑒𝑐𝑡𝑒𝑑 𝑖𝑛 𝑓𝑟𝑜𝑛𝑡 𝑜𝑓 3.75 × 10−2 𝑀.
𝐶𝐻3 𝐶𝑂𝑂𝐻: 𝑝𝐾𝑎 − 𝑝𝐶𝑎 = (4.8) + log(6.25 × 10−2 ) = 3.59 > 2 ⇒ 𝑆𝑃𝐴 ⇒ 𝑥 𝑖𝑠 𝑛𝑒𝑔𝑙𝑒𝑐𝑡𝑒𝑑 𝑖𝑛 𝑓𝑟𝑜𝑛𝑡 𝑜𝑓 6.25 × 10−2 𝑀.

[𝐻𝑁𝑂2 ][𝐶𝐻3 𝐶𝑂𝑂−] 𝑥2

𝐾= = ⇒ 𝑥 = 7.67 × 10−3
[ 𝐶𝐻3 𝐶𝑂𝑂𝐻][𝑁𝑂2− ] (3.75 × 10−2 )(6.25 × 10−2 )

Therefore, we can write the concentrations of different species as follow:

[ 𝐶𝐻3 𝐶𝑂𝑂𝐻] = 6.25 × 10−2 𝑀, [𝑁𝑂2− ] = 3.1 × 10−2 𝑀, [𝐶𝐻3 𝐶𝑂𝑂− ] = [𝐻𝑁𝑂2 ] = 7.67 × 10−3 M
The Henderson-Hasselbalch equation is used for calculating the 𝑝𝐻.
[𝐶𝐻3 𝐶𝑂𝑂− ] 7.67 × 10−3
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 = 4.8 + 𝑙𝑜𝑔 = 𝟑. 𝟖𝟖
[ 𝐶𝐻3 𝐶𝑂𝑂𝐻] 6.25 × 10−2
Or
[𝑁𝑂2−] 3.75 × 10−2
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 = 3.2 + 𝑙𝑜𝑔 = 𝟑. 𝟖𝟖
[𝐻𝑁𝑂2 ] 7.67 × 10−3

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𝑴 − 𝟒: 𝐶₆𝐻₅𝑁𝐻₂ (25𝑚𝐿, 0.01 𝑚𝑜𝑙 ) + 𝐶₅𝐻₅𝑁(25𝑚𝐿, 0.01 𝑚𝑜𝑙).

−9.4
𝐶₆𝐻₅𝑁𝐻₂ (𝑙) + 𝐻2 𝑂 (𝑙) ⇌ 𝐻𝑂− (𝑎𝑞) + 𝐶₆𝐻₅𝑁𝐻₂ + (𝑎𝑞) … … … … … … … . . 𝐾𝑏,1 = 10
−8.8
𝐶₅𝐻₅𝑁 (𝑙) + 𝐻2 𝑂 (𝑙) ⇌ 𝐻𝑂− (𝑎𝑞) + 𝐶₅𝐻₅𝑁 + (𝑎𝑞) … … … … … … … . . 𝐾𝑏,2 = 10
2𝐻2 𝑂 (𝑙) ⇌ 𝐻3 𝑂 + (𝑎𝑞) + 𝐻𝑂− (𝑎𝑞) … … … … … … … . . 𝐾𝑤
Let’s calculate the concentration of the bases in the mixture:
𝑛𝑏1,𝑖 0.01
𝐶𝑏1,𝑚 = = = 0.2𝑀
𝑉𝑡𝑜𝑡 50 × 10−3
𝑛𝑏2,𝑖 0.01
𝐶𝑏2,𝑚 = = = 0.2𝑀
𝑉𝑡𝑜𝑡 50 × 10−3
−9.4
𝐾𝑏,1 𝐶𝑏1,𝑚 10 × 0.2
= −8.8 = 0.1 < 0.25 < 10 ⇒ b𝑜𝑡ℎ 𝑏𝑎𝑠𝑒𝑠 𝑎𝑟𝑒 considered
𝐾𝑏,2 𝐶𝑏2,𝑚 10 × 0.2
Let’s locate the dissociation equilibrium applying (𝑝𝐾𝑏 − 𝑝𝐶𝑏 ) for both bases
𝑝𝐾𝑏,1 − 𝑝𝐶𝑏1,𝑚 = 9.4 + log(0.2) = 8.7 > 2 ⇒ 𝑠𝑙𝑖𝑔ℎ𝑡𝑙𝑦 𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑒 𝑏𝑎𝑠𝑒
𝑝𝐾𝑏,2 − 𝑝𝐶𝑏2,𝑚 = 8.8 + log(0.2) = 8.1 > 2 ⇒ 𝑠𝑙𝑖𝑔ℎ𝑡𝑙𝑦 𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑒 𝑏𝑎𝑠𝑒
1 1
Supposing APN ⇒ 𝑝𝑂𝐻 = − 𝑙𝑜𝑔 (𝐾𝑏,1 𝐶𝑏,1 + 𝐾𝑏,2 𝐶𝑏,2 ) = − 𝑙𝑜𝑔(10−9.4 × 0.2 + 10−8.8 × 0.2) = 4.7
2 2
𝑝𝐻 = 14 − 4.7 = 𝟗. 𝟑 > 7.5(𝐴𝑃𝑁 𝑣𝑒𝑟𝑖𝑓𝑖𝑒𝑑)
and 𝑝𝐻 > 𝑝𝐾𝑎,1 + 1, 𝑝𝐻 > 𝑝𝐾𝑎,2 + 1

𝑴 − 𝟓: 𝐻𝐶𝑁 (10−5.5 𝑀) + 𝐻𝐶𝑁𝑂 (10−5.5 𝑀).

− −9.2
𝐻𝐶𝑁 (𝑎𝑞) + 𝐻2 𝑂 (𝑙) ⇌ 𝐻3𝑂+ (𝑎𝑞) + 𝐶𝑁 (𝑎𝑞) … … … … … … … . . 𝐾𝑎,1 = 10
− −3.6
𝐻𝐶𝑁𝑂 (𝑎𝑞) + 𝐻2 𝑂 (𝑙) ⇌ 𝐻3 𝑂+ (𝑎𝑞) + 𝐶𝑁𝑂 (𝑎𝑞) … … … … … … … . . 𝐾𝑎,2 = 10
2𝐻2 𝑂 (𝑙) ⇌ 𝐻3 𝑂 + (𝑎𝑞) + 𝐻𝑂− (𝑎𝑞) … … … … … … … . . 𝐾𝑤
𝐾𝑎,2 𝐶𝑎2,𝑚 10−3.6 × 10−5.5
= = 105.6 ⇒ Only the second acid is considered
𝐾𝑎,1 𝐶𝑎1,𝑚 10−9.2 × 10−5.5
Let’s locate the dissociation equilibrium of the acid applying (𝑝𝐾𝑎,2 − 𝑝𝐶𝑎,2 );
(𝑝𝐾𝑎,2 − 𝑝𝐶𝑎,2 ) = 3.6 + log(10−5.5 ) = −1.9 < −1 ⇒ 𝑡𝑜𝑡𝑎𝑙𝑙𝑦 𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑒𝑑 𝑎𝑐𝑖𝑑
𝑆𝑢𝑝𝑝𝑜𝑠𝑖𝑛𝑔 𝐴𝑃𝑁: 𝑝𝐻 = −𝑙𝑜𝑔(10−5.5 ) = 𝟓. 𝟓 < 6.5 (𝐴𝑃𝑁 𝑣𝑒𝑟𝑖𝑓𝑖𝑒𝑑)
and 𝑝𝐻 > 𝑝𝐾𝑎,2 + 1

Exercise 8. (Buffer solutions)

I. Consider a buffer solution with a 𝑝𝐻 of 9.07 prepared from 0.4 𝑀 𝑁𝐻3 solution (500 𝑚𝐿) and
𝑁𝐻4 𝐶𝑙 solution (500 𝑚𝐿).
1. Determine the mass of 𝑁𝐻4 𝐶𝑙 dissolved in the solution used for this preparation.
𝐻2 𝑂
𝑁𝐻4 𝐶𝑙(𝑠) → 𝑁𝐻4 + (𝑎𝑞) + 𝐶𝑙− (𝑎𝑞)
2𝐻2 𝑂(𝑙) ⇌ 𝐻3 𝑂 (𝑎𝑞) + 𝐻𝑂 − (𝑎𝑞)
+

The preponderant reaction in the medium is:

𝑁𝐻3 (𝑎𝑞) + 𝑁𝐻4 + (𝑎𝑞) ⇌ 𝑁𝐻3 (𝑎𝑞) + 𝑁𝐻4 + (𝑎𝑞) … … … … . 𝐾 = 1
The concentrations of 𝑁𝐻3 and 𝑁𝐻4 + are constants.
Using the Henderson-Hasselbalch Equation, we can deduce the concentration of [𝑁𝐻4 + ] in the buffer
mixture or directly in the initial solution:
[𝑁𝐻3 ]𝑖 × 𝑉𝑖
[𝑁𝐻3 ]𝑚 𝑉𝑚 [𝑁𝐻3 ]𝑖
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 + = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 + = 𝑝𝐾𝑎 + 𝑙𝑜𝑔
[𝑁𝐻4 ]𝑚 [𝑁𝐻4 ]𝑖 × 𝑉𝑖 [𝑁𝐻4 + ]𝑖
𝑉𝑚
[𝑁𝐻3 ]𝑖 [𝑁𝐻3 ]𝑖 [𝑁𝐻3 ]𝑖 0.4
𝑝𝐻 − 𝑝𝐾𝑎 = 𝑙𝑜𝑔 + ⇒ + = 10
(𝑝𝐻−𝑝𝐾𝑎 )
⇒ [𝑁𝐻4 + ]𝑖 = (𝑝𝐻−𝑝𝐾 ) = (9.07−9.25) = 0.6 𝑀
[𝑁𝐻4 ]𝑖 [𝑁𝐻4 ]𝑖 10 𝑎 10
+
𝑛𝑁𝐻4 𝐶𝑙 𝑚𝑁𝐻4 𝐶𝑙
[𝑁𝐻4 ]𝑖 = 𝐶𝑁𝐻4𝐶𝑙 = = ⇒ 𝑚𝑁𝐻4𝐶𝑙 = 𝐶𝑁𝐻4 𝐶𝑙 × 𝑉𝑖 × 𝑀𝑁𝐻4 𝐶𝑙
𝑉𝑖 𝑉𝑖 × 𝑀𝑁𝐻4𝐶𝑙
𝑚𝑁𝐻4 𝐶𝑙 = 0.6 × 0.5 × 53.491 = 𝟏𝟔. 𝟎𝟒𝟕 𝒈

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The concentrations of 𝑁𝐻3 and 𝑁𝐻4 + in the mixture are:

[𝑁𝐻3 ]𝑖 × 𝑉𝑖 0.4 × 500 [𝑁𝐻4 +]𝑖 × 𝑉𝑖 0.6 × 500
[𝑁𝐻3 ]𝑚 = = = 0.2 𝑀, [𝑁𝐻4 + ]𝑚 = = = 0.3 𝑀
𝑉𝑚 1000 𝑉𝑚 1000
2. Calculate the 𝑝𝐻 change when:
a) 100 𝑚𝐿 of 0.05 𝑀 𝑁𝑎𝑂𝐻 is added to 400 𝑚𝐿 of the buffer solution.
𝐻2𝑂
𝑁𝑎𝑂𝐻(𝑠) → 𝑁𝑎+ (𝑎𝑞) + 𝐻𝑂 − (𝑎𝑞)
Let’s calculate the concentration of different species in the new mixture (m-1);
0.05 ×100 −2 0.2 ×400 0.3 ×400
𝐶𝑁𝑎𝑂𝐻 = = 10 𝑀, [𝑁𝐻3 ]𝑚,1 = = 0.16 𝑀, [𝑁𝐻4 + ]𝑚,1 = = 0.24 𝑀
500 500 500
The preponderant reaction that takes place in the medium is:
14−9.25 4.75 3
𝑁𝐻4 + (𝑎𝑞 ) + 𝐻𝑂 − (𝑎𝑞 ) ⇌ 𝑁𝐻3 (𝑎𝑞 ) + 𝐻2 O (𝑙 ) 𝐾 = 10 = 10 > 10 ⇒ 𝑄𝑃𝑅

I 0.24 0.01 0.16 excess

Eq 0.23 ⟶0 0.17 excess

[𝑁𝐻3 ]𝑚1,𝑒𝑞 0.17
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 + = 9.25 + 𝑙𝑜𝑔 = 9.11
[𝑁𝐻4 ]𝑚1,𝑒𝑞 0.23
𝜟𝒑𝑯 = 9.11 − 9.07 = 𝟎. 𝟎𝟒 > 𝟎

b) 10 𝑚𝑚𝑜𝑙 𝐻𝐶𝑙 is added to 400 𝑚𝐿 of the buffer solution.

𝐻𝐶𝑙(𝑎𝑞) + 𝐻2 𝑂 (𝑙) ⟶ 𝐻3 𝑂+ (𝑎𝑞) + 𝐶𝑙− (𝑎𝑞)
Let’s calculate the number of moles of different species in the new mixture (m-2);
𝑛𝑁𝐻3 = 0.2 × 0.4 = 0.08 𝑚𝑜𝑙, 𝑛𝑁𝐻4 + = 0.3 × 0.4 = 0.12 𝑚𝑜𝑙.
The preponderant reaction that takes place in the medium is:
9.25−0 9.25 3
𝑁𝐻3 (𝑎𝑞 ) + 𝐻3 𝑂+ (𝑎𝑞 ) ⇌ 𝑁𝐻4 + (𝑎𝑞 ) + 𝐻2 O (𝑙 ) 𝐾 = 10 = 10 > 10 ⇒ 𝑄𝑃𝑅
I 0.08 𝑚𝑜𝑙 0.01 𝑚𝑜𝑙 0.12 𝑚𝑜𝑙 excess

Eq 0.07 ⟶0 0.13 excess

𝑛𝑁𝐻3 0.07
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 = 9.25 + 𝑙𝑜𝑔 = 8.98
𝑛𝑁𝐻 + 0.13
4
𝜟𝒑𝑯 = 8.98 − 9.07 = −𝟎. 𝟎𝟗 < 𝟎

c) Is the buffer capacity of the solution destroyed by the additional species? Justify your
response.
The buffer capacity is not destroyed by adding 𝑁𝑎𝑂𝐻 or 𝐻𝐶𝑙. While the 𝑝𝐻 does change slightly in both
cases, the changes in 𝑝𝐻 is still between 𝑝𝐾𝑎 − 1 and 𝑝𝐾𝑎 + 1.
[𝑁𝐻3 ]
Therefore, the ratio of concentration is : 0.1 < < 10.
[𝑁𝐻4+ ]
Supplementary question: Calculate the buffer capacity of the solution before and after addition of
strong species.
 Buffer capacity of the initial buffer solution:
2.3 𝐶0 𝐾𝑎 [𝐻3 𝑂+ ]
Method 1: 𝛽 =
(𝐾𝑎 +[𝐻3 𝑂+ ])2

𝐶0 = [𝑁𝐻3 ]𝑚 + [𝑁𝐻4 + ]𝑚 = 0.2 + 0.3 = 0.5 𝑀

2.3 × 0.5 × 10−9.25 × 10−9.07
𝛽= = 0.276 𝑀
(10−9.25 + 10−9.07 )2
Method 2: 𝛽 = 2.3 𝐶0 𝑥(1 − 𝑥)
[𝑁𝐻3 ]𝑚 0.2 [𝑁𝐻4 +]𝑚 0.3
𝑥= = = 0.4 𝑥′ = = = 0.6
𝐶0 0.5 𝐶0 0.5
𝑥 + 𝑥′ = 1
𝛽 = 2.3 𝐶0 𝑥(1 − 𝑥) = 2.3 × 0.5 × 0.4 × (1 − 0.4) 𝛽 = 2.3 𝐶0 𝑥 ′ (1 − 𝑥 ′ ) = 2.3 × 0.5 × 0.6 × (1 − 0.6)
𝛽 = 0.276 𝑀 𝛽 = 0.276 𝑀
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ENSTI-Annaba-CPST-2nd year Solutions chemistry (2024/2025)

 Case 1. Calculation of 𝛽 when 𝑁𝑎𝑂𝐻 is added.

2.3 𝐶0 𝐾𝑎 [𝐻3 𝑂+ ]
Method 1: 𝛽 =
(𝐾𝑎 +[𝐻3 𝑂+ ])2

𝐶0 = [𝑁𝐻3 ]𝑚1,𝑒𝑞 + [𝑁𝐻4+ ]𝑚1,𝑒𝑞 = 0.17 + 0.23 = 0.4 𝑀

2.3 × 0.4 × 10−9.25 × 10−9.11
𝛽= = 0.22 𝑀
(10−9.25 + 10−9.11 )2
Method 2: 𝛽 = 2.3 𝐶0 𝑥(1 − 𝑥)
[𝑁𝐻3 ]𝑚1,𝑒𝑞 0.17 [𝑁𝐻4 +]𝑚1,𝑒𝑞 0.23
𝑥= = = 0.425 𝑥′ = = = 0.575
𝐶0 0.4 𝐶0 0.4
𝑥 + 𝑥′ = 1
𝛽 = 2.3 𝐶0 𝑥(1 − 𝑥) = 2.3 × 0.4 × 0.425(1 − 0.425) 𝛽 = 2.3 𝐶0 𝑥 ′ (1 − 𝑥 ′ ) = 2.3 × 0.4 × 0.575(1 − 0.575)
𝛽 = 0.22 𝑀 𝛽 = 0.22 𝑀

 Case 2. Calculation of 𝛽 when 𝐻𝐶𝑙 is added, considering that there is no change in volume.
2.3 𝐶0 𝐾𝑎 [𝐻3 𝑂+ ]
Method 1: 𝛽 =
(𝐾𝑎 +[𝐻3 𝑂+ ])2
𝑛0 0.2
𝑛0 = 𝑛𝑁𝐻3 + 𝑛𝑁𝐻+4 = 0.07 + 0.13 = 0.2 𝑚𝑜𝑙 ⟹ 𝐶0 = = = 0.5𝑀
𝑉𝑡𝑜𝑡 0.4
2.3 × 0.5 × 10−9.25 × 10−8.98
𝛽= = 0.26 𝑀
(10−9.25 + 10−8.98 )2
Method 2: 𝛽 = 2.3 𝐶0 𝑥(1 − 𝑥)
𝑛𝑁𝐻3 0.07 𝑛𝑁𝐻4+ 0.13
𝑥= = = 0.35 𝑥′ = = = 0.65
𝑛0 0.2 𝑛0 0.2
𝑥+ 𝑥′ =1
𝛽 = 2.3 𝐶0 𝑥(1 − 𝑥) = 2.3 × 0.4 × 0.35(1 − 0.35) 𝛽 = 2.3 𝐶0 𝑥 ′ (1 − 𝑥 ′ ) = 2.3 × 0.4 × 0.65(1 − 0.65)
𝛽 = 0.26 𝑀 𝛽 = 0.26 𝑀

After addition of strong species, the buffer capacity values remain close to the initial buffer capacity,
proving that the buffer capacity of the solution has not been destroyed.

II. Consider two solutions: S1(𝐶𝐻3 𝐶𝑂𝑂𝐻) and S2(𝐶𝐻3 𝐶𝑂𝑂𝑁𝑎), both with the same
concentration of 0.2𝑀.
1. How to prepare a 100 𝑚𝐿 of buffer solution at 𝑝𝐻 = 4.4 using 50 𝑚𝐿 of solution S1.
𝐻2 𝑂
𝐶𝐻3 𝐶𝑂𝑂𝑁𝑎(𝑠) → 𝐶𝐻3 𝐶𝑂𝑂 − (𝑎𝑞) +𝑁𝑎+ (𝑎𝑞)
2𝐻2 𝑂(𝑙) ⇌ 𝐻3 𝑂 + (𝑎𝑞) + 𝐻𝑂 − (𝑎𝑞)
The preponderant reaction that takes place in the medium is:
𝐶𝐻3 𝐶𝑂𝑂𝐻(𝑎𝑞) + 𝐶𝐻3 𝐶𝑂𝑂 − (𝑎𝑞) ⇌ 𝐶𝐻3 𝐶𝑂𝑂𝐻(𝑎𝑞) + 𝐶𝐻3 𝐶𝑂𝑂− (𝑎𝑞) … … … … . 𝐾 = 1
The concentrations of 𝐶𝐻3 𝐶𝑂𝑂𝐻 𝑎𝑛𝑑 𝐶𝐻3 𝐶𝑂𝑂− are constants.
Let us calculate the concentration of 𝐶𝐻3 𝐶𝑂𝑂𝐻 in the mixture;
0.2 × 50
[𝐶𝐻3 𝐶𝑂𝑂𝐻 ]𝑚 = = 𝟎. 𝟏 𝑴
100
Determining the concentration of acetate in the mixture using the Henderson-Hasselbalch equation:
[𝐶𝐻3 𝐶𝑂𝑂 − ]𝑚
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 ⇒ [𝐶𝐻3 𝐶𝑂𝑂− ]𝑚 = 10(𝑝𝐻−𝑝𝐾𝑎 ) × [𝐶𝐻3 𝐶𝑂𝑂𝐻]𝑚
[𝐶𝐻3 𝐶𝑂𝑂𝐻]𝑚
[𝐶𝐻3 𝐶𝑂𝑂 − ]𝑚 = 10(4.4−4.8) × 0.1 ≈ 𝟎. 𝟎𝟒 𝑴
Let us calculate the volume needed to achieve this concentration in the final volume of 100 𝑚𝐿.
Knowing that: [𝐶𝐻3 𝐶𝑂𝑂− ]𝑖 × 𝑉𝑖 = [𝐶𝐻3 𝐶𝑂𝑂− ]𝑚 × 𝑉𝑚
[𝐶𝐻3 𝐶𝑂𝑂 − ]𝑚 × 𝑉𝑚 0.04 × 100
𝑉𝑖 = = = 𝟐𝟎 𝒎𝑳
[𝐶𝐻3 𝐶𝑂𝑂 − ]𝑖 0.2

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To prepare 100 𝑚𝐿 of buffer solution with 𝑝𝐻 = 4.4, using 50 𝑚𝐿 of acetic acid (S1), we add 20 𝑚𝐿 of
sodium acetate (S2) and 30 𝑚𝐿 of distilled water to bring the total volume to 100 𝑚𝐿.

2. Calculate the concentration of the buffer solution.

−
𝐶0 = [𝐶𝐻3 𝐶𝑂𝑂𝐻 ]𝑚 + [𝐶𝐻3 𝐶𝑂𝑂 ]𝑚 = 𝟎. 𝟏𝟒 𝑴
3. Calculate the acidic and basic buffer capacities of this solution at the limits of the buffer zone.
 The acid buffer capacity at the limit of buffer zone corresponds to 𝑝𝐻 = 𝑝𝐾𝑎 − 1 = 3.8
4.8−0 4.8 3
𝐶𝐻3 𝐶𝑂𝑂− (𝑎𝑞) + 𝐻3 𝑂+ (𝑎𝑞) ⇌ 𝐶𝐻3 𝐶𝑂𝑂𝐻(𝑎𝑞) + 𝐻2O (𝑙) 𝐾 = 10 = 10 > 10 ⇒ 𝑄𝑃𝑅
I 0.04 𝐶𝑎 0.1 excess

Eq 0.04 − 𝐶𝑎 ⟶0 0.1 + 𝐶𝑎 excess

Using the Henderson-Hasselbalch Equation, we can deduce the concentration of 𝐻3 𝑂+ .

[𝐶𝐻3 𝐶𝑂𝑂− ]𝑚 0.04 − 𝐶𝑎
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 = 4.8 + 𝑙𝑜𝑔 = 3.8 ⇒ 𝐶𝑎 = 𝟎. 𝟎𝟐𝟕𝑴
[𝐶𝐻3 𝐶𝑂𝑂𝐻]𝑚 0.1 + 𝐶𝑎

 The basic buffer capacity at the limit of buffer zone corresponds to 𝑝𝐻 = 𝑝𝐾𝑎 + 1 = 5.8
14−4.8 9.2 3
𝐶𝐻3 𝐶𝑂𝑂𝐻 + 𝐻𝑂− (𝑎𝑞) ⇌ 𝐶𝐻3 𝐶𝑂𝑂 − (𝑎𝑞)(𝑎𝑞) + 𝐻2O (𝑙) 𝐾 = 10 = 10 > 10 ⇒ 𝑄𝑃𝑅
I 0.1 𝐶𝑏 0.04 excess

Eq 0.1 − 𝐶𝑏 ⟶0 0.04 + 𝐶𝑎 excess

Using the Henderson-Hasselbalch Equation, we can deduce the concentration of 𝐻𝑂− .

[𝐶𝐻3 𝐶𝑂𝑂− ]𝑚 0.04 + 𝐶𝑏
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 = 4.8 + 𝑙𝑜𝑔 = 5.8 ⇒ 𝐶𝑏 = 𝟎. 𝟎𝟖𝟕𝑴
[𝐶𝐻3 𝐶𝑂𝑂𝐻]𝑚 0.1 − 𝐶𝑏

𝑝𝐻 = 4.4

𝑝𝐾𝑎 − 1 = 3.8 𝑝𝐾𝑎 = 4.8 𝑝𝐾𝑎 − 1 = 5.8

𝑎𝑐𝑖𝑑 𝑏𝑢𝑓𝑓𝑒𝑟 𝑐𝑎𝑝𝑎𝑐𝑖𝑡𝑦 < 𝑏𝑎𝑠𝑖𝑐 𝑏𝑢𝑓𝑓𝑒𝑟 𝑐𝑎𝑝𝑎𝑐𝑖𝑡𝑦

Supplementary question: To achieve the maximum buffer capacity, which strong species should be
added to the solution? Calculate the required amount of the strong species and determine the maximum
buffer capacity value.
At maximum buffer capacity, the concentrations of the weak acid and its conjugate base are equal.
Therefore, the 𝑝𝐻 of the solution is equal to the 𝑝𝐾𝑎 of the acid-base pair.
𝑝𝐻 = 4.4 < 𝑝𝐾𝑎 = 4.8 ⇒ an amount of strong base must be added to increase the 𝑝𝐻 until 4.8.

 Let’s calculate the amount of the strong base must be added.

14−4.8 9.2 3
𝐶𝐻3 𝐶𝑂𝑂𝐻 + 𝐻𝑂− (𝑎𝑞) ⇌ 𝐶𝐻3 𝐶𝑂𝑂 − (𝑎𝑞)(𝑎𝑞) + 𝐻2O (𝑙) 𝐾 = 10 = 10 > 10 ⇒ 𝑄𝑃𝑅
I 0.1 𝐶𝑏 0.04 excess

Eq 0.1 − 𝐶𝑏 ⟶0 0.04 + 𝐶𝑎 excess

Using the Henderson-Hasselbalch Equation, we can deduce the concentration of 𝐻𝑂− .

[𝐶𝐻3 𝐶𝑂𝑂− ] 0.04 + 𝐶𝑏
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 = 4.8 + 𝑙𝑜𝑔 = 4.8 ⇒ 𝐶𝑏 = 𝟎. 𝟎𝟑 𝑴
[𝐶𝐻3 𝐶𝑂𝑂𝐻] 0.1 − 𝐶𝑏
[𝐶𝐻3 𝐶𝑂𝑂𝐻] = [𝐶𝐻3 𝐶𝑂𝑂− ] = 0.07 𝑀
The total concentration is always constant :
[𝐶𝐻3 𝐶𝑂𝑂𝐻] + [𝐶𝐻3 𝐶𝑂𝑂− ] = 0.14 𝑀
The maximum buffer capacity is calculated as ;
2.3 𝐶0 2.3 × 0.14
𝛽𝑚𝑎𝑥 = = = 𝟎. 𝟎𝟖 𝑴
4 4
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