Tutorial (2SC-Part2) Solution
Tutorial (2SC-Part2) Solution
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 + ]
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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− ]
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I C 0 0
F 0 3C C
2𝐻2 𝑂 (𝑙) ⇌ 𝐻3 𝑂 + (𝑎𝑞) + 𝐻𝑂− (𝑎𝑞)…….…….𝐾𝑤 = 10−14
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 − ]
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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
[𝐻3 𝑂+ ] ≈ 0.01𝑀 ⇒ 𝒑𝑯 = 𝟐
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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)
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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
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.
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
𝑝𝐻 = 4.4
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.