National Higher School of Technology and Engineering- Annaba
Preparatory classes of sciences and technology
Second year
University year: 2024/2025
Solutions Chemistry Course
Chapter 1 : Acid-base equilibria
-Part 5-
Dr. A. AMIRA
Email : [Link]@[Link]
Buffer solutions
Buffer is defined as a solution that resists changes in 𝒑𝑯 when it is moderately diluted or when a small
amount of a strong acid or a strong base are added to it.
Buffers are used in all types of chemical applications whenever it is important to maintain the 𝑝𝐻 of a solution
at a constant and predetermined level.
A buffer solution consists of a mixture of :
Weak acid + its conjugate base: 𝐶𝐻3 𝐶𝑂𝑂𝐻 𝑎𝑛𝑑 𝐶𝐻3 𝐶𝑂𝑂− .
Weak base + its conjugate acid: 𝑁𝐻3 𝑎𝑛𝑑 𝑁𝐻4+ .
The preparation of buffer solution depends on several parameters:
The desired 𝒑𝑯 determines the choice of acid/base pair to be used , possessing a close 𝑝𝐾𝑎 value to the 𝑝𝐻,
and the ratio to be obtained in the buffer solution.
The nature of solution to use; a buffer solution can be prepared in three different ways:
1) The two weak species are present initially in solution such as:
a) Weak acid + its conjugate base (salt) b) Weak base + its conjugate acid (salt) c) (two salts)
(𝐶𝐻3 𝐶𝑂𝑂𝐻 𝑎𝑛𝑑 𝐶𝐻3 𝐶𝑂𝑂Na) (𝑁𝐻3 𝑎𝑛𝑑 𝑁𝐻4 𝐶𝑙) (𝐾𝐻2 𝑃𝑂4 𝑎𝑛𝑑 𝐾2 𝐻𝑃𝑂4 )
2) Weak acid + strong base: 𝐶𝐻3 𝐶𝑂𝑂𝐻 𝑎𝑛𝑑 NaOH.
3) Weak base+ strong acid: 𝑁𝐻3 𝑎𝑛𝑑 HCl.
2
Buffer zone and equation
Consider a buffer solution containing a weak acid 𝐻𝐴 and its conjugate base 𝐴− :
The Henderson-Hasselbalch Equation is used to calculate the 𝑝𝐻:
𝑨−
𝒑𝑯 = 𝒑𝑲𝒂 + 𝒍𝒐𝒈
𝑯𝑨
𝑯𝑨 ≥ 10 𝑨− 𝑯𝑨 ≈ 𝑨− 𝑨− ≥ 10 𝑯𝑨
0 𝒑𝑲𝒂 − 𝟏 𝑝𝐾𝑎 𝒑𝑲𝒂 + 𝟏 14 pH
𝐴− 𝑨−
𝑝𝐾𝑎 − 1 < 𝑝𝐾𝑎 + 𝑙𝑜𝑔 < 𝑝𝐾𝑎 + 1 ⟹ 𝟎. 𝟏 < < 𝟏𝟎
𝐻𝐴 𝑯𝑨
The total concentration of buffer solution is the sum of the both concentrations, 𝑪𝟎 = 𝑯𝑨 + 𝑨−
Application: Calculate the 𝑝𝐻 of solution that is (10−2 M) in acetic acid and (10−2 M) in sodium acetate.
𝑝𝐾𝑎 (𝐶𝐻3 𝐶𝑂𝑂𝐻/𝐶𝐻3 𝐶𝑂𝑂− ) = 4.8 𝐻2 𝑂
𝐶𝐻3 𝐶𝑂𝑂𝑁𝑎 𝑠 𝐶𝐻3 𝐶𝑂𝑂− 𝑎𝑞 + 𝑁𝑎+ (𝑎𝑞)
The reaction that takes place in the medium is :
𝐶𝐻3 𝐶𝑂𝑂𝐻 𝑎𝑞 + 𝐶𝐻3 𝐶𝑂𝑂− 𝑎𝑞 ⇌ 𝐶𝐻3 𝐶𝑂𝑂𝐻 𝑎𝑞 + 𝐶𝐻3 𝐶𝑂𝑂− 𝑎𝑞 … … … 𝐾 = 1 𝑇ℎ𝑒 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛𝑠 𝑎𝑟𝑒 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡𝑠
𝐴− 10−2
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 −2 = 4.8
𝐻𝐴 10 3
Preparation of buffer solution
Consider the following chemical solutions:
• 𝐶𝐻3 𝐶𝑂𝑂𝐻 1 𝑀 and 𝐶𝐻3 𝐶𝑂𝑂𝑁𝑎 0, 85 𝑀 𝑝𝐾𝑎 (𝐶𝐻3 𝐶𝑂𝑂𝐻/𝐶𝐻3 𝐶𝑂𝑂− ) = 4.8
• 𝐻𝐶𝑂𝑂𝐻 1 𝑀 and 𝐻𝐶𝑂𝑂𝑁𝑎 0, 85 𝑀 𝑝𝐾𝑎 (𝐻𝐶𝑂𝑂𝐻/𝐻𝐶𝑂𝑂− ) = 3.8
-Indicate how to prepare 500𝑚𝐿 of a buffer solution with a 𝑝𝐻 of 3.6 and a molar concentration of 0.15𝑀?
The pair (𝐻𝐶𝑂𝑂𝐻/𝐻𝐶𝑂𝑂− )allows to obtain a buffer solution with the required 𝑝𝐻, 𝒑𝑲𝒂 − 𝟏 < 𝒑𝑯 < 𝒑𝑲𝒂 + 𝟏
𝐻2 𝑂
𝐻𝐶𝑂𝑂𝑁𝑎 𝑠 𝐻𝐶𝑂𝑂− 𝑎𝑞 + 𝑁𝑎+ (𝑎𝑞)
The reaction that takes place in the medium is :
𝐻𝐶𝑂𝑂𝐻 𝑎𝑞 + 𝐻𝐶𝑂𝑂− 𝑎𝑞 ⇌ 𝐻𝐶𝑂𝑂𝐻 𝑎𝑞 + 𝐻𝐶𝑂𝑂− 𝑎𝑞 … … … 𝐾 = 1 𝑇ℎ𝑒 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛𝑠 𝑎𝑟𝑒 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡𝑠
Using the Henderson-Hasselbalch Equation, we can deduce the ratio of concentrations:
𝐻𝐶𝑂𝑂− 𝐻𝐶𝑂𝑂− 𝑯𝑪𝑶𝑶−
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 = 3.8 + 𝑙𝑜𝑔 = 3.6 ⇒ = 𝟎. 𝟔𝟑𝟏
𝐻𝐶𝑂𝑂𝐻 𝐻𝐶𝑂𝑂𝐻 𝑯𝑪𝑶𝑶𝑯
Knowing that :
𝑯𝑪𝑶𝑶𝑯 + 𝑯𝑪𝑶𝑶− = 𝟎. 𝟏𝟓 𝐌 We can deduce 𝐻𝐶𝑂𝑂𝐻 = 0.09 M 𝐻𝐶𝑂𝑂− = 0.06 M
Now, we can calculate the initial volumes used from the concentrated solutions to prepare the buffer solution :
𝐶𝐻𝐶𝑂𝑂𝐻 × 𝑉𝑡𝑜𝑡 𝐶𝐻𝐶𝑂𝑂− × 𝑉𝑡𝑜𝑡
𝑉 𝑖,𝐻𝐶𝑂𝑂𝐻 = = 𝟒𝟓 𝒎𝑳 𝑉 𝑖,𝑁𝑎𝐶𝑂𝑂𝐻 = = 𝟑𝟓. 𝟐𝟗 𝒎𝑳 𝑉𝐻2 𝑂 = 500 –(45 + 35.29) = 𝟒𝟏𝟗. 𝟕𝟏 𝒎𝑳
𝐶𝑖,𝐻𝐶𝑂𝑂𝐻 𝐶𝑖,𝑁𝑎𝐶𝑂𝑂𝐻
4
The composition of buffer solution: 𝒙 fraction
Consider the previous buffer solution with the following concentrations :
𝐻𝐶𝑂𝑂𝐻 = 0.09 M 𝐻𝐶𝑂𝑂− = 0.06 M
Calculate the change in 𝑝𝐻, when 0.01 𝑀 of a strong acid (𝐻𝐶𝑙) is added (without variation in volume).
The reaction that takes place is : 𝐻𝐶𝑂𝑂− 𝑎𝑞 + 𝐻3 𝑂+ 𝑎𝑞 ⇌ 𝐻𝐶𝑂𝑂𝐻 𝑎𝑞 + 𝐻2 O 𝑙 𝐾 = 10 3.8 > 10 3 (QPR)
I 0.06 0.01 0.09 excess
Eq 0.05 ⟶0 0.1 excess
Let’s express the concentration of the acid and base as function of 𝑥, the fraction of the total concentration of base or
, 𝑥′ the fraction of total concentration of the acid, as:
𝐻𝐶𝑂𝑂− 𝐻𝐶𝑂𝑂𝐻
𝑥= 𝑥′ =
𝐶0 𝐶0
𝐻𝐶𝑂𝑂− = 𝑥𝐶0 𝐻𝐶𝑂𝑂𝐻 = 𝑥′𝐶0
𝐻𝐶𝑂𝑂𝐻 = 𝐶0 − 𝑥𝐶0 = 𝐶0 (1 − 𝑥) 𝐻𝐶𝑂𝑂− = 𝐶0 − 𝑥′𝐶0 = 𝐶0 (1 − 𝑥′)
0.05 0.1
𝑥= = 0.33 𝑥′ = = 0.67
0.15 0.15
Fraction values are unitless ratios whose sum must equal unity. That is, 𝒙 + 𝒙′ = 𝟏
Substituting, acid and base concentrations in 𝑝𝐻 relationship, we obtain the same result:
𝐻𝐶𝑂𝑂− 𝑥 𝐻𝐶𝑂𝑂− 1 − 𝑥′
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 = 3.8 + 𝑙𝑜𝑔 = 𝟑. 𝟓 𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 = 3.8 + 𝑙𝑜𝑔 = 𝟑. 𝟓
𝐻𝐶𝑂𝑂𝐻 1−𝑥 𝐻𝐶𝑂𝑂𝐻 𝑥′
𝚫𝒑𝑯 = 3.5 − 3.6 = −𝟎, 𝟏 < 𝟎 5
The composition of buffer solution: 𝒙 fraction
Consider the previous buffer solution with the following concentrations :
𝐻𝐶𝑂𝑂𝐻 = 0.09 M 𝐻𝐶𝑂𝑂− = 0.06 M
Calculate the change in 𝑝𝐻, when 0.01 M of a strong base (𝑁𝑎𝑂𝐻) is added (without variation in volume).
The reaction that takes place is :
𝐻𝐶𝑂𝑂𝐻 𝑎𝑞 + 𝐻𝑂− 𝑎𝑞 ⇌ 𝐻𝐶𝑂𝑂− 𝑎𝑞 + 𝐻2 O 𝑙 𝐾 = 10 14−3.8 = 10 10.2 > 10 3
(QPR)
I 0.09 0.01 0.06 excess
Eq 0.08 ⟶0 0.07 excess
Let’s express the concentration of the acid and base as function of 𝑥, the fraction of the total concentration of acid or
, 𝑥′ the fraction of total concentration of the base, as:
𝐻𝐶𝑂𝑂𝐻 𝐻𝐶𝑂𝑂 −
𝑥= 𝑥′ =
𝐶0 𝐶0
𝐻𝐶𝑂𝑂𝐻 = 𝑥𝐶0 𝐻𝐶𝑂𝑂 − = 𝑥′𝐶0
𝐻𝐶𝑂𝑂 − = 𝐶0 − 𝑥𝐶0 = 𝐶0 (1 − 𝑥) 𝐻𝐶𝑂𝑂𝐻 = 𝐶0 − 𝑥′𝐶0 = 𝐶0 (1 − 𝑥′)
0.08 0.07
𝑥= = 0.53 𝑥′ = = 0.47
0.15 0.15
Fraction values are unitless ratios whose sum must equal unity. That is, 𝒙 + 𝒙′ = 𝟏
Substituting, acid and base concentrations in 𝑝𝐻 relationship, we obtain the same result:
𝐻𝐶𝑂𝑂− 1−𝑥 𝐻𝐶𝑂𝑂− 𝑥′
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 = 3.8 + 𝑙𝑜𝑔 = 𝟑. 𝟕𝟒 𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 = 3.8 + 𝑙𝑜𝑔 = 𝟑. 𝟕𝟒
𝐻𝐶𝑂𝑂𝐻 𝑥 𝐻𝐶𝑂𝑂𝐻 1 − 𝑥′
𝚫𝒑𝑯 = 3.74 − 3.6 = 𝟎, 𝟏𝟒 > 𝟎 6
𝒑𝑯 expression using 𝒙 fraction
Consider a buffer solution is prepared by adding 10 mL o𝑓 0.5𝑀 HCl to 50mL of 0.5 M of sodium formate;
calculate the pH of the buffer. 𝑝𝐾𝑎 (𝐻𝐶𝑂𝑂𝐻/𝐻𝐶𝑂𝑂−) = 3.8
𝐻𝐶𝑙 𝑎𝑞 + 𝐻2 O(𝑙) ⟶ 𝐻3 𝑂+ (𝑎𝑞) + 𝐶𝑙− (𝑎𝑞) 𝐻𝐶𝑂𝑂𝑁𝑎 𝑠 + 𝐻2 O(𝑙) ⟶ 𝐻𝐶𝑂𝑂− (𝑎𝑞) + 𝑁𝑎+ (𝑎𝑞)
Let’s calculate the concentrations of reactants in the mixture:
0.5 ×10 0.5 ×50
𝐶𝑎 = = 8.33 × 10 −2 𝑀 𝐶𝐵 = = 0.42 𝑀
60 60
Let’s use the ICE table : 𝐻𝐶𝑂𝑂− 𝑎𝑞 + 𝐻3 𝑂+ 𝑎𝑞 ⇌ 𝐻𝐶𝑂𝑂𝐻 𝑎𝑞 + 𝐻2 O 𝑙 𝐾 = 10 3.8 > 10 3 (QPR)
I 𝐶𝐵 𝐶𝑎 0 excess
Eq 𝐶𝐵 −𝐶𝑎 ⟶0 𝐶𝑎 excess
𝐻3 𝑂+ provided from 𝐻𝐶𝑙 added is the limitig reactant.
We then define 𝑥, the fraction of the total concentration of acid, as:
𝐻𝐶𝑂𝑂𝐻 𝐶𝑎
𝑥= = = 0.2 𝑇ℎ𝑒𝑟𝑒𝑓𝑜𝑟𝑒: 𝐶𝑎 = 𝑥𝐶𝐵
𝐶0 𝐶𝐵
𝐻𝐶𝑂𝑂− 𝐶𝐵 − 𝑥𝐶𝐵
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔
𝐻𝐶𝑂𝑂𝐻 𝑥𝐶𝐵
𝟏 −𝒙
𝒑𝑯 = 𝒑𝑲𝒂 + 𝒍𝒐𝒈
𝒙
1 − 0.2
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 = 𝟒. 𝟒𝟎
0.2 7
𝒑𝑯 expression using 𝒙 value
Consider a buffer solution is prepared by adding 20 mL o𝑓 0.1𝑀 𝑁𝑎𝑂𝐻 to 50mL of 0.1 M of formic acid;
calculate the pH of the buffer. 𝑝𝐾𝑎 (𝐻𝐶𝑂𝑂𝐻/𝐻𝐶𝑂𝑂−) = 3.8
𝑁𝑎𝑂𝐻(𝑠) ⟶ 𝑁𝑎+ (𝑎𝑞) + 𝐻𝑂− (𝑎𝑞)
Let’s calculate the concentrations of reactants in the mixture:
0.1 ×20 0.1 ×50
𝐶𝑏 = = 2.85 × 10 −2 𝑀 𝐶𝐴𝐻 = = 7.14 × 10 −2 𝑀
70 70
Let’s use the ICE table : 𝐻𝐶𝑂𝑂𝐻 𝑎𝑞 + 𝐻𝑂− 𝑎𝑞 ⇌ 𝐻𝐶𝑂𝑂− 𝑎𝑞 + 𝐻2 O 𝑙 𝐾 = 10 14−3.8 = 10 10.2 > 10 3
I 𝐶𝐴𝐻 𝐶𝑏 0 excess
(QPR)
Eq 𝐶𝐴𝐻 −𝐶𝑏 ⟶0 𝐶𝑏 excess
𝐻𝑂− provided from NaOH added is the limitig reactant.
We then define 𝑥, the fraction of the total concentration of base, as:
𝐻𝐶𝑂𝑂𝐻 𝐶𝑏 𝑇ℎ𝑒𝑟𝑒𝑓𝑜𝑟𝑒: 𝐶𝑏 = 𝑥𝐶𝐴𝐻
𝑥= = = 0.4
𝐶0 𝐶𝐴𝐻
𝐻𝐶𝑂𝑂− 𝑥𝐶𝐴𝐻
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔
𝐻𝐶𝑂𝑂𝐻 𝐶𝐴𝐻 − 𝑥𝐶𝐴𝐻
𝒙
𝒑𝑯 = 𝒑𝑲𝒂 + 𝒍𝒐𝒈
𝟏 −𝒙
0.4
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 = 𝟑. 𝟔𝟐
1 − 0.4 8
Buffer capacity
Buffer capacity (𝜷) refers to the ability of a buffer solution to resist changes in 𝑝𝐻 (𝒅𝒑𝑯) when small amounts
of an acid (𝒅𝑪𝒂 ) or base (𝒅𝑪𝒃 ) are added.
It represents the number of moles of strong acid or strong base that need to be added to 1 L of buffer
solution to undergo a 1.00-unit change in 𝑝𝐻.
Mathematically, it is defined by the following relationship:
𝟐. 𝟑 𝑪𝟎
𝜷𝒎𝒂𝒙 =
𝒅𝑪𝒂 𝒅𝑪𝒃 𝟒
𝜷=− 𝜷=
𝒅𝒑𝑯 𝒅𝒑𝑯
A buffer capacity is always positive, a solution with high buffer capacity can maintain
a stable 𝑝𝐻 even when challenged with external substances.
Buffer capacity depends not only on the total concentration of the two buffer
components but also on their concentration ratio.
The maximum buffer capacity occurs when the concentrations of acid and conjugate base
1
are equal, that is, when 𝑥 = 𝑥’ = . Therefore 𝑝𝐻 = 𝑝𝐾𝑎 (The opposite curve)
2
The buffer capacity can calculated by two formulas which give the same result :
𝟐. 𝟑 𝑪𝟎 𝑲𝒂 𝑯𝟑 𝑶+
𝜷 = 𝟐. 𝟑 𝑪𝟎 𝒙 𝟏 − 𝒙 𝜷=
(𝑲𝒂 + 𝑯𝟑 𝑶+ )𝟐 9
Buffer capacity expressions
Buffer capacity (𝜷) expressions are obtained using two methods:
Approximate differentiation method 𝜷 = 𝒇(𝒙) Chemical method 𝜷 = 𝒇(𝑯𝟑 𝑶+ )
𝒅𝑪𝒃 𝑑(𝐶0 𝑥) 𝑑𝑥 𝒅𝑪𝒂 𝑑𝐶𝑎 𝑑 𝐻3 𝑂+
𝛽= = × 𝛽=− =− ×
𝒅𝒑𝑯 𝑑𝑥 𝑑𝑝𝐻 𝒅𝒑𝑯 𝑑 𝐻3 𝑂+ 𝑑𝑝𝐻
𝑥 𝑑𝑝𝐻 𝟏 𝟏
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 𝑝𝐻 = −𝑙𝑜𝑔 𝐻3 𝑂 + ⇒ =− ×
1 −𝑥 𝑑 𝐻3 𝑂+ 𝒍𝒏 𝟏𝟎 𝑯𝟑 𝑶+
To convert the relationship from the decimal logarithm Adding a strong acid decreases the concentration of the weak
(log, 𝑏𝑎𝑠𝑒 10) to the natural logarithm (𝑙𝑛, 𝑏𝑎𝑠𝑒 𝑒), we can base 𝐴− and increases the concentration of the weak acid 𝐴𝐻.
write : 1 𝑥 𝑑𝐶𝑎 𝑑 𝐴−
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑛 =−
𝑙𝑛 10 1 −𝑥 𝑑 𝐻3 𝑂+ 𝑑 𝐻3 𝑂+
The derivative of 𝑝𝐻 with respect to 𝑥 gives: Let’s express 𝐴− as function of 𝐶0 , 𝐾𝑎 𝑎𝑛𝑑 𝐻3 𝑂+ :
𝑑𝑝𝐻 1 𝑑 𝑥 𝟏 𝟏 𝐴− 𝐻3 𝑂+ 𝐴− 𝐻3 𝑂+ −
𝐶0 𝐾𝑎
= 𝑙𝑛 = × (∗) 𝐾𝑎 = = ⇒ 𝐴 =
𝑑𝑥 𝑙𝑛10 𝑑𝑥 1 −𝑥 𝒍𝒏𝟏𝟎 𝒙 (𝟏 − 𝒙) 𝐻𝐴 𝐶0 − 𝐴− (𝐾𝑎 + 𝐻3 𝑂+ )
and substitute into 𝛽 formula, The derivative of 𝐴− with respect to 𝐻3 𝑂+ gives:
𝐶0 𝑑𝑥 𝑑𝑥 𝑑𝐶𝑎 𝑑 𝐴− 𝑪𝟎 𝑲𝒂
𝛽= × = 𝐶0 × 𝑙𝑛10 × 𝑥 (1 − 𝑥) =− =−
𝑑𝑥 𝑑𝑝𝐻 𝑑 𝐻3 𝑂+ 𝑑 𝐻3 𝑂+ (𝑲𝒂 + 𝑯𝟑 𝑶+ )𝟐
The formula becomes: The formula becomes: 𝟐. 𝟑 𝑪𝟎 𝑲𝒂 𝑯𝟑 𝑶+
𝜷=
𝜷 = 𝟐. 𝟑 𝑪𝟎 𝒙 𝟏 − 𝒙 (𝑲𝒂 + 𝑯𝟑 𝑶+ )𝟐 10
Acid and base buffer capacity
𝒑𝑯 of buffer solution
Acid buffer capacity, it’s the Base buffer capacity, it’s the
amount of strong acid to add amount of strong base to add
to one liter to change the 𝑝𝐻 to one liter to change the 𝑝𝐻
until 𝑝𝐾𝑎 −1 until 𝑝𝐾𝑎 + 1
The 𝑝𝐻 value and the molarity of the buffer are responsible for the buffer capacity:
• According to the 𝑝𝐻 value
𝑝𝐻 = 𝑝𝐾𝑎 ⇒ acid buffer capacity = basic buffer capacity
𝑝𝐻 < 𝑝𝐾𝑎 ⇒ basic buffer capacity > acid buffer capacity
𝑝𝐻 > 𝑝𝐾𝑎 ⇒ acid buffer capacity > basic buffer capacity
• According to the molarity; if the buffer is diluted, the buffer capacity is divided by the dilution factor.
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Buffer solutions
Application 1:
Consider the buffer solutions prepared from 𝐶𝐻3 𝐶𝑂𝑂𝐻 0.19 𝑀 and 𝐶𝐻3 𝐶𝑂𝑂𝑁𝑎 0, 3 𝑀 with 𝑝𝐻 = 5.
1. What strong acid or base must be added to change the 𝑝𝐻 to 4.8 ? Calculate the amount of this strong species.
2. Is the buffer capacity of this solution at its maximum? Calculate its value.
𝑝𝐾𝑎 (𝐶𝐻3 𝐶𝑂𝑂𝐻/𝐶𝐻3 𝐶𝑂𝑂− ) = 4.8
Solution:
1. 𝑝𝐻 = 5 > 𝑝𝐾𝑎 = 4.8 ⇒ an amount of strong acid must be added to decrease the 𝑝𝐻 until 4.8.
The reaction that takes place in the medium is:
𝐶𝐻3 𝐶𝑂𝑂− 𝑎𝑞 + 𝐻3 𝑂 + 𝑎𝑞 ⇌ 𝐶𝐻3 𝐶𝑂𝑂𝐻 𝑎𝑞 + 𝐻2 O 𝑙 𝐾 = 10 4.8 > 10 3 (QPR)
I 0.3 𝐶𝑎 0.19 excess
Eq 0.3 − 𝐶𝑎 ⟶0 0.19 + 𝐶𝑎 excess
𝐻𝐶𝑂𝑂− 0.3 − 𝐶𝑎 0.3 − 𝐶𝑎
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 = 4.8 + 𝑙𝑜𝑔 = 4.8 ⇒ = 𝟏 ⇒ 𝑪𝒂 = 𝟎. 𝟎𝟓𝟓𝑴
𝐻𝐶𝑂𝑂𝐻 0.19 + 𝐶𝑎 0.19 + 𝐶𝑎
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2. At 𝑝𝐻 = 𝑝𝐾𝑎, The concentrations are equals 𝐻𝐶𝑂𝑂− = 𝐻𝐶𝑂𝑂𝐻 = 0.245𝑀 and 𝑥 = 𝑥’ = 2
So, the buffer capacity is at maximum. 𝟐. 𝟑 𝑪𝟎 𝟐. 𝟑 × 𝟎. 𝟒𝟗
𝜷𝒎𝒂𝒙 = = = 𝟎. 𝟐𝟖 𝑴
𝟒 𝟒 12
Buffer solutions
Application 2:
Consider two buffer solutions 𝐵1 and 𝐵2 with the same 𝑝𝐻.
𝐵1 : 𝐻𝐶𝑂𝑂𝐻 5 × 10−2 𝑀, 1𝐿 + 1.476 𝑔 𝑜𝑓 𝑁𝑎𝑂𝐻 𝐵2 : 𝐶𝐻3 𝐶𝑂𝑂𝐻 8 × 10−2 𝑀, 1𝐿 + 704 𝑚𝑔 𝑜𝑓 𝑁𝑎𝑂𝐻
1. Calculate the pH using x expression. [Link] solution 𝐵1 and 𝐵2 has the best buffer capacity ?
𝐷𝑎𝑡𝑎: 𝑀𝑁𝑎𝑂𝐻 = 40 𝑔/𝑚𝑜𝑙, 𝑝𝐾𝑎 (𝐻𝐶𝑂𝑂𝐻/𝐻𝐶𝑂𝑂− ) = 3.8, 𝑝𝐾𝑎 (𝐶𝐻3 𝐶𝑂𝑂𝐻/𝐶𝐻3 𝐶𝑂𝑂− ) = 4.8
Solution:
B1: Let’s calculate the number of moles of weak acid and strong base the mixture.
𝑚𝑁𝑎𝑂𝐻
𝑛𝐻𝐶𝑂𝑂𝐻 = 𝐶𝐻𝐶𝑂𝑂𝐻 × 𝑉 = 0.05 mol, 𝑛𝑁𝑎𝑂𝐻 = = 0.037 mol
𝑀𝑁𝑎𝑂𝐻
𝐻𝐶𝑂𝑂𝐻 𝑎𝑞 + 𝐻𝑂− 𝑎𝑞 ⇌ 𝐻𝐶𝑂𝑂− 𝑎𝑞 + 𝐻2 O 𝑙 𝐾 = 10 3.8 > 10 3 (QPR)
I 0.05 0.037 0 excess
Eq 0.013 ⟶0 0.037 excess
𝐻𝐶𝑂𝑂− 𝑛𝑏 0.037
𝑥= = = = 0.74
𝐶0 𝑛𝐴𝐻 0.05
𝒙 0.74
𝒑𝑯 = 𝒑𝑲𝒂 + 𝒍𝒐𝒈 𝑝𝐻 = 𝑝𝐾 𝑎 + 𝑙𝑜𝑔 = 𝟒. 𝟐𝟓
𝟏 −𝒙 1 − 0.74
𝜷 = 𝟐. 𝟑 𝑪𝟎 𝒙 𝟏 − 𝒙 = 2.3 × 0.05 × 0.74 × 1 − 0.74 = 𝟎. 𝟎𝟐𝟐 M 13
Buffer solutions
B2: Let’s calculate the number of moles of weak acid and strong base in the mixture.
𝑚𝑁𝑎𝑂𝐻
𝑛𝐶𝐻3 𝐶𝑂𝑂𝐻 = 𝐶𝐶𝐻3 𝐶𝑂𝑂𝐻 × 𝑉 = 0.08 mol, 𝑛𝑁𝑎𝑂𝐻 = = 0.0176 mol
𝑀𝑁𝑎𝑂𝐻
𝐶𝐻3 𝐶𝑂𝑂𝐻 𝑎𝑞 + 𝐻𝑂− 𝑎𝑞 ⇌ 𝐶𝐻3 𝐶𝑂𝑂− 𝑎𝑞 + 𝐻2 O 𝑙 𝐾 = 10 4.8 > 10 3 (QPR)
I 0.08 0.0176 0 excess
Eq 0.0624 ⟶0 0.0176 excess
𝐶𝐻3 𝐶𝑂𝑂− 𝑛𝑏 0.0176
𝑥= = = = 0.22
𝐶0 𝑛𝐴𝐻 0.08
𝒙 0.22
𝒑𝑯 = 𝒑𝑲𝒂 + 𝒍𝒐𝒈 𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 = 𝟒. 𝟐𝟓
𝟏 −𝒙 1 − 0.22
𝟐. 𝟑 𝑪𝟎 𝑲𝒂 𝑯𝟑 𝑶+ 2.3 × 0.08 × 10−4.8 × 10−4.25
𝜷= = = 𝟎. 𝟎𝟑𝟐 𝐌
(𝑲𝒂 + 𝑯𝟑 𝑶+ )𝟐 10−4.8 + 10−4.25 𝟐
Conclusion: The more concentrated buffer solution has the higher and the best buffer capacity.
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