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 1-

Dr. A. AMIRA

Email : [email protected]
 Definition of acids and bases
The classical theory of Arrhenius (1887)
 An Arrhenius acid is a substance that, when dissolved in water, produces 𝐻 + ion.
𝑯𝟐 𝑶
𝑯𝑪𝒍 (𝑎𝑞) 𝑯+ (𝑎𝑞) + 𝑪𝒍− (𝑎𝑞)
 An Arrhenius base is a substance that, when dissolved in water, produces 𝐻𝑂⁻ ion.
S. Arrhenius
𝑯𝟐 𝑶
𝑵𝒂𝑶𝑯(𝒔) 𝑵𝒂+ (𝑎𝑞) + 𝑯𝑶− (𝑎𝑞) (1859-1927)

This theory is insufficient because it does not explain the basic properties of 𝑁𝐻₃. It does not contain 𝐻𝑂− .

Bronsted-Lowry Protolytic Theory (1923)

 An acid is any substance that donates a proton 𝐻⁺.
𝑪𝑯𝟑 𝑪𝑶𝑶𝑯 𝑎𝑞 + 𝑯𝟐 𝑶(𝑙) ⇌ 𝑯𝟑 𝑶+ (𝑎𝑞) + 𝑪𝑯𝟑 𝑪𝑶𝑶− (𝑎𝑞)
 A base is any substance that accepts a proton 𝐻⁺. J. N. Brønsted T. M. Lowry
(1879-1947) (1874-1936)
𝑵𝑯𝟑 (𝑎𝑞) + 𝑯𝟐 𝑶(𝑙) ⇌ 𝑵𝑯+ −
𝟒 (𝑎𝑞) + 𝑯𝑶 (𝑎𝑞)
Lewis Theory (1923)

 An acid is an electron pair acceptor and has an empty quantum orbital.

 A base is an electron pair donor, possessing a lone pair that can form a coordinate bond with a Lewis acid.

∎𝑨𝒍𝑪𝒍3 + ∶ 𝑵𝑯3 ⇌ 𝑪𝒍3 𝑨𝒍− —+ 𝑵𝑯3 G. N. Lewis

(1875–1946)
2
 acid-base behavior of water
The water acts as acid and gives up a proton, the species base 𝑯𝑶− formed is called conjugate base, as
shown by the reaction: + −
𝐇2 𝐎 ⇌ 𝐇 + 𝐇𝐎

Similarly, the water acts as base and accepts a proton, the species acid 𝐇3 𝐎+ formed is called conjugate acid,
as shown by the reaction:
𝐇2 𝐎 + 𝐇+ ⇌ 𝐇3 𝐎+

Water participates in both donating and accepting protons in chemical reactions, it acts as an acid only in the
presence of a base and vice versa. 𝐻 + ions do not exist in a free state.
When these two processes are combined, the result is an acid-base reaction called autoprotolysis:
𝑯2 𝑶 (𝑙) + 𝑯2 𝑶(𝑙) ⇌ 𝑯3 𝑶+ (𝑎𝑞) + 𝑯𝑶− (𝑎𝑞)
acid base conjugate acid conjugate base

(𝐚𝐜𝐢𝐝 − 𝐜𝐨𝐧𝐣𝐮𝐠𝐚𝐭𝐞 𝐛𝐚𝐬𝐞) 𝐩𝐚𝐢𝐫 of water (𝐂𝐨𝐧𝐣𝐮𝐠𝐚𝐭𝐞 𝐚𝐜𝐢𝐝 − 𝐛𝐚𝐬𝐞) 𝐩𝐚𝐢𝐫 of water
(𝑯𝟐 𝑶/𝑯𝑶− ) (𝐇3 𝐎+ /𝐇2 𝐎)

Water have both acidic and basic properties, which means it has two acid-base pairs: it is a amphoteric species.
3
 Acid/base reaction
An acid-base reaction is characterized by the transfer of a proton 𝑯+ between an acid and a base. These two
chemical species form a pair by changing from one to the other through the loss or gain of a proton 𝐻 + .
Any reaction between an acid and a base involves two acid/base pairs, and is written as follows:

𝑨𝒄𝒊𝒅 𝟏 + 𝑩𝒂𝒔𝐞 𝟐 ⇌ 𝒄𝒐𝒏𝒋𝒖𝒈𝒂𝒕𝒆 𝒃𝒂𝒔𝒆 𝟏 + 𝒄𝒐𝒏𝒋𝒖𝒈𝒂𝒕𝒆 𝒂𝒄𝒊𝒅 𝟐

Examples: 𝐶𝐻3 𝐶𝑂𝑂𝐻 𝑎𝑞 + 𝐻2 𝑂(𝑙) ⇌ 𝐻3 𝑂+ (𝑎𝑞) + 𝐶𝐻3 𝐶𝑂𝑂−(aq)

Acid 1 Base 2 conjugate acid 2 conjugate base 1
(𝐚𝐜𝐢𝐝 − 𝐜𝐨𝐧𝐣𝐮𝐠𝐚𝐭𝐞 𝐛𝐚𝐬𝐞) 𝐩𝐚𝐢𝐫 (𝐂𝐨𝐧𝐣𝐮𝐠𝐚𝐭𝐞 𝐚𝐜𝐢𝐝 − 𝐛𝐚𝐬𝐞) 𝐩𝐚𝐢𝐫 of water
(𝐶𝐻3 𝐶𝑂𝑂𝐻/𝐶𝐻3 𝐶𝑂𝑂− ) (𝐇3 𝐎+ /𝐇2 𝐎)

𝑁𝐻3 𝑎𝑞 + 𝐻2 𝑂 (𝑙) ⇌ 𝑁𝐻4 + 𝑎𝑞 + 𝐻𝑂− 𝑎𝑞

Base 1 Acid 2 conjugate acid 1 conjugate base 2
(𝐂𝐨𝐧𝐣𝐮𝐠𝐚𝐭𝐞 𝐚𝐜𝐢𝐝 − 𝐛𝐚𝐬𝐞) 𝐩𝐚𝐢𝐫 (𝐚𝐜𝐢𝐝 − 𝐜𝐨𝐧𝐣𝐮𝐠𝐚𝐭𝐞 𝐛𝐚𝐬𝐞) 𝐩𝐚𝐢𝐫 of water
(𝑁𝐻4 + /𝑁𝐻3 ) (𝑯𝟐 𝑶/𝑯𝑶− )

4
 Autoprotolysis of water
Autoprotolysis of water, also known as self-ionization, is the process by which water molecules spontaneously
dissociate into ions. This can be represented by the following equilibrium reaction:
2𝑯2 𝑶 (𝑙) ⇌ 𝑯3 𝑶+ (𝑎𝑞) + 𝑯𝑶− (𝑎𝑞)

The concentration of hydroxide and hydronium ions is the same in one liter of pure water.
𝑯3 𝑶+ = 𝑯𝑶− = 10−7 𝑴

The equilibrium constant for the autoprotolysis of water, is expressed as:

𝑎(𝑯 𝑶+ ) ×𝑎(𝑯𝑶−)
3
𝑲= 2
𝑎(𝐻
, 𝑎(𝐻2 𝑂) ≈ 1
2 𝑂)

In terms of concentrations, the ion product constant is represented as 𝐾𝑤 . At 25°C, its value is approximately
1.0 × 10−14 .
𝑲𝒘 = 𝑯𝟑 𝑶+ 𝑯𝑶− = 𝟏𝟎−𝟏𝟒

Frequently, the constant in very low values is expressed in terms of its 𝒑-function. The 𝑝-function is the
negative logarithm (to the base 10) of the value. Thus, for equilibrium constant of water.

𝒑𝑲𝒘 = −log 𝑲𝒘 = 14
5
 Strengths of Acids and Bases
-Dissociation constants of reference acid-base pairs-
In aqueous solution, the acidity constants of the two pairs in water, (𝐇3 𝐎+ /𝐇2 𝐎) and (𝑯𝟐 𝑶/𝑯𝑶− ) , play an
essential role.
Consider the acid-base reaction of the acid 𝐇𝟑 𝐎+ with a molecule of water:
𝑯3 𝑶+ 𝑎𝑞 + 𝑯2 𝑶 𝑙 ⇌ 𝑯3 𝑶+ 𝑎𝑞 + 𝑯2 𝑶(𝑙)
𝑯3 𝑶 +
𝑲𝒂 = +
= 1 ⇒ 𝒑𝑲𝒂 (𝐇3 𝐎+ /𝐇2 𝐎) = 𝟎
𝑯3 𝑶

Consider the acid-base reaction of the acid 𝐇2 𝐎 with a molecule of water:

𝑯2 𝑶 (𝑙) + 𝑯2 𝑶 (𝑙) ⇌ 𝑯3 𝑶+ (𝑎𝑞) + 𝑯𝑶− (aq)

𝑲𝒂 = 𝑯3 𝑶+ 𝑶𝑯− = 10−14 ⇒ 𝒑𝑲𝒂 (𝑯𝟐 𝑶/𝑯𝑶− ) = 𝟏𝟒

The two pairs of water limit the 𝑝𝐾𝑎 scale. For weak acid-base pairs in water, apart from strong acids and
strong bases, their pKa is :
0 ≤ pKa ≤ 14 at 25°C
6
 Strengths of Acids and Bases
-Strong Acids and Bases-
Strong acids and bases are strong electrolytes that react completely with water, dissociating completely, only
the conjugate forms existing in solution and the reaction being complete.
𝑯𝑨 + 𝑯𝟐 𝑶 ⟶ 𝑯𝟑 𝑶+ + 𝑨−
𝑩 + 𝑯𝟐 𝑶 ⟶ 𝑩𝑯+ + 𝑯𝑶−
Example : 𝐻𝐶𝑙, 𝐻𝑁𝑂3 , 𝑁𝑎𝑂𝐻, 𝐾𝑂𝐻
In non-aqueous solvents, different strong acids and bases can exhibit varying strengths. However, in water,
they show no differences in strength, water is a leveling solvent for strong acids and bases.
No acid stronger than 𝐻3 𝑂+ or base stronger than 𝐻𝑂− exist in aqueous solution. We say that strong acids and
bases are levelled by water.
When strong acids and bases dissociate in solution, they often produce spectator ions. They are ions that do
not participate in a chemical reaction and remain unchanged in the solution.

𝐻𝐶𝑙 𝑎𝑞 + 𝐻2 𝑂(𝑙) → 𝐻3 𝑂+ 𝑎𝑞 + 𝐶𝑙− 𝑎𝑞 𝑁𝑎𝑂𝐻(𝑠) → 𝑁𝑎+ 𝑎𝑞 + 𝐻𝑂− 𝑎𝑞

(Strong acid/spectator base) (spectator acid/strong base)

0 14 pKa
𝑝𝐾𝑎(𝐻𝐶𝑙/𝐶𝑙⁻) = −7 𝑝𝐾𝑎(𝑁𝑎+ /𝑁𝑎𝑂𝐻) = 15,7
7
 Strengths of Acids and Bases
-Weak Acids and Bases-
Weak acids and bases are weak electrolytes that react partially with water. Their dissociation is incomplete,
they establish an equilibrium in water between their undissociated form and their ions.
𝑯𝑨(𝑎𝑞) + 𝑯𝟐 𝑶 (𝑙) ⇌ 𝑯𝟑 𝑶+ (𝑎𝑞) + 𝑨− (𝑎𝑞)
𝑩(𝑎𝑞) + 𝑯𝟐 𝑶 𝑙 ⇌ 𝑩𝑯+ (𝑎𝑞) + 𝑯𝑶− (𝑎𝑞)
Example : 𝐶𝐻3 𝐶𝑂𝑂𝐻, 𝐻𝐶𝑁, 𝑁𝐻3

The strength of weak electrolyte is often measured by their dissociation constant, which quantifies the extent of
ionization.
The equilibrium expression for the dissociation constant for acid and base are respectively:
𝑯𝟑 𝑶+ 𝑨− 𝑩𝑯+ 𝑯𝑶−
𝑲𝒂 = 𝑲𝒃 =
𝑯𝑨 𝑩

𝐾𝑎 and 𝐾𝑏 values are very low, 𝑝𝐾𝑎 and 𝑝𝐾𝑏 are commonly used :
𝒑𝑲𝒂 = − 𝒍𝒐𝒈 𝑲𝒂 𝒑𝑲𝒃 = − 𝒍𝒐𝒈 𝑲𝒃

* Water is the solvent and is present in large excess. Its concentration remains relatively constant during the
dissociation of acids and bases. 8
 Strengths of Acids and Bases
-relationship between constants-
For a conjugate acid-base pair, the relationship between the dissociation constants can be expressed as:

Consider the acid-base pair (𝐴𝐻/𝐴− ):

The reaction of the acid in water gives:
+ −
𝑯3 𝑶+ 𝑨−
𝑯𝑨 + 𝑯2 𝑶 ⇌ 𝑯3 𝑶 + 𝑨 𝑲𝒂 =
𝑯𝑨
The reaction of the conjugate base in water gives:
− −
𝑯𝑨 𝑯𝑶−
𝑨 + 𝑯2 𝑶 ⇌ 𝑯𝑶 + 𝑯𝑨 𝑲𝒃 =
𝑨−
The product of the both constant gives:

𝑯3 𝑶+ 𝑨− 𝑯𝑨 𝑯𝑶− + 𝑯𝑶− = 𝑲 = 10−14

𝑲𝒂 × 𝑲𝒃 = × = 𝑯 3 𝑶 𝒘
𝑯𝑨 𝑨−

𝒑𝑲𝒂 + 𝒑𝑲𝒃 = 𝒑𝑲𝒘 = 𝟏𝟒 𝑎𝑡 25°𝐶

9
 Strengths of Acids and Bases
-Classification of acid-base pairs-
The value of the 𝐾𝑎 (and therefore the 𝑝𝐾𝑎 ) determines the ability of the acid and its conjugate base to react
with water, so the pairs can be classified.
 The stronger the acid, the higher the 𝐾𝑎 ​ of its pair and the lower the 𝑝𝐾𝑎 .

 The base is stronger, the higher its 𝐾𝑏 (or lower its 𝑝𝐾𝑏 ), therefore the smaller the 𝐾𝑎 of its pair (or the higher its 𝑝𝐾𝑎 ).
pKa
Acceptor of 𝐻 +
Donor of 𝐻 +
(Base) (Acid)

𝐴−
2 𝐻𝐴2
Increasing strength
Increasing strength
of acids
of bases
𝐴1− 𝐻𝐴1

The smaller the 𝑝𝐾𝑎 , the stronger the acid 𝐻𝐴1 in a pair (𝐻𝐴1 /𝐴1− ) and the weaker the conjugate base 𝐴1− .
The greater the 𝑝𝐾𝑎 , the stronger the base 𝐴− −
2 in a pair (𝐻𝐴2 /𝐴2 ) and the weaker the conjugate acid 𝐻𝐴2 .

*On this diagram, it is essential that the bases are plotted on the left of the axis, and the acids on the right of the axis.
10
 The pH scale
In 1909, Soren Sorensen proposed the definition of 𝑝𝐻 to express the concentration of 𝐻3 𝑂+ ions, in a similar way to the
definition of 𝑝𝐾𝑎. 𝑝𝐻 = − log 𝑎 + (𝑯3 𝑶 )

For sufficiently dilute solutions [𝑯𝟑 𝑶+ ] < 0,1 𝑚𝑜𝑙/𝐿 , the 𝑝𝐻 is then defined by :
𝒑𝑯 = − 𝐥𝐨𝐠 𝑯𝟑 𝑶+
𝑝𝑂𝐻 indicates the concentration of hydroxide ions (HO⁻) in the solution. It is defined in analogous way to pH as:

𝒑𝑶𝑯 = − 𝐥𝐨𝐠 𝑯𝑶−

𝑝𝑂𝐻 is related to 𝑝𝐻 by the following relationship at 25°C, taking logarithms of both sides of the ionic product.

𝐾𝑤 = 𝑯3 𝑶+ 𝑯𝑶− = 10−14 ⇒ 𝒑𝑯 + 𝒑𝑶𝑯 = 𝟏𝟒

The 𝑝𝐻 scale typically ranges from 0 to 14 in aqueous solutions, with:

acidic 𝑯3 𝑶+ > 𝑯𝑶− neutral 𝑯𝑶− > 𝑯3 𝑶+ basic

𝑯3 𝑶+ = 𝑯𝑶−
-The pH of some common solutions- 11
 Predominance diagram of a pair (acid/base)
A predominance diagram represents the various forms (species) of an acid and its conjugate base in relation to
𝑝𝐻 and concentration.
Consider the acid-base pair (𝐴𝐻/𝐴− ):
The reaction of the acid in water gives:
𝑯3 𝑶+ 𝑨− 𝑯𝑨 𝑲𝒂
𝑯𝑨 + 𝑯2 𝑶 ⇌ 𝑯3 𝑶+ + 𝑨− 𝑲𝒂 = ⇒ 𝑯3 𝑶+ =
𝑯𝑨 𝑨−
The logarithmic expression of equation leads to the Henderson-Hasselbalch relationship:

𝑯𝑨 𝑲𝒂 𝑯𝑨
−𝒍𝒐𝒈 𝑯3 𝑶+ = −𝒍𝒐𝒈 −𝒍𝒐 𝒈 𝑯3 𝑶+ = −𝒍𝒐𝒈𝑲𝒂 − 𝒍𝒐𝒈
𝑨− 𝑨−
𝑨− pH
𝒑𝑯 = 𝒑𝑲𝒂 + 𝒍𝒐𝒈
𝑯𝑨 14
𝑨− 𝑨−
If, 𝑯𝑨 > 𝑨− ⇒ 𝒍𝒐𝒈 < 𝟎 ⇒ 𝒑𝑯 < 𝒑𝑲𝒂
𝑯𝑨
pKa
𝑨− 𝑯𝑨 𝑨−
If, 𝑨− > 𝑯𝑨 ⇒ 𝒍𝒐𝒈 > 𝟎 ⇒ 𝒑𝑯 > 𝒑𝑲𝒂
𝑯𝑨
pH 𝑯𝑨
0 pKa 14
𝑨−
If, 𝑯𝑨 = 𝑨− ⇒ 𝒍𝒐 𝒈 = 𝟎 ⇒ 𝒑𝑯 = 𝒑𝑲𝒂 0
𝑯𝑨
12
 Predominance diagram of a pair (acid/base) at 10%
The existence diagram at 10% is often used in acid-base problems. One species is considered major compared
to another if its concentration is 10 times higher.
𝑨−
𝒑𝑯 = 𝒑𝑲𝒂 + 𝒍𝒐𝒈
𝑯𝑨

𝑨−
If, 𝑯𝑨 ≥ 10 𝑨− ⇒ 𝒍𝒐𝒈 ≤ −𝟏 ⇒ 𝒑𝑯 ≤ 𝒑𝑲𝒂 − 𝟏
𝑯𝑨
𝑨−
If, 𝑨− ≥ 10 𝑯𝑨 ⇒ 𝒍𝒐𝒈 ≥ +𝟏 ⇒ 𝒑𝑯 ≥ 𝒑𝑲𝒂 + 𝟏
𝑯𝑨

If, 𝑯𝑨 ≈ 𝑨− ⇒ 𝒑𝑲𝒂 − 𝟏 < 𝒑𝑯 < 𝒑𝑲𝒂 + 𝟏

𝑯𝑨 ≥ 10 𝑨− 𝑯𝑨 ≈ 𝑨− 𝑨− ≥ 10 𝑯𝑨

0 pKa-1 pKa pKa+1 14 pH

13
 Evolution of acid-base reactions
-Gamma rule-
Consider the reaction between two (acid/base) pairs:
(𝐻𝐴1 /𝐴1− ) and (𝐻𝐴2 /𝐴−
2 ) with acid constants 𝐾𝑎,1 𝑎𝑛𝑑 𝐾𝑎,2 respectively

𝑯𝑨𝟏 𝑎𝑞 + 𝑨− −
𝟐 𝑎𝑞 ⇌ 𝑨𝟏 𝑎𝑞 + 𝑯𝑨𝟐 𝑎𝑞 𝐾

Case 1. 𝐾 > 1 (the reaction favors products) Case 2. 𝐾 < 1 (the reaction favors reactants)
𝐾𝑎,1 > 𝐾𝑎,2 or (𝑝𝐾𝑎,1 < 𝑝𝐾𝑎,2 ) 𝐾𝑎,1 < 𝐾𝑎,2 or (𝑝𝐾𝑎,1 > 𝑝𝐾𝑎,2 )
pKa
Acceptor of 𝐻 +
Donor of 𝐻 + pKa
(Acid) Acceptor of 𝐻 +
Donor of 𝐻 +
(Base)
(Base) (Acid)
𝐴−
2
𝑝𝐾𝑎,2 𝐴1−
𝑝𝐾𝑎,1
𝐻𝐴2
𝐻𝐴1
𝐴1−
𝑝𝐾𝑎,1 𝐴−
2
𝑝𝐾𝑎,2
𝐻𝐴1
𝐻𝐴2

𝐾 = 10(𝑝𝐾𝑎,2 −𝑝𝐾𝑎,1 ) 𝐾 = 10(𝑝𝐾𝑎,2 −𝑝𝐾𝑎,1 )

When 𝑝𝐾𝑎,2 − 𝑝𝐾𝑎,1 > 3 ⇒ 𝐾 > 103 , the reaction is quasi-total or quantitative. 14