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Revision: Std XII >> Ionic Equilibrium MAH-MHT CET (PCM/PCB) Ionic Equilibrium

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Definitions [21]

Definition: Ionic Equilibrium

The equilibrium which is established between the unionised molecules and the ions present in a solution of weak electrolytes is called ionic equilibrium.

Define the degree of dissociation.

The degree of dissociation (α) of an electrolyte is defined as a fraction of the total number of moles of the electrolyte that dissociates into its ions when the equilibrium is attained.

Degree of dissociation is defined as the fraction of the total number of moles of solute which undergoes dissociation in the solution.

Definition: Electrolyte

The substance that conducts electric current when dissociated into positively and negatively charged ions is called an electrolyte.

Definition: Degree of Dissociation (α)

It is the fraction of total number of moles of the electrolyte that dissociates into its ions when the equilibrium is attained.

It is denoted by symbol α.

\[\alpha=\frac{\text{Number of moles dissociated}}{\text{Total number of moles}}\]

Define conjugate acid-base pair.

A pair of an acid and a base differing by a proton is called conjugate acid-base pair.

Define acids according to Bronsted-Lowry theory.

A substance that donates a proton \[\ce{(H+)}\] to another substance is known as an acid.

Definition: Acid-Base Indicators

The materials which indicate the presence of an acid or a base in a solution. These are called Acid-Base Indicators or sometimes simple indicators.

Define pOH.

The pOH of a solution can be defined as the negative logarithm to the base 10, of the molar concentration of OH ions in solution.

pOH = -log10[OH-]

Definition: pH scale

pH scale is a scale for measuring the hydrogen ion concentration in a solution.

Define pH.

The pH of a solution is defined as the negative logarithm to the base 10, of the concentration of H+ ions in solution in mol dm–3.

pH is expressed mathematically as

pH = -log10 [H+] or pH = -log10 [H3O+]

Define Hydrolysis of salt.

Hydrolysis of salt is defined as the reaction in which cations or anions or both ions of a salt react with ions of water to produce acidity or alkalinity (or sometimes even neutrality).

Definition: Hydrolysis

The reaction of an anion or cation of a salt with water that produces an acidic or basic solution is called hydrolysis.

Define hydrolysis.

Hydrolysis of salt is defined as the reaction in which cations or anions or both ions of a salt react with ions of water to produce acidity or alkalinity (or sometimes even neutrality).

Define Acidic buffer solution.

A solution containing a weak acid and its salts with strong base is called an acidic buffer solution.

Definition: Basic Buffer

A buffer solution having a pH more than 7 is called a basic buffer. Weak base with its salt of strong acid gives basic buffer.

e.g. NH4OH + NH4Cl, C6H5NH2 + C6H5NH3Cl

Define buffer solution.

A buffer solution is defined as a solution which resists drastic changes in pH when a small amount of strong acid, strong base, or water is added to it.

Definition: Buffer Solution

The solution maintains its pH constant or retains an acidic or basic nature even upon the addition of small amounts of acid or base.

Definition: Buffer Action

The ability of a buffer solution to resist changes in pH on the addition of acid or base is called buffer action.

Definition: Acidic Buffer

A buffer solution of pH less than 7 is called an acidic buffer. Weak acid with its salt of strong base gives acidic buffer.

e.g. CH3COOH + CH3COONa; HCN + NaCN

Definition: Molar Solubility

The number of moles of a compound that dissolves to give one litre of saturated solution is called its molar solubility.

\[\text{Molar solubility (mol/L)}=\frac{\text{Solubility in g/L}}{\text{Molar mass in g/mol}}\]

Definition: Solubility Product

It is defined as the product of molar concentration of its ions in a saturated solution each concentration terms raised to the power equal to the number of ions produced on dissociation of one molecule of an electrolyte.

\[A_{x}B_{y}\rightleftharpoons xA^{y+}+yB^{x-}\]

\[K_{\mathrm{sp}}=[A^{y^{+}}]^{x-}[B^{x^{-}}]^{y}\]

Theorems and Laws [1]

Law: Ostwald's Dilution Law

The degree of dissociation of a weak electrolyte is inversely proportional to the square root of its concentration.

Feature Weak Acid Weak Base
Dissociation HA ⇌ H⁺ + A⁻ BOH ⇌ B⁺ + OH⁻
Constant Acid dissociation constant (Ka) Base dissociation constant (Kb)
Expression \[K_{a}=\frac{[H^{+}][A^{-}]}{[HA]}\] \[K_{b}=\frac{[B^{+}][OH^{-}]}{[BOH]}\]
Ostwald’s Dilution Law \[\alpha=\sqrt{\frac{K_{a}}{C}}\] or \[\alpha=\sqrt{K_{a}\cdot V}\] \[\alpha=\sqrt{\frac{K_{b}}{C}}\] or \[\alpha=\sqrt{K_{b}\cdot V}\]

Key Points

Key Points: Types of Electrolyte
Type Nature Extent of Ionisation Examples
Strong electrolytes Ionise completely or almost completely in solution Near 100% HCl, H₂SO₄, NaOH, KOH, NaCl, KCl
Weak electrolytes Ionise partially; poor conductors Small extent CH₃COOH, H₃BO₃, NH₄OH, HCN
Key Points: Acids and Bases (Theories)

Three Theories Compared:

Theory Acid Base
Arrhenius Contains H; produces H⁺ ions in aqueous solution Contains OH group; produces OH⁻ ions in aqueous solution
Bronsted–Lowry Proton donor (H⁺) Proton acceptor
Lewis Accepts a share in an electron pair Donates a share in an electron pair

All Bronsted bases are Lewis bases, but not all Bronsted acids are Lewis acids.

Key Points: Ionisation of Acids and Bases
  • Acids ionise in water to give H⁺/H₃O⁺ ions; bases give OH⁻ ions.
  • The extent of ionisation depends on the strength + concentration.
  • Strong → almost complete ionisation; weak → partial (equilibrium exists).
  • Represented as: HA ⇌ H⁺ + A⁻
  • The degree of ionisation, α, increases with dilution.
  • Basis of pH and equilibrium calculations.

Classification Based on Extent of Dissociation

Type Examples
Strong acids HCl, H₂SO₄, HNO₃
Weak acids HF, CH₃COOH, H₂S
Strong bases NaOH, KOH
Weak bases Fe(OH)₃, Cu(OH)₂
Key Points: Autoionisation of Water

Pure water is a weak electrolyte that self-ionises:

H2O(l) + H2O(l) ⇌ H3O+(aq) + OH(aq)

Ionic product of water:

Kw = [H3O+][OH]

At 298 K (pure water): [H₃O⁺] = [OH⁻] = 1.0 × 10-7 mol/L

∴ Kw = 1.0 × 10−14
Key Points: The pH Scale

pH = negative logarithm of H₃O⁺ ion concentration (mol/L).

pH = −log⁡10[H3O+]
pOH = −log⁡10[OH]
pH + pOH = 14
  • The pH scale (0–14) measures the concentration of H⁺ ions in a solution; values < 7 indicate acids, > 7 indicate bases, and 7 is neutral.
  • A universal indicator shows different colours at different pH levels, helping to determine the strength of an acid or base.
  • Strong acids/bases produce more H⁺ or OH⁻ ions in solution, while weak acids/bases produce fewer ions at the same concentration.
Key Points: Hydrolysis of Salts
Salt Hydrolysis Solution Nature Example
Strong acid + strong base Does not hydrolyse Neutral (pH = 7)

NaCl, KNO3, NaSO4

Strong acid + weak base Cation hydrolyses Acidic

NH4Cl, NH4NO3, (NH4)2SO4

Weak acid + strong base Anion hydrolyses Basic

CH3COONa, KCN, Na2SO3

Weak acid + weak base Both hydrolyse Depends: acidic if Ka > Kb; basic if Ka < Kb; neutral if Ka = Kb

CH3COONH4, NH4CN, (NH4)2CO3

Key Points: Common Ion Effect

Ionisation of a weak electrolyte is suppressed when a strong electrolyte with a common ion is added. According to Le Chatelier’s Principle, equilibrium shifts left due to increased concentration of a common ion.

Example 1 (Weak Acid):

  • Reaction:
    CH₃COOH ⇌ H⁺ + CH₃COO⁻
  • Add: CH₃COONa (gives CH₃COO⁻)
  • Effect: Ionisation of CH₃COOH decreases

Example 2 (Weak Base):

  • Reaction:
    NH₄OH ⇌ NH₄⁺ + OH⁻
  • Add: NH₄Cl (gives NH₄⁺)
  • Effect: Ionisation of NH₄OH decreases
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