Equilibrium – Theory Notes

(Memorisation)

Dynamic Equilibrium
 Dynamic equilibrium: The state where the rates of forward and reverse reactions are
equal, and concentrations of reactants and products remain constant.
 At equilibrium, both opposing processes occur simultaneously at the same rate.
 The mixture of reactants and products at equilibrium is called an equilibrium
mixture.

Equilibrium in Physical Processes

General Characteristics

1. Equilibrium is possible only in a closed system at a given temperature.

2. Both opposing processes occur at the same rate (dynamic but stable condition).
3. All measurable properties remain constant.
4. Characterized by a constant value of a parameter at given temperature.

Specific Equilibria

 Solid ⇌ Liquid: Equilibrium at melting/freezing point; mass of both phases constant

Liquid ⇌ Vapour: Vapour pressure constant at given temperature.

if no heat exchange.

Solid ⇌ Vapour: Sublimation equilibrium (e.g., I₂, camphor, NH₄Cl).



Solute (solution) ⇌ Solute (solid): Solubility constant at given temperature.



Gas (g) ⇌ Gas (aq): Concentration ratio constant at given temperature.




Henry's Law

 The mass of gas dissolved in a solvent is proportional to the pressure of the gas
above the solvent.

Equilibrium in Chemical Processes

 Chemical equilibrium is dynamic: forward and reverse reactions continue at equal
rates.
 Equilibrium can be reached from either direction (reactants or products).
Law of Chemical Equilibrium
For a general reaction:

aA +bB ⇌ cC+ dD

Equilibrium Constant (Kc)

K c =¿ ¿

 Kc: Equilibrium constant in terms of molar concentrations (mol L⁻¹).

 Concentrations are equilibrium values.
 Valid only at constant temperature.

Important Relations

' 1
 For reverse reaction: K c =
Kc
 If equation multiplied by n: K 'c' =¿
 If equation multiplied by ½: K 'c' =√ K c

Equilibrium Constant for Gaseous Systems (Kp)

 For gases, equilibrium expressed in partial pressures.
 Ideal Gas Equation: p=[gas ] RT (where R = 0.0831 bar L mol⁻¹ K⁻¹)

Relation between Kp and Kc

K p=K c ¿

Where:

Δ n=(moles of gaseous products)−(moles of gaseous reactants)

 If Δn = 0, then Kp = Kc
 Pressure must be in bar (standard state = 1 bar)

Homogeneous vs Heterogeneous Equilibria

Homogeneous Equilibrium
  All reactants and products in same phase.

Heterogeneous Equilibrium

 More than one phase present.

 Pure solids and liquids have constant concentration, so they are omitted from Kc
expression.

Example:

CaCO3 (s)⇌ CaO (s)+CO2 ( g) K c =[CO2 ]

Applications of Equilibrium Constants

1. Predicting Extent of Reaction

 Kc > 10³: Products predominate (reaction nearly complete).

 Kc < 10⁻³: Reactants predominate (reaction proceeds rarely).
 10⁻³ < Kc < 10³: Appreciable concentrations of both.

2. Predicting Direction of Reaction

Reaction Quotient (Qc)

Qc =¿ ¿

(value at any time t )

 Qc < Kc: Reaction proceeds forward (right).

 Qc > Kc: Reaction proceeds backward (left).
 Qc = Kc: Reaction at equilibrium.

Relationship between K, Q and Gibbs Energy

0
Δ G=Δ G + RT ln ⁡Q

At equilibrium (ΔG = 0):

0

Δ G =−RT ln ⁡K K=e−Δ G / RT
0

 ΔG⁰ < 0: K > 1 (spontaneous, products predominate).

 ΔG⁰ > 0: K < 1 (non-spontaneous, reactants predominate).
Le Chatelier's Principle
Statement: When a system at equilibrium is disturbed, it shifts to reduce or counteract the
effect of the change.

Effect of Concentration

 Adding reactant/product: Equilibrium shifts to consume the added substance.

 Removing reactant/product: Equilibrium shifts to replenish it.

Effect of Pressure (for gaseous reactions)

 Increase pressure: Equilibrium shifts toward fewer moles of gas.

 Decrease pressure: Equilibrium shifts toward more moles of gas.
 If Δn = 0, pressure has no effect.

Effect of Inert Gas

 At constant volume: No effect (partial pressures unchanged).

Effect of Temperature

 Exothermic reaction (ΔH < 0): K decreases with temperature increase.

 Endothermic reaction (ΔH > 0): K increases with temperature increase.

Effect of Catalyst

 No effect on equilibrium position or K.

 Increases rate of both forward and reverse reactions equally.
 Does not appear in equilibrium expression.

Ionic Equilibrium in Solution

Electrolytes

 Strong electrolytes: Almost completely ionized (e.g., NaCl, HCl, NaOH).

 Weak electrolytes: Partially ionized (e.g., CH₃COOH, NH₄OH).

Acids, Bases and Salts – Definitions

1. Arrhenius Concept
  Acid: Produces H⁺ (or H₃O⁺) in aqueous solution.
 Base: Produces OH⁻ in aqueous solution.

2. Brønsted-Lowry Concept

 Acid: Proton (H⁺) donor.

 Base: Proton (H⁺) acceptor.
 Conjugate acid-base pair: Differ by one proton.
o Conjugate base = acid – H⁺
o Conjugate acid = base + H⁺

3. Lewis Concept

 Lewis acid: Electron pair acceptor (e.g., BF₃, AlCl₃, H⁺).

 Lewis base: Electron pair donor (e.g., NH₃, OH⁻, H₂O).

Ionization of Acids and Bases

Strong Acids

 Almost completely dissociated: HClO₄, HCl, HBr, HI, HNO₃, H₂SO₄.

Strong Bases

 Almost completely dissociated: LiOH, NaOH, KOH, CsOH, Ba(OH)₂.

Weak Acids

 Partially ionized (e.g., HF, CH₃COOH, HNO₂).

Weak Bases

 Partially ionized (e.g., NH₃, amines).

Ionization Constants
Acid Ionization Constant (Ka)

For weak acid HA:

−¿¿

HA ⇌ H
+ ¿+ A ¿
K a =¿ ¿

If degree of ionization = α, initial concentration = c:

 2
cα
Ka=
1−α

Base Ionization Constant (Kb)

For weak base MOH:

−¿ ¿

MOH ⇌M
+¿+OH ¿
K b =¿ ¿

If degree of ionization = α, initial concentration = c:

2
cα
Kb=
1−α

Relation between Ka and Kb

For conjugate acid-base pair:

K a × K b =K w

Where Kw = ionic product of water = 1.0 × 10⁻¹⁴ (at 298 K).

Ionization of Water
−¿¿
+¿+OH ¿
H2 O+ H2 O ⇌ H3 O

Ionic product of water (Kw):

K w =¿

In pure water:

The pH Scale
Definition

pH=−log ⁡¿

pOH, pKa, pKb, pKw

 pOH=−log ⁡¿ pK a=−log ⁡K a pK b=−log ⁡K b pK w =−log ⁡K w =14 (at 298 K)

Important Relation

pH+ pOH=pK w =14

For conjugate pair:

pK a +pK b=14

Nature of Solutions

 Acidic: pH < 7, [H⁺] > 10⁻⁷ M

 Neutral: pH = 7, [H⁺] = 10⁻⁷ M
 Basic: pH > 7, [H⁺] < 10⁻⁷ M

Polyprotic Acids
 Acids with more than one ionizable proton (e.g., H₂SO₄, H₃PO₄, H₂CO₃).

For dibasic acid H₂X:

K a 1=¿ ¿ K a 2=¿ ¿

 Generally: Ka1 > Ka2 > Ka3 (successive ionization becomes harder).

Factors Affecting Acid Strength

1. H-A bond strength: Weaker bond → stronger acid.
2. H-A bond polarity: More polar → stronger acid.

Periodic Trends:

 Down a group: Acid strength increases (bond strength decreases).

o HF < HCl < HBr < HI
 Across a period: Acid strength increases (electronegativity increases).
o CH₄ < NH₃ < H₂O < HF

Common Ion Effect

  Definition: Shift in equilibrium on adding a substance that provides an ion already
present.
 Suppresses ionization of weak acid/base.
 Based on Le Chatelier's principle.

Example: Adding CH₃COONa to CH₃COOH solution suppresses ionization of acetic acid.

Hydrolysis of Salts
 Hydrolysis: Interaction of cations/anions of a salt with water.

Types

1. Salt of strong acid + strong base: No hydrolysis, pH = 7 (neutral).

o Example: NaCl, KBr
2. Salt of weak acid + strong base: Anion hydrolyzes, pH > 7 (basic).

o CH₃COO⁻ + H₂O ⇌ CH₃COOH + OH⁻

o Example: CH₃COONa

3. Salt of strong acid + weak base: Cation hydrolyzes, pH < 7 (acidic).

o NH₄⁺ + H₂O ⇌ NH₄OH + H⁺

o Example: NH₄Cl

4. Salt of weak acid + weak base: Both hydrolyze. $$\text{pH} = 7 + \frac{1}{2}(\

text{pK}_a - \text{pK}_b)

Buffer Solutions
 Definition: Solutions that resist change in pH on dilution or addition of small
amounts of acid/base.

Examples:

 CH₃COOH + CH₃COONa (pH ≈ 4.75)

 NH₄Cl + NH₄OH (pH ≈ 9.25)

Solubility Equilibria
Solubility Categories

1. Soluble: S > 0.1 M

2. Slightly soluble: 0.01 M < S < 0.1 M
3. Sparingly soluble: S < 0.01 M
Solubility Product (Ksp)

For sparingly soluble salt:

q−¿(aq) ¿

M x X y (s)⇌ x M p+¿(aq)+ y X ¿
K sp =¿

If molar solubility = S:
1/(x + y)
K sp
K sp =¿ S=( x y
)
x ⋅y

Precipitation Conditions

Ionic Product (Qsp): Same form as Ksp but for non-equilibrium conditions.

 Qsp < Ksp: Unsaturated, no precipitation.

 Qsp = Ksp: Saturated, at equilibrium.
 Qsp > Ksp: Supersaturated, precipitation occurs.

Common Ion Effect on Solubility

 Adding common ion decreases solubility of sparingly soluble salt.

Effect of pH on Solubility

 For salts of weak acids: Solubility increases at lower pH (higher [H⁺]).

S= √ K sp ¿ ¿ ¿

Important Numerical Relations

For Equilibrium Calculations

Net Reaction Equilibrium Constant

K net =K 1 × K 2 × ⋯

Percent Dissociation

% dissociation=¿ ¿

Weak Acid/Base (if α << 1):

 2 2
K a ≈ c α or K b ≈ c α α ≈
√ Ka
c √
or α ≈
Kb
c

Key Constants (at 298 K)

 Kw = 1.0 × 10⁻¹⁴ M²
 pKw = 14
 [H⁺] in pure water = 1.0 × 10⁻⁷ M
 R = 0.0831 bar L mol⁻¹ K⁻¹ (for Kp calculations)
 1 bar = 10⁵ Pa