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Chemical Equilibrium Study Guide

Equilibrium: A State of Balance
Chemical equilibrium is a state in a reversible reaction where the rates of the forward and reverse
reactions are equal, and the net change in concentrations of reactants and products is zero.
Equilibrium can be observed in various processes involving different phases:
Solid-Liquid Equilibrium: e.g., the equilibrium between a solid solute and its saturated
solution.
Liquid-Gas Equilibrium: e.g., the equilibrium between water and water vapor.
Solid-Gas Equilibrium: e.g., the equilibrium between solid iodine and iodine vapor.
Saturated solution: A solution in which no more solute can be dissolved at a given temperature
and pressure. The maximum amount of solute that can dissolve in 100g of solvent at a given
temperature is called its solubility.

Equilibrium Constant (K)

The equilibrium constant (K) is a value that expresses the relationship between the concentrations
of reactants and products at equilibrium. For a reversible reaction:

aA + bB ⇌ cC + dD

The equilibrium constant is given by:

[C] c [D] d
K= [A] a [B] b

Note: The equilibrium constant is temperature dependent.

K > 1: The equilibrium favors products.

K < 1: The equilibrium favors reactants.
K = 1: The concentrations of reactants and products are approximately equal at equilibrium.

Types of Equilibrium Constants

For different types of equilibrium involving gases and solutions, we can define equilibrium constants
using partial pressures or concentrations:

Equilibrium
Equilibrium Type Expression
Constant

Homogeneous Gas Equilibrium Kp Using partial pressures of gases

Homogeneous Solution Using molar concentrations of reactants and
Kc
Equilibrium products

Le Chatelier's Principle
Le Chatelier's Principle: If a change of condition (temperature, pressure, concentration) is
applied to a system in equilibrium, the system will shift in a direction that relieves the stress.

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Changes in Concentration: Increasing the concentration of a reactant shifts the equilibrium to the
right (favoring product formation), and vice versa.
Changes in Pressure: Increasing the pressure shifts the equilibrium to the side with fewer moles of
gas, and vice versa. This effect is only significant for gaseous reactions.
Changes in Temperature: This depends on whether the reaction is exothermic or endothermic.
For an exothermic reaction (heat is a product), increasing the temperature shifts the
equilibrium to the left.
For an endothermic reaction (heat is a reactant), increasing the temperature shifts the
equilibrium to the right.

Gibbs Free Energy and Equilibrium 🫙

The standard Gibbs free energy change (ΔG°) is related to the equilibrium constant (K) by the
equation:

ΔG° = −RT ln K

where:

R is the ideal gas constant

T is the temperature in Kelvin.

At equilibrium (ΔG = 0), this equation becomes:

0 = ΔG° + RT ln Q

where Q is the reaction quotient. This allows us to calculate the equilibrium constant K from
thermodynamic data.

Electrolytes and Equilibrium

Electrolytes
A substance which either in molten state or in aqueous solution can conduct electricity.
Examples are acids, bases, and salts.

Strong electrolytes: Dissociate completely in solution. Examples: NaCl, HCl, H₂SO₄, NaOH.
Weak electrolytes: Partially dissociate in solution to a smaller extent. Examples: CH₃COOH,
NH₄OH, H₂O.

Equilibrium of Weak Electrolytes

Strong electrolytes dissociate completely. The reaction is expressed by a single arrow pointing towards
the right. For example:

$NaCl_{(s)} \rightarrow Na^+{(aq)} + Cl^-{(aq)}$

Weak electrolytes ionize to a smaller extent. There is an equilibrium between the unionized electrolyte
and the ions formed in the solution. This is called dynamic equilibrium. For example:

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$CH_3COOH_{(aq)} + H_2O_{(l)} \rightleftharpoons CH_3COO^-{(aq)} + H_3O^+{(aq)}$

Acids and Bases

Arrhenius Concept (1884)

An acid is defined as a substance that yields hydrogen ions (H + ) and produces H + ions in an
aqueous solution. A base is defined as a substance that yields hydroxide ions (OH − ) and
produces OH − ions in an aqueous solution.

Examples:

Acid Reaction Base Reaction

H 2 SO 4 H 2 SO 4 (aq) → 2H + (aq) + SO 2−
4 (aq) NaOH NaOH(aq) → Na + (aq) + OH − (aq)
HCl HCl(aq) → H + (aq) + Cl − (aq) KOH KOH(aq) → K + (aq) + OH − (aq)
CH 3 COOH CH 3 COOH(aq) ⇌ CH 3 COO (aq) + H (aq) NH 4 OH NH 4 OH(aq) ⇌ NH 4+ (aq) + OH − (aq)
− +

According to this concept, neutralization involves the combination of H + ions and OH − ions to form
water, which is neutral.

H + (aq) + OH − (aq) → H 2 O(l)

Brønsted-Lowry Concept (1923)

An acid is a substance (molecule or ion) which has a tendency to donate a proton, and a base
is a substance (molecule or ion) which has a tendency to accept a proton.

Examples:

Brønsted-Lowry Acid Brønsted-Lowry Base

H 2 SO 4 , HCl, H 3 O + , H 2 O NH 3 , HSO −
4 , OH , H 2 O
−

Amphoteric/Amphiprotic species: A species that in a particular case can act as an acid, but in other cases
can act as a base. Examples include H 2 O.

Conjugate Acid-Base Pair: An acid after losing a proton becomes a base, and a base after accepting a
proton becomes an acid. Every acid has a corresponding base called its conjugate base.

HCl + H 2 O ⇌ Cl − + H 3 O +

NH 3 + H 2 O ⇌ NH 4+ + OH −

Lewis Concept of Acids & Bases

Lewis acids are electron pair acceptors. Examples: AlCl₃, BF₃, FeCl₃.

Lewis bases are electron pair donors. Examples: NH₃, R-NH₂, H₂O.

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Ionization of Water
Pure water is a very weak electrolyte and undergoes self-ionization to a small extent, where one water
molecule acts as a Lewis-Brønsted acid and the other water molecule acts as a Lewis-Brønsted base:

H 2 O(l) + H 2 O(l) ⇌ H 3 O + (aq) + OH − (aq)

Applying the law of mass action, the equilibrium constant for the ionization of water is:

K w = [H 3 O + ][OH − ]

Here, K w is known as the ionic product of water. For pure water at 25°C, [H 3 O + ] = [OH − ] = 10 −7 M.
Therefore:

K w = (10 −7 )(10 −7 ) = 10 −14

Dissociation/Ionization of Acids & Bases

The equilibrium constant for the dissociation of a weak acid HA is given by:

HA(aq) + H 2 O(l) ⇌ H 3 O + (aq) + A − (aq)

The equilibrium will shift towards the dissociation of the weaker acid. Similarly, for bases, the equilibrium
shifts towards the dissociation of the weaker base.

pH
pH = −log[H 3 O + ]

The pH scale ranges from 0 to 14. At 298 K, [H 3 O + ] ranges from 1 to 10 −14 M.

For acidic solutions: [H 3 O + ] > [OH − ]

For basic solutions: [H 3 O + ] < [OH − ]
For neutral solutions: [H 3 O + ] = [OH − ]

Lecture Notes: Acids, Bases, and Equilibria

Determining the Strength of Acids and Bases
The strength of an acid or base is determined by its dissociation constant, K a for acids and K b for bases.

K a is the equilibrium constant for the dissociation of an acid, HA ⇌ H + + A − . A larger K a

value indicates a stronger acid.

K b is the equilibrium constant for the dissociation of a base, B + H 2 O ⇌ BH + + OH − . A

larger K b value indicates a stronger base.

The pKa and pKb values are also used to represent acid and base strength. They are defined as:

pK a = − log K a

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pK b = − log K b

A lower pK a value indicates a stronger acid; a lower pK b value indicates a stronger base.

K a and K b are dimensionless.

Polybasic Acids and Polyacidic Bases

Polybasic acids contain more than one ionizable proton. The dissociation of a dibasic acid, H 2 X,
occurs in two steps: H 2 X(aq) ⇌ H + (aq) + HX − (aq) K a1 HX − (aq) ⇌ H + (aq) + X 2− (aq) K a2
K a1 and K a2 are different because of electrostatic interactions. It's harder to remove a proton from a
negatively charged ion.

Polyacidic bases contain more than one ionizable hydroxide ion. Similar stepwise dissociation
occurs, with different K b values for each step due to electrostatic effects.

Factors Affecting the Strength of Acids

The strength of an acid depends on several factors:

Bond strength: A weaker H-A bond leads to a stronger acid.

Electronegativity: Increased electronegativity of A increases the acid strength.
Resonance stabilization: Increased resonance stabilization of the conjugate base (A − ) makes the
acid stronger.
Inductive effects: Electron-withdrawing groups increase acid strength, while electron-donating
groups decrease it.

Hydrolysis of Salts
Salts can undergo hydrolysis, reacting with water to produce an acidic or basic solution. The extent of
hydrolysis depends on the strength of the acid and base from which the salt is derived.

For example, the hydrolysis of a salt formed from a strong acid and a weak base produces an
acidic solution.

Solubility Product Constant (K sp )

K sp represents the equilibrium constant for the dissolution of a sparingly soluble salt. For a salt A x B y ,
the solubility product is given by:

K sp = [A + ] x [B − ] y

A higher K sp value means greater solubility.

Predicting Ionic or Precipitation Reactions

The reaction quotient, Q, can be used to predict whether a precipitate will form.

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If Q < K sp , the solution is unsaturated and no precipitate forms. If Q > K sp , the solution is
supersaturated, and a precipitate will form. If Q = K sp , the solution is saturated, and the
system is at equilibrium.

Applications of K sp and the Common-Ion Effect

Selective precipitation: By controlling the concentration of a common ion, specific ions can be
selectively precipitated.
Purification: The common ion effect helps to purify samples by suppressing the solubility of
impurities.

Buffer Solutions
A buffer solution resists changes in pH upon addition of small amounts of acid or base. Buffer solutions
are typically made of a weak acid and its conjugate base or a weak base and its conjugate acid. The
ability of a buffer to resist pH changes is called buffer action.

Henderson-Hasselbalch Equation and Buffer

Solutions
Acidic Buffer Action
The buffer action of an acidic buffer, like a mixture of acetic acid and sodium acetate, works as follows:

Adding a small amount of HCl introduces H⁺ ions.

These H⁺ ions combine with CH₃COO⁻ ions to form weakly ionized acetic acid:
CH ₃COO⁻(aq) + H ⁺(aq) → CH ₃COOH(aq) + H ₂O(l)

Since H⁺ ions are neutralized, the pH remains relatively constant.

Adding NaOH introduces OH⁻ ions.

These OH⁻ ions are neutralized by the acetic acid:

OH ⁻(aq) + CH ₃COOH(aq) → CH ₃COO⁻(aq) + H ₂O(l)

Again, the pH remains relatively constant.

Basic Buffer Action

A basic buffer, such as a mixture of ammonium hydroxide and ammonium chloride, functions similarly:

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Adding HCl introduces H⁺ ions which combine with OH⁻ ions forming H₂O:
H ⁺(aq) + OH ⁻(aq) → H ₂O(l) The pH remains unchanged.

Adding NaOH introduces OH⁻ ions.

These combine with NH₄⁺ ions to form NH₄OH, which is weakly ionized:
OH ⁻(aq) + NH ₄⁺(aq) → NH ₄OH(aq)

The pH remains relatively constant.

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