EQUILIBRIUM

Equilibrium
The state where the concentrations of all reactants and products
remain constant with time is called equilibrium.
When a liquid evaporates in a closed container, molecules
escape the liquid surface into the vapour phase and number of
liquid molecules from the vapour phase strike the liquid surface
and remain in the liquid phase. This is called equilibrium state.
Thus at equilibrium the rate of evaporation is equal to the rate of
condensation.
H2O (l) H2O (vap)
The mixture of reactants and products in the equilibrium state is
called an Equilibrium mixture
Dynamic Equilibrium

When the reactants in a closed vessel at a particular

temperature react to give products then the concentrations of
the reactants keep on decreasing, while those of products keep
on increasing for some time after which there is no change in
the concentrations of either of the reactants or products. This
stage of the system is the Dynamic equilibrium .
The rates of the forward and reverse reactions become equal.
Based on the extent to which the reactions proceed to reach the state of
chemical equilibrium. These are classified into three groups:

The reactions that proceed nearly to completion of the reactants

or with negligible concentrations of the reactants are left.
The reactions in which only small amounts of products are formed
and most reactants remain unchanged at equilibrium stage.
The reactions in which the concentrations of the reactants and
products are comparable when the system is in equilibrium.
 The extent of a reaction in equilibrium varies with the
experimental conditions such as concentrations of reactants,
temperature etc.
The equilibrium involving ions in aqueous solutions is known as
Ionic Equilibrium
 Equilibrium in Physical Processes

Phase transformation processes

Solid liquid
Liquid gas
Solid gas

Solid-Liquid Equilibrium
Liquid-Vapour Equilibrium
Solid – Vapour Equilibrium
Equilibrium Involving Dissolution of Solid or Gases in
Liquids
For solid liquid equilibrium, there is only one temperature
(melting point) at 1 atm (1.013 bar) at which the two phases can
coexist. If there is no exchange of heat with the surroundings, the
mass of the two phases remains constant.
For liquid vapour equilibrium, the vapour pressure is constant at
a given temperature.
For dissolution of solids in liquids, the solubility is constant at a given
temperature.
For dissolution of gases in liquids, the concentration of a gas in liquid
is proportional to the pressure (concentration) of the gas over the
liquid.
 Equilibrium In Chemical Processes – Dynamic
Equilibrium

Chemical reactions attain a state of equilibrium when the

reactions which occur both in forward and backward directions
reaction rates are equal.
This equilibrium is said to be dynamic equilibrium when
forward reaction in which the reactants give product(s) and
reverse reaction in which product(s) gives the original reactants.
Consider the general equation as
A+B → C+D
 Law Of Chemical Equilibrium and
Equilibrium Constant
A mixture of reactants and products in the equilibrium state is called
an equilibrium mixture.

Consider a general reversible reaction:

A+B → C+D
Equilibrium Equation

The concentrations in an equilibrium mixture are related by the

equilibrium equation.
[C][D]
Kc or Kp =
[A][B]

Where Kc is the equilibrium constant

Law of Chemical Equilibrium

At a given temperature, the product of concentrations of the reaction

products raised to the respective stoichiometric coefficient in the
balanced chemical equation divided by the product of concentrations
of the reactants raised to their individual stoichiometric coefficients
has a constant value. This is known as the Equilibrium Law or Law of
Chemical Equilibrium.
 Law of Mass Action
• Law of Mass Action: For a reversible reaction at equilibrium and
constant temperature, a certain ratio of reactant and product
concentrations has a constant value (K).
• Equilibrium Constant (K): A number equal to the ratio of the
equilibrium concentrations of products to the equilibrium
concentrations of reactants each raised to the power of its
stoichiometric coefficient.
For the general reaction:

aA (g) + bB (g) cC (g) + dD (g)

[C]c[D]d
Kc or Kp =
[A]a[B]b
 Homogeneous Equilibria
All the reactants and products are in the same phase in Homogeneous
system.

Equilibrium Constant in Gaseous Systems

Equilibrium constant in gaseous systems is expressed in terms of partial
pressure.
Ideal gas equation is pV = nRT
p = cRT; where c = (n/V)
Thus p = [gas]RT
Hence at constant temperature, the pressure of the gas is proportional to
its concentration
p ∝ [gas]
For the general reaction:

aA (g) + bB (g) cC (g) + dD (g)

where Δn= (number of moles of gaseous products) – (number of moles of

gaseous reactants)
 Heterogeneous Equilibria
Equilibrium in a system having more than one phase is called
Heterogeneous Equilibrium
Example: CaCO3 (s) ↔ CaO (s) + CO2 (g)

[CaO] (PCO 2 )
Hence K eq 
[CaCO3 ]
K p  PCO 2
Even though the concentrations of the solids or liquids do not appear in
the equilibrium expression, the substances must be present to achieve
equilibrium.
Features of Equilibrium constants
Equilibrium constant is applicable only when concentrations of the
reactants and products have attained their equilibrium state.
The value of equilibrium constant is independent of initial
concentrations of the reactants and products.
Equilibrium constant is temperature dependent having one unique
value for a particular reaction represented by a balanced equation at
a given temperature.
The equilibrium constant for the reverse reaction is equal to the
inverse of the equilibrium constant for the forward reaction.
The Equilibrium Constant is taken as a dimensionless number with
all concentration values referenced to a standard state
 Applications Of Equilibrium Constants

predict the extent of a reaction on the basis of its magnitude,

predict the direction of the reaction
calculate equilibrium concentrations
 Predicting the Extent of a Reaction
The numerical value of the equilibrium constant for a reaction
indicates the extent of the reaction
• K >>1, Reaction proceeds nearly to completion
• K<<1 reaction does not occur to any appreciable extent
• 103 > K >10-3 appreciable concentrations of both reactants and
products are present
 Predicting the Direction of the Reaction
Reaction Quotient (Q): Similar to Kc, where concentrations are not at
equilibrium plugged into the equilibrium expression

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

Qc > Kc, the reaction will proceed in the direction of reactants Reverse
reaction dominates

Qc < Kc, the reaction will proceed in the direction of the products
Forward reaction dominates
 Relationship Between K, Q and G
 If ΔG is negative, then the reaction is spontaneous
 If ΔG is positive, then reaction is non-spontaneous
 If ΔGis 0, then reaction has achieved equilibrium

The equilibrium equation is

ΔG= ΔGѳ + RT lnQ
At equilibrium, when ΔG= 0 and Q= Kc
ΔG= ΔGѳ + RTln K= 0
ΔGѳ = – RT lnK
lnK = – ΔGѳ/ RT
K = e– ΔGѳ/ RT
The reaction spontaneity can be interpreted in terms of the value of ΔGѳ as
If ΔGѳ < 0, then –ΔGѳ /RT is positive, and e– ΔGѳ/ RT >1, making K >1,
which implies a spontaneous reaction or the reaction which proceeds in
the forward direction to such an extent that the products are present
predominantly.
If ΔGѳ > 0, then –ΔGѳ/RT is negative, and e– ΔGѳ/ RT < 1, that is , K < 1,
which implies a non-spontaneous reaction or a reaction which
proceeds in the forward direction to such a small degree that only a
very minute quantity of product is formed( Backward reaction).
 Factors affecting Equilibria
Le Chatelier’s principle:
It states that a change in any of the factors that determine the
equilibrium conditions of a system will cause the system to change
in such a manner so as to reduce or to counteract the effect of the
change.
 Effect of Concentration Change
Changing the concentration of a reactant or product will shift the
position of an equilibrium to minimise the change

 No change in Keq

CO(g) + 3H2(g) → CH4(g) + H2O(g) ∆H˚= -206.5 KJ

 Adding reactants: Equilibrium shifts right

 Removing reactants: Equilibrium shifts left
 Adding products: Equilibrium shifts left
 Removing products: Equilibrium shifts right
 Effect of Pressure Change

 Keq does not change

CO(g) + 3H2(g) → CH4(g) + H2O(g), ∆H˚= -206.5 KJ

 Increase in pressure – decrease in volume
Equilibrium shifts towards less moles
 Decrease in pressure – increase in volume
Equilibrium shifts towards more moles
Effect of Inert Gas Addition

If the volume is kept constant and an inert gas such as argon is

added which does not take part in the reaction, the equilibrium
remains undisturbed.
The addition of an inert gas at constant volume does not change the
partial pressures or the molar concentrations of the substance
involved in the reaction.
Effect of Temperature Change
When a change in temperature occurs, the value of equilibrium
constant, Kc is changed.

CO(g) + 3H2(g) → CH4(g) + H2O(g) + 206.5 KJ

Exothermic reaction – Increase in temp.

 Equilibrium shifts left
 Keq decreases
Exothermic reaction – Decrease in temperature
 Equilibrium shifts right
 Keq increases
The temperature dependence of the equilibrium constant depends on
the sign of ΔH for the reaction.
The equilibrium constant for an exothermic reaction (negative ΔH)
decreases as the temperature increases.
The equilibrium constant for an endothermic reaction (positive ΔH)
increases as the temperature increases.
Effect of a Catalyst

A catalyst increases the rate of the chemical reaction by making

available a new low energy pathway for the conversion of reactants
to products.
Speeds up a reaction equally in both directions.
Catalyst does not affect the equilibrium composition of a reaction
mixture.
Reactions reaches equilibrium quickly, but no change in the amount
of product.
 Ionic Equilibrium in Solution
The type of equilibrium involving ions in aqueous solution is called
Ionic equilibrium.
The acid-base dissociation equilibrium of a weak acid HA

HA(aq) + H2O(l) → H3O+(aq) + A–(aq)

acid base conjugate conjugate
acid base

The equilibrium moves in the direction of formation of weaker acid and

weaker base because the stronger acid donates a proton to the stronger
base
Strong acids have very weak conjugate bases
 Acids, Bases and Salts
Arrhenius Concept of Acids and Bases

• Acids produce hydrogen ions (H+) in an aqueous solution, while

bases produce hydroxide ion (OH-).
Acid: HCl (aq)  H+ (aq) + Cl- (aq)
Base: NaOH(aq)  Na+(aq) + OH-(aq)
 Brönsted-Lowry Acids and Bases
• An acid is a proton (H+) donor.
• A base is a proton (H+) acceptor.
• Example:
HF + H2O  H3O+ + F- ( H3O+ : Hydronium ion)
Acid Base

Conjugate Acids and Bases

• General expression:
HA (aq) + H2O (l)  H3O+ (aq) + A- (aq)
Acid Base Conjugate Conjugate
Acid Base
Conjugate acid is the particle formed that has received the proton. (ex:
H3O+)
Conjugate base is the particle left from the acid once it has donated
the proton

H+ H+

NH3(aq) + H2O (l)  NH4 + (aq) + OH- (aq)

Base Acid Conjugate Conjugate
Acid Base

The acid-base pair that differs only by one proton is called a conjugate
acid-base pair.
 Lewis Acids and Bases
An acid accepts a pair of electrons
A base donates a pair of electrons

Example: NH3 + H+  NH4+

The Lewis theory defines an acid as a species that can accept an electron
pair from another atom, and a base as a species that can donate an
electron pair to complete the valence shell of another atom
 Three Models of Acids and Bases

Model Definition of Definition of

Acid Base
Arrhenius H+ producer OH- producer

Bronsted-Lowry H+ donor H+ acceptor

Lewis Electron-pair Electron-pair

acceptor donor
 Ionization of Acids and Bases
Ionization Constant of Water and its Ionic Product

• All aqueous solutions will contain H+ and OH- ions

• For an acid solution [H+] > [OH-]
• For an alkaline solution [H+] < [OH-]
• For an neutral solution [H+] = [OH-]
H2O(l) + H2O (l) H3O+(aq) + OH-(aq)

H2O(l) H+(aq) + OH-(aq)

Kc = [H+][OH-]
[H2O]
 In pure water [H+] = [OH-]

At 298K, [H+] = 1 x 10-7

So at 289K the pH of pure water is 7

Ionic Product Of Water: Kw = [H+][OH-] mol2dm-6

At 298K the value of Kw is 1 x 10-14 mol2dm-6

By increasing temperature pH of water will decrease

 pH Scale
The pH of a solution is defined as the negative logarithm of the molar
hydrogen-ion concentration

pH   log[ H ]

Neutral solution: Hydrogen-ion concentration is 1.0 x 10-7, the pH = 7.00

Acidic solutions: the hydrogen-ion concentration is greater than 1.0 x 10-
7
, so the pH is less than 7.00
Basic solution: It has a pH greater than 7.004
 Relation between Ka and Kb

Considering the example of NH4+ and NH3

NH4+(aq) + H2O(l) → H3O+(aq) + NH3(aq)

Ka = [H3O+][ NH3] / [NH4+] = 5.6 x10–10

NH3(aq) + H2O(l) → NH4+(aq) + OH–(aq)

Kb =[ NH4+][ OH–] / NH3 = 1.8 X 10–5

Net: 2 H2O(l) → H3O+(aq) + OH–(aq)

Kw = [H3O+][ OH– ] = 1.0 X 10–14 M

The equilibrium constant of the net reaction is equal to the product of
equilibrium constants Ka and Kb for the reactions added

Ka Kb = {[H3O+][ NH3] / [NH4+ ]}{[NH4+ ] [ OH–] / [NH3]}

= [H3O+][ OH–] = Kw
= (5.6 X10–10) (1.8 X10–5) = 1.0 X 10–14 M
Hence KNET = K1 K2 ……

For conjugate acid-base pair, Ka Kb = Kw

pK values of the conjugate acid and base are

pKa + pKb = pKw = 14 (at 298K)
 Hydrolysis of Salts and the pH of their Solutions
Process of interaction between water and cations/anions or both of
salts is called hydrolysis.
Types of hydrolysis of the salts are:
• Salts of weak acid and strong base.
Eg:CH3COONa.
• Salts of strong acid and weak base
Eg:NH4Cl,
• Salts of weak acid and weak base
Eg:CH3COONH4.
The degree of hydrolysis is independent of concentration of solution.
And the pH value of the solution depends on the pK values
pH = 7 + (pK – pK )
 Buffer Solutions
“Solutions which resist changes in pH when small
quantities of acid or alkali are added.”
Acidic Buffer (pH < 7) made from a weak acid + its sodium or potassium salt
ethanoic acid sodium ethanoate

Alkaline Buffer (pH > 7) made from a weak base + its chloride
ammonia ammonium chloride
 Solubility Equilibria of Sparingly Soluble Salts
The solubility depends on the lattice enthalpy of the salt and the
solvation enthalpy of the ions in a solution
For a salt to be able to dissolve in a particular solvent its solvation
enthalpy must be greater than its lattice enthalpy

Classification of salts on the basis of their solubility

Solubility Product Constant

The equilibrium constant for the equilibrium established between a

solid solute and its ions in a saturated solution
CaSO4(s) Ca2+(aq) + SO42-(aq)

Ksp = [Ca2+][SO42-]

Ksp >> 1 for all the substances that are 100% ionized
Common Ion Effect on Solubility of Ionic Salts

The ion product (Qsp) is related to the solubility product (Ksp) by

Qsp < Ksp, more solute can dissolve

Qsp > Ksp, precipitate forms

Qsp = Ksp, the solution is saturated

The solubility S increases with increase in [H+] or decrease in pH