Equilibrium
Equilibrium in physical processes:
Solid-liquid equilibrium
For any pure substance at atmospheric pressure, the temperature at which the solid and
liquid phases are at equilibrium is called the normal melting point or normal freezing point
of the substance.
Liquid-vapour equilibrium
Solid-vapour equilibrium
Equilibrium in chemical processes-Dynamic equilibrium:
Fig: Attainment of chemical equilibrium
Law of chemical equilibrium and equilibrium constant:
A+B⇔C+D
Equilibrium equation:
Where, Kc = Equilibrium constant
Relations between equilibrium constants for a general reaction and its multiples:
aA + bB ⇔ cC + dD ; Kc
cC + dD ⇔ aA + bB ;
= (1/Kc)
naA + nbB ⇔ ncC + ndD ;
Homogeneous equilibria:
All the reactants and products are in the same phase.
Equilibrium constants in gaseous systems:
Or, Kp = Kc (RT)Δn
Heterogeneous equilibria:
Having more than one phase:
[As the molar concentration of a pure solid or liquid is constant, therefore, [Ni(s)] is
constant]
Applications of equilibrium constants:
Predicting the extent of a reaction
1. If Kc > 103, then products predominate over reactants.
2. If Kc < 10–3, then reactants predominate over products.
3. If Kc is in the range of 10–3 to 103, then appreciable concentrations of both reactants and
products are present at equilibrium.
Predicting the direction of the reaction,
aA + bB ⇔ cC + dD
Reaction quotient,
(The concentrations in Qc are not necessarily equilibrium values)
1. If Qc > Kc, then the reaction will proceed in the reverse direction.
2. If Qc < Kc, then the reaction will proceed in the forward direction.
3. If Qc = Kc, then the reaction mixture is already at equilibrium.
Relation between K, Q, and G (Gibbs energy):
∆G = ∆GƟ + RT lnQ
At equilibrium, ∆G = 0, and Q = K
Therefore, ∆GƟ= –RT lnK
Or, lnK = –∆GƟ/RT
Or, K = e-ΔGn/RT
If ∆GƟ< 0, then –∆GƟ/RT is positive and e-ΔGn/RT > 1, therefore, K > 1. That is a spontaneous
reaction.
If ∆GƟ > 0, then –∆GƟ/RT is negative and e-ΔGn/RT < 1, therefore, K < 1. That is a non-
spontaneous reaction.
Le Chatelier’s principle 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.
Concentration change
When a reactant/product is added, the net reaction proceeds in the direction in which the
added substance is consumed.
When a reactant/product is removed, the net reaction proceeds in the direction in which
the removed substance is replenished.
Pressure change
When pressure is increased, the equilibrium shifts in the direction in which the number of
moles of gas or pressure decreases.
Addition of inert gas
At constant volume, addition of inert gas does not affect the equilibrium of a reaction.
Temperature change
The equilibrium constant for an exothermic reaction decreases with increase in
temperature.
The equilibrium constant for an endothermic reaction increases with increase in
temperature.
Effect of catalyst
Catalyst does not affect the equilibrium of a reaction.
Acids, Bases, and Salts
Arrhenius concept of acids and bases:
1. Acids are substances which dissociate in water to give H+ ions.
2. Bases are substances which dissociate in water to give OH– ions.
Bronsted–Lowry acids and bases:
1. Acids are substances that can donate H+ ions.
2. Bases are substances that can accept H+ ions.
3. The conjugate base of a strong acid is a weak base and vice-versa.
Lewis acids and bases:
1. Acids are species that accept electron pair.
2. Bases are species that donate electron pair.
Arrhenius concept of acids and bases
Strong acids and bases completely dissociate in aqueous solutions producing H3O+ and
OH− ions, respectively
Bronsted-Lowry concept of acids and bases
Based on conjugate pairs of acids and bases
Strong acid or base has weak conjugate base or acid
Strong and weak electrolytes
Strong electrolytes ionise in wate completely
Weak electrolytes undergo partial ionisation in water
Degree of dissociation
Extent to which an electrolyte dissociates in a solvent
Depends on the following factors:
Nature of solvent and electrolyte
Dilution
Temperature
The pH scale
pH = –log [H+]
pKw = pH + pOH = 14
For acidic solution, pH < 7
For basic solution, pH > 7
For neutral solution, pH = 7
Ionization constant and ionic product of water:
Ionization constant of water,
Ionic product of water,
At 298K, Kw = 1 × 10–14 M2
For acidic solution, [H3O+] > [OH–]
For neutral solution, [H3O+] = [OH–]
For basic solution, [H3O+] < [OH–]
The pH scale
pH = –log [H+]
pKw = pH + pOH = 14
For acidic solution, pH < 7
For basic solution, pH > 7
For neutral solution, pH = 7
pH =
= −log {[H+] / mol L−1}( = [H+]/mol L−1 = activity of H+ ion)
For pure water:
pH = −log (10−7)
=7
For acidic solution − pH < 7
For basic solution − pH > 7
For neutral solution − pH = 7
Kw = [H3O+] [OH−] = 10−14
⇒ pKw = pH + pOH = 14
Determination of pH: Using pH paper
Can be accurately determined by a pH meter.
Ionization constant for weak acids:
pKa = −log(Ka)
Ionization constants for weak bases:
Kb
Relation between Ka and Kb
Ka × Kb
pKa × pKb = pKw = 14
Factors affecting acid strength (the strength of H-A bonds is an important factor in
determining the strength of acids):
Hydrolysis:
Interaction of the anion or the cation (or both) of a salt with water to produce an acidic or a
basic solution.
Salts of strong acids and strong bases are neutral (pH = 7).
Salts of strong acids and strong bases are acidic (pH < 7).
Salts of weak acids and strong bases are basic (pH > 7).
Buffer solutions:
Buffer solutions are the solutions in which pH does not change on dilution or with the
addition of small amounts of acid or alkali.
General formula:
Where,
Solubility product:
