EQUILIBRIUM

EQUILIBRIUM
IN a reversible process where the rate of forward process is equal to rate of backward process, then
the condition is called equilibrium where all observable quantities become constant

What is Physical Equilibrium?

Physical equilibrium is defined as the equilibrium which develops between different phases or
physical properties. In these processes, there is no change in chemical composition. It represents the
existence of the same substance in two different physical states. The physical equilibrium can be:
 Phase equilibrium
 Solute-solid equilibrium
 Gas-liquid equilibrium

Type of Physical Equilibrium

 Types of Physical Equilibrium
 Solute-Solid Equilibrium
 Examples
 Liquid-Gas Equilibria
 Solid-Vapour Equilibria
Equilibrium indicates the constancy of content and composition (as measured by colour, pressure or
temperature) of an item of interest in a system, irrespective of the time period. In the Equilibrium
state, the rate of the forward reaction is equal to the rate of the backward reaction.
A book on a table, liquid in a closed container, saturated solution, ionic substances in polar
solvents, manufacture of ammonia are some examples of equilibrium

Types of Physical Equilibrium

Phase Equilibrium:
At 0°C, the number of water molecules becoming ice is equal to the water molecules as ice melting
to form liquid water. Rate of freezing of water is equal to the rate of melting of ice. Thus, there is an
equilibrium between solid ice and liquid water.
Ice (s) ⇌ Water (l)
The number of molecules of a liquid becoming vapour will be equal to the number of molecules
condensing into liquid in a closed container. Rate of evaporation of liquid water is equal to the rate
of condensation of water vapour. Liquid phase is in equilibrium with its own vapour phase.
Water (l) ⇌ Water (g)

Solute-Solid Equilibrium:
When a solute in a saturated solution is in contact with undissolved solute, the number of molecules
going (depositing) out of the solution is equal to the number of molecules entering (dissolving) from
the solid into the liquid. So the solute in a solution is in equilibrium with the undissolved solid.
Solute (aq) ⇌ Solute (s)

Gas-Liquid Equilibrium:
Gases that do not react with liquid may dissolve directly related to the pressure in the liquid. In a
closed container, there is an equilibrium between the gas inside the liquid and the gas present above
the liquid. In soft drinks, for example, carbon dioxide gas in the liquid is in equilibrium with the gas in
the empty space of the container.
Gas (solution) ⇌ Gas (g)

Examples of Physical Equilibrium

Examples of Solid-Liquid Equilibria:
Consider ice and water in a perfectly insulated thermos flask at 00C in an open atmosphere. There
will be no change in the level of water and quantity of ice, which implies that the rate of transfer of
molecules from water to ice is equal to the rate of transfer of molecules from ice to water.
Hence, we can conclude that this system is in a steady state. This can be represented by the
following equation:
H2O (s)⇌ H2O (l)
The rate of melting = Rate of freezing

Examples of Liquid-Gas Equilibria:

Take distilled water in a closed container and start heating, the water converts to vapour. After a
certain time, we will observe that the level of water becomes constant implying that there is no
more conversion of water to vapour and vice-versa.
We can technically say that the rate of evaporation (liquid to vapour) is equal to the rate
of condensation (vapour to liquid) thus achieving a steady state. This equation can be represented
by the following equation:
H2O (l) ⇌ H2O (g)
The rate of evaporation = Rate of condensation

Examples of Solid-vapour Equilibria:

This kind of equilibrium can exist only in the case of sublimates (solid directly converts to vapour).
Consider heating of solid iodine in a closed container, slowly the vessel is filled with violet coloured
vapour and the intensity of colour increases with time.
After a certain time, the intensity of colour doesn’t change with time. This implies a steady state is
attained where the rate of sublimation of solid iodine is equal to the rate of deposition of iodine
vapour.
I2 (s) ⇌ I2 (vapour)
The rate of sublimation = Rate of deposition.

What is Chemical Equilibrium?

Chemical equilibrium refers to the state of a system in which the concentration of the reactant and
the concentration of the products do not change with time and the system does not display any
further change in properties.
 Types of Chemical Equilibrium
When the rate of the forward reaction is equal to the rate of the reverse reaction, the state of
chemical equilibrium is achieved by the system. When there is no further change in the
concentrations of the reactants and the products due to the equal rates of the forward and reverse
reactions, the system is said to be in a state of dynamic equilibrium.

State of Chemical Equilibrium

A graph with the concentration on the y-axis and time on the x-axis can be plotted. Once the
concentration of both the reactants and the products stops showing change, chemical equilibrium is
achieved.
Why Chemical Equilibrium is called Dynamic Equilibrium?
The stage at which the rate of the forward reaction is equal to the rate of backward reaction is called
an equilibrium stage. At this point, the number of reactant molecules converting into products and
product molecules into reactants are the same. The same equilibrium can be carried out with the
same reactants anywhere with similar conditions with continuous interchanging of molecules hence
chemical equilibrium is dynamic.

Types of Chemical Equilibrium

There are two types of chemical equilibrium:
 Homogeneous Equilibrium
 Heterogeneous Equilibrium

Homogenous Chemical Equilibrium

In this type, the reactants and the products of chemical equilibrium are all in the same
phase. Homogenous equilibrium can be further divided into two types: Reactions in which the
number of molecules of the products is equal to the number of molecules of the reactants. For
example,
 H2 (g) + I2 (g) ⇌ 2HI (g)
 N2 (g) + O2 (g) ⇌ 2NO (g)
Reactions in which the number of molecules of the products is not equal to the total number of
reactant molecules. For example,
 2SO2 (g) + O2 (g) ⇌ 2SO3 (g)
 COCl2 (g) ⇌ CO (g) + Cl2 (g)

Heterogeneous Chemical Equilibrium

In this type, the reactants and the products of chemical equilibrium are present in different phases.
A few examples of heterogeneous equilibrium are listed below.
 CO2 (g) + C (s) ⇌ 2CO (g)
 CaCO3 (s) ⇌ CaO (s) + CO2 (g)
Thus, the different types of chemical equilibrium are based on the phase of the reactants and
products.
⇒ Check: Ionic Equilibrium

Factors Affecting Chemical Equilibrium

 Chemical Equilibrium – Factors Affecting Equilibrium
According to Le-Chatelier’s principle, if there is any change in the factors affecting the equilibrium
conditions, the system will counteract or reduce the effect of the overall transformation. This
principle applies to both chemical and physical equilibrium.
There are several factors like temperature, pressure, and concentration of the system which affect
equilibrium. Some important factors affecting chemical equilibrium are discussed below.

Change in Concentration:
 The concentration of the reactants or products added is relieved by the reaction which
consumes the substance which is added.
 The concentration of reactants or products removed is relieved by the reaction which is in
the direction that replenishes the substance which is removed.
 When the concentration of the reactant or product is changed, there is a change in the
composition of the mixture in chemical equilibrium.

Change in Pressure:
Change in pressure happens due to the change in the volume. If there is a change in pressure it can
affect the gaseous reaction as the total number of gaseous reactants and products are now different.
According to Le Chatelier’s principle, in heterogeneous chemical equilibrium, the change of pressure
in both liquids and solids can be ignored because the volume is independent of pressure.

Change in Temperature:
The effect of temperature on chemical equilibrium depends upon the sign of ΔH of the reaction and
follows Le-Chatelier’s Principle.
 As temperature increases the equilibrium constant of an exothermic reaction decreases.
 In an endothermic reaction the equilibrium constant increases with increase in temperature.
Along with equilibrium constant, the rate of reaction is also affected by the change in temperature.
As per Le Chatelier’s principle, the equilibrium shifts towards the reactant side when the
temperature increases in case of exothermic reactions, for endothermic reactions the equilibrium
shifts towards the product side with an increase in temperature.
Effect of a Catalyst:
A catalyst does not affect the chemical equilibrium. It only speeds up a reaction. In fact, catalyst
equally speeds up the forward as well as the reverse reaction. This results in the reaction reaching its
equilibrium faster.
The same amount of reactants and products will be present at equilibrium in a catalysed or a non-
catalysed reaction. The presence of a catalyst only facilitates the reaction to proceed through a
lower-energy transition state of reactants to products.

Effect of Addition of an Inert Gas:

When an inert gas like argon is added to a constant volume it does not take part in the reaction so
the equilibrium remains undisturbed. If the gas added is a reactant or product involved in the
reaction then the reaction quotient will change.

Examples of Chemical Equilibrium

In chemical reactions, reactants are converted into products by the forward reaction and the
products may be converted into the reactants by the backward reaction. The two states, reactants
and products are different in composition.
After some time of the start of the reaction, the rate of the forward and the backward reactions may
become equal. After this, the number of reactants converted will be formed again by the reverse
reaction such that the concentration of reactants and products do not change any more. Hence, the
reactants and products are in chemical equilibrium.
 N2O4 ⇌ 2NO2
 PCl5 ⇌ PCl3 +PCl2
 N2 + H2 ⇌ 2NH3

Importance of Chemical Equilibrium?

It is useful in many industrial processes like,
 Preparation of ammonia by Haber’s process: In this nitrogen combines with hydrogen to
form ammonia, the yield of ammonia is more at low temperature, high pressure and in the
presence of iron as catalyst.
 Preparation of sulphuric acid by contacts process: In this process, the fundamental reaction
is the oxidation of sulphur dioxide into sulphur trioxide. This involves chemical equilibrium.

Problems on Chemical Equilibrium

1. The equilibrium constant KP for the reaction N2 (g) + 3H2 (g) ⇌ 2NH3 (g) is 1.6 × 10-4 atm-2 at 400oC.
What will be the equilibrium constant of the Chemical equilibrium at 500 oC if the heat of the
reaction at this temperature range is -25.14 kcal?
Solution:
Equilibrium constants at different temperature and heat of the reaction are related by the equation,
Log KP2 = -25140/2.303 × 2 [773 – 673 / 773 × 673] + log 1.64 × 10-4
Log KP2 = -4.835
KP2 = 1.462 × 10-5 atm-2
2. Given the equation, N2 (g) + 3H2 (aq) ⇌ 2NH3 (g), Find Q and determine which direction the
reaction will shift in order to reach the state of chemical equilibrium.
Solution:
Given, [N2] = 0.04M, [H2] = 0.09M, and K = 0.040
Since only nitrogen and hydrogen concentration is given, it can be assumed as the reactants and
ammonia as the product. Since ammonia concentration is not given it can be assumed to be zero.
As q is the ratio of the relative concentration of products to reactants, here Q =0.
Since K = 0.04 is larger than Q, nitrogen and hydrogen will combine to form product ammonia.

Ionic Equilibrium - Ostwald Dilution law

In Ionic equilibrium, the ionic substance dissociates into their ions in polar solvents. The ions formed
are always in equilibrium with its undissociated solute in the solution.
⇒ Representation of Ionic Equilibrium: Xa Yb ⇌ aXb+ + bYa-

Introduction to Ionic Equilibrium

Reactants and products coexist in equilibrium so that reactant conversion to product is always less
than 100%. Equilibrium reactions may involve the decomposition of a covalent (non-polar) reactant
or ionization of ionic compounds into their ions in polar solvents.
In this section, we will learn about the ionic equilibrium in ionic solutions. Substances in Ionic
Equilibrium can be classified into two categories on the basis of their ability to conduct electricity
given as under,

Non-Electrolytes
These are substances that consist of molecules that bear no electric charge, do not dissociate into
their constituent ions and thus do not conduct electricity in their aqueous solution or molten state.
For example sugar solution.

Electrolytes
These are substances that dissociate into their constituent ions in their aqueous solution and thus
conduct electricity in their aqueous solutions or molten state. Example, salt solution, acid solution,
base solution etc.
Electrolytes in ionic equilibrium can be further classified into strong and weak electrolytes.
Strong electrolytes are substances that upon dissociation in their ionic solution ionize completely
while in the case of weak electrolytes, the dissociation is partial in nature.
For example, NaCl undergoes complete ionization in its aqueous solution to render sodium ions (Na +)
and chloride (Cl–) ions, whereas, acetic acid undergoes partial ionization to render some amount of
acetate ions(CH3COO–) and hydrogen(H+) ions.
  In case of a strong electrolyte, the dissociation reaction is said to be complete, thus moving
in the forward direction only, whereas, in case of a weak electrolyte, the reaction is said to
be reversible in nature.
 In the case of the weak electrolyte, the equilibrium is established between the ions and the
unionized molecules, which can be termed as ionic equilibrium. The same can be understood
with the following example.

Ostwald’s Dilution Law: Degree of Dissociation

Ostwald’s dilution law is the application of the law of mass action to weak electrolytes in solution.
A binary electrolyte AB which dissociates into A+ and B– ions.

Degree of ionization increases on dilution. Thus, degree of dissociation of a weak electrolyte is

proportional to the square root of dilution.

Limitations of Ostwald’s Dilution law

The law holds good only for weak electrolytes and fails completely in the case of strong electrolytes.
Acids and Bases
Earlier Definitions of Acids and Bases
Earlier definitions of acids and bases was given by Robert Boyle, who classified them on the basis of
their properties. According to him, acids are the substance which have sour taste. Turns blue litmus
red. Liberate hydrogen with metals, conduct electricity in aqueous solution and neutralise bases.
Bases are the substance which have bitter taste, turns red litmus blue, soapy to touch, conduct
electricity in aqueous solution and neutralise acids.
Arrhenius Concept of Acids and Bases
 Acid is a chemical substance which dissociates in aqueous solution to give hydrogen ions (H +)
or hydronium ions (H3O+).
  Base is a chemical substance which dissociates in aqueous solution to give hydroxyl ions
(OH–).
 Arrhenius theory fails to explain the acidic and basic behaviour in non-aqueous solutions. It
cannot explain the acidic character of A1Cla. BFa and basic character of NH3, PH3, etc.
Bronsted & Lowry Concept of Acids and Bases
Acid is a chemical substance that can donate a proton (H+) to some other substance and a base is a
chemical substance that can accept a proton from other substance. Thus, an acid is a proton donor
(protongenic) and a base is proton acceptor (protopbilic).

Strong acid has weak conjugate base and weak acid has strong conjugate base Strong base has weak
conjugate acid and weak base has strong conjugate acid.
HClO4 is the strongest while HCN is the weakest hydracid known.
CsOH is the strongest base known.
Amphoteric or arnphiprotic substance or ampholytes are the substance which act as an acid as well
as a base, e.g.• water acts as an acid with NH3 and a base with acetic acid.
The order of acidic strength of some acids is
HClO4 > HBr> H2SO4 > HCl> HNO3
Greater the Ka value of an acid (or lesser the pKa), stronger is the acid. Similarly. greater the Kb (or
lesser the pKb) of a base. stronger is the base.

Lewis Concept of Acids and Bases

Lewis acid is a chemical substance which can accept a pair of electrons,
e.g.,
1. Molecules with incomplete octet of central atom like AlCl3 ,BeCl2, MgCl2, etc.
2. Simple cations like Ag+, Na+, etc.
3. Molecules in which the central atom has vacant d-orbital, e.g.,SF4, SnC14 PF3 etc.
Lewis base is a chemical substance which can donate a pair of electrons. e.g.,
1. Neutral molecules containing lone pairs like NH3, RNH2, ROH etc.
2. Negatively charged species like CN, Cl. OH, etc.
3. In coordination complexes, the ligands act as Lewis base.
Limitations of Lewis Concept
1. It does not explain the behaviour of protonic acids such as HCl, H4SO4, HNO3 etc.
2. It does not predict the magnitude of relative strength of acids and bases.
All Bronsted-Lowry’s acids are Lewis acids while acids need not be Bronsted-Lowry’s acids.
IONIC PRODUCT OF WATER
The Ionization Constant of Water Ionic product is the product of the concentration of hydronium
ions and hydroxyl ion in pure water, which remains constant at a particular temperature. It is
symbolized by Kw. At 298 K, ionic product of water (KW) is given as K w :=¿
The value of Kw increases with increase in temperature.
The pH Scale
pH is defined as the negative logarithm of hydrogen ion concentration.
pH = – log [H+]
Total [H+] or [OH–] in a mixture of two strong acids or bases similarly, negative logarithm of hydroxyl
ion concentration is pOH.

pH value of an acid having H+ concentration less than 10-7, is always in between 6 and 7. For 10-8 N
HCl solution. it is 6.958.Similarly for 10-8 NaOH solution, the pH is 7.04 (because basic solutions
always have pH 77.)
pH of solution is accurately measured by pH meter or emf method or roughly by pH paper or
indicator paper.
(PH can be zero in 1 N HCl solution or it can be negative for more. concentrated solution like 2N, 3N,
lON, etc,
pH range for some important substances are :
Gastric juice = 1 – 3
Vinegar = 2.4 – 3.4
Dissociation Constant of Weak
Acid and Weak Base
Let us consider the dissociation of weak acid (HA) as
Dissociation constant for polyprotic acids and bases. For a tribasic acid,

The overall dissociation constant (K) is given as

K = K 1 x K2 x K3
where, K1 x K2 x K3

Similarly, for a dibasic acid like H2CO3

pH = pka1 + pka2/2)
Buffer Solution
Solution which resists the change in its pH value by addition of a small amount of acid or a base, is
called buffer solution.
 Acidic buffer They have pH value < 7, e.g., CH3COOH/CH3COONa, bone acid/borax.
 Basic buffer They have pH value> 7 e.g., NH4OH/NH34Cl
Buffer system present in blood is H2CO3 + NaHCO3.
Henderson-Hesselbalch Equation
Equation used to calculate the pH of a buffer solution.
(i) For acidic buffer,
pH = pKa + log[salt/acid]
(i) pOH = pKb + log[salt/acid]
and pH = 14 – pOH
Here, pKa = -log Ka, pKb = -log Kb and Ka and Kb are dissociation constants of acid and base.
[salt), [acid] and [base) represent molar concentrations of salt, acid and base respectively.
If addition of a strong acid or base changes the pH of a buffer by/unit, the buffer solution is assumed
to destroyed, i.e.,
New pH = pKo ± 1
This means the ratio.
[salt]/[acid) or [salt]/[base] = 10 or (1/10)
Buffer Capacity
It is defined as the number of moles of acid or base added in 1 L of solution Lochange the pH by
unity.
Buffer capacity (φ)
= (no. of moles of acids or base added to 1 L of buffer/change in pH)
Salts
These are the product of reaction between an acid and a base.
This reaction is called neutralisation reaction.
Types of Salts
(a) Normal salts These are obtained by complete neutralisation of an acid with a base, e.g., NaCI,
K2SO4, etc.
(b) Acidic salts These are formed by incomplete neutralisation of polybasic acids. e.g., NaHCO3,
Na2SO4 etc.
(c) Basic salts These are formed by incomplete neutralization of polyacidic base, e.g., Mg(OH)Cl,
Bi(OH)2Cl, etc.
(d) Double salts These are formed by the combination of two simple salts and exist only in solid
state, e.g., Mohr salt or ferrous ammonium sulphate (FeSO4.(NH4)2SO4.6H2O], alum, etc.
(e) Complex salts These are formed by the combination of simple salts or molecular compounds.
These are stable in solid state well as in solutions.
The properties of their solutions are different from the properties of substances from which they
have been constituted.
(f) Mixed salts These salts furnish more than one cation or more than one anion when dissolved in
water, e.g., Ca(OCl)Cl, NaKSO4, etc.
Salt Hydrolysis
Salts are strong electrolytes and on dissolution in water split up into ions which react with H + or OH–
ions furnished by water yielding acidic or basic solution. The process is known as salt hydrolysis.

Aqueous solution of salt of strong acid and strong base is neutral Aqueous solution of salt of a weak
acid and a strong base is alkaline due to anionic hydrolysis, and aqueous solution of salt of strong
acid and a weak base is acidic due to cationic hydrolysis with dilution degree of hydrolysis increases.
Hydrolysis is a reverse process of neutralisation.
Common Ion Effect
It is.defined as the suppression of the dissociation of a weak electrolyte by the addition of a strong
electrolyte having some common ion, e.g., degree of dissociation of ammonium hydroxide decreases
in the presence of ammonium chloride.
According to Le-Chatelier principle, because of the presence of common ion. degree of dissociation
of NH4OH decreases.
Colnmon ion effect is used in
1. Purification of common salt
2. Salting out of soap
3. Qualitative analysis, II group radicals are precipitated out in the presence of HCI which
suppress the S2- ion concentration, which is just sufficient to precipitate only II group
radicals.
Similarly in group III, NH4OH is added in presence ofNH4Cl to avoid the precipitation of V group
radicals.
Isohydric Solutions
If the concentration of the common ions in the solution of two electrolytes, e.g., OH- ion
concentration in Ca(OH)2 and Ba(OH)2 solutions, is same then on mixing them there is no change in
degree of dissociation of either of the electrolytes. Such solution are called isohydric solutions.
Solubility Product
It is defined as the product of the concentrations of the ions of the salt in its saturated solution at a
given temperature raised to the power of the ions produced by the dissociation of one mole of the
salt. It is denoted by Ksp.
Consider the dissociation of an electrolyte AxBy

Application of Solubility
1. The concept Product of Ksp helps in predicting the formation of precipitate. In general if
1. Ionic product < Ksp,no ppt. is formed.
2. Ionic product > Ksp, ppt. is formed.
2. In predicting the solubility of a sparingly soluble salt

knowing the values of Ksp, x and y, the solubility of the salt can be Computed.
Ksp of AgI is lower than t.hat of Agel. So the former gets precipitated in preference to later.
Distinction Between Solubility Product and Ionic Product

Acid-Base Indicator

Ionic Equilibrium Formulas

It becomes necessary to know what fraction of the initial amount of the reactants are converted into
products at equilibrium.
The fraction of the initial molecules that are converted at equilibrium is called the degree of
Dissociation/ionization.
Number of reactant molecules dissociated ¿ at the start
Degree of dissociation or ionization = α =
Number of reactant molecules at the start

Degree of dissociation in Ionic equilibrium can be expressed in percentage.

% Degree of dissociation or
Number of reactant molecules dissociated∨ionized at the start
ionization ¿ α = ×100
( Number of reactant molecules at the start )

Degree of Ionization
The degree of ionization depends on
 Nature of the electrolyte: strong, weak, insoluble
 Nature of the solvent: High dielectric solvents increase ionization
 Dilution: larger the dilution higher the ionization
 Temperature: higher the temperature, larger the ionization and
 Presence of common ions decreases the ionization of the weak electrolyte.

Dissociation of Ionic Compounds in Polar Solvents

Ionic compounds dissolve in polar solvents with ionization into cations and anions.
The ionized ions are in equilibrium with the un-dissociated molecules.
x−¿ ¿
¿
Ax+ By ⇌ x A y+¿+ y B
Ionic Solids in Solutions
Strong electrolytes (α ≈100% ionization), Weak electrolytes (α ≈ 10% ionization), Sparingly soluble (α
≈100% ionization)
Example: HCl, NaOH, Salts NH4OH, Organic acids AgCl, BaSO4

Ionization of Weak Electrolytes

In infinite dilution, all electrolytes are fully ionized. In a concentrated solution, weak electrolytes
exist in equilibrium with their unionized molecules. Concentrations of the ions are important in
many practical situations like acid-base solubility, and conductance of the solution.

Common Ion Effect on Degree of Dissociation

Weak electrolytes are poorly ionized in aqueous solution. Their ionization may further be reduced if
one of the ions are present from another source. This called a common ion effect.
i) Ammonium hydroxide is a weak base. On addition of ammonium chloride (a salt) ammonium ion
from it, will make the ammonium ions to combine with the hydroxide to form unionized ammonium
hydroxide.
NH4Cl → NH4+ + Cl–
NH4OH ⇌ NH4+ + OH–
ii) In the base hydrolysis of oil, the sodium salt of the fatty acid (soap) is in a dissolved state.
When sodium chloride salt is added, the concentration of Na+ ions increases considerably.
CnH2n+1 + COONa ⇌ CnH2n+1 COO– + Na+
NaCl ⇌ Na+ + Cl–
Hence, the ionic product [CnH2n+1COO–] [Na+] exceeds the solubility product of soap and, therefore,
soap precipitates out from the solution. This is called salting out of soap.
(iii) Manufacture of sodium bicarbonate (baking soda):
In Solvay’s soda process. The CO2 gas is passed through ammonical brine to precipitate out NaHCO3.
NH4OH + CO2 → NH4HCO3
NH4HCO3 + NaCl → NH4HCO3 + NH4Cl
NaHCO3 is precipitated first because of its lower solubility product as compared to those of NH 4Cl,
NH3HCO3 and NaCl.