CHAPTER 7

EQUILIBRIUM

Equilibrium is actually a state, when forces from both the side become equal. According
to chemistry: It is a point in a chemical reaction, when rate of forward reaction becomes
equal to rate of backward reaction.
In other words,’The state of a system in which the measurable properties of the system
(like temperature,pressure etc.) do not undergo any further noticeable change under a
particular set of conditions is called state of equilibrium.
• Chemical Equilibrium
In a chemical reaction chemical equilibrium is defined as the state at which there is no
further change in concentration of reactants and products.
For example,

At equilibrium the rate of forward reaction is equal to the rate of backward reaction.
Equilibrium mixture: The mixture of reactants and products in the equilibrium state is
called an equilibrium mixtures.
Based on the extent to which the reactions proceed to reach the state of equilibrium,
these may be classified in three groups:
(i) The reactions which proceed almost to completion and the concentrations of the
reactants left are negligible.
(ii) The reactions in which most of the reactants remains unchanged, i.e. only small
amounts of products are formed.
(iii) The reactions in which the concentrations of both the reactants and products are
comparable when the system is in equilibrium.
• Equilibrium in Physical Processes
(i) Solid-Liquid Equilibrium: The equilibrium is represented as

Rate of melting of ice = Rate of freezing of water.

The system here is in dynamic equilibrium and following can be inferred.
(a) Both the opposing processes occur simultaneously
(b) Both the processes occur at the same rate so that the amount of ice and water –
remains constant.
(ii) Liquid-Vapour Equilibrium
The equilibrium can be represented as

Rate of evaporation = Rate of condensation

When there is an equilibrium between liquid and vapours, it is called liquid-vapour
equilibrium.
(iii) Solid-Vapour Equilibrium
This type of equilibrium is attained where solids sublime to vapour phase. For example,
when solid iodine is placed in a closed vessel, violet vapors start appearing in the vessel
whose intensity increases with time and ultimately, it becomes constant.

• Equilibrium between a Gas and its Solution in Liquid

This type of equilibrium can be seen by the following example:
Let us consider a sealed soda water bottle in which C02 gas is dissolved under high
pressure. A state of equilibrium is attained between CO2 present in the solution and
vapours of the gas.

Henry’s law: The solubility of a gas in a liquid at a certain temperature is governed by

Henry’s law. It states that the mass of a gas that dissolves in a given mass of a
solvent at any temperature is proportional to the pressure of the gas above the
surface of the solvent.

• Characteristics of Equilibria Involving Physical Processes

(i) The equilibrium can be attained only in closed systems at a given temperature.
(ii) At the equilibrium the measurable properties of the system remain constant.
(iii) The equilibrium is dynamic since both the forward and backward processes occur at
same rate.
(iv) At equilibrium, the concentrations of substances become constant at constant
temperature.
(v) The value of equilibrium constant represents the extent to which the process
proceeds before equilibrium is achieved.
• Equilibrium in Chemical Processes
Like equilibria in physical systems it can also be achieved in chemical process involving
reversible chemical reactions carried in closed container.

The dynamic nature of chemical equilibrium can be demonstrated in the synthesis of

ammonia by Haber’s process.

• Equilibrium in Homogeneous System(Homogeneous equilibrium)

When in a system involving reversible reaction, reactants and products are in the same
phase, then the system is called as homogeneous system.
For Example,

Heterogeneous Equilibrium
When the reactants and products involved in Equilibria are present in different phases,it
is called heterogeneous Equilibria.
For eg:
CaCO3(s) ===CaO(s)+CO2(g)
Law of mass action. It states that: Rate of a reaction is directly proportional to
concentration of reactants raised to their respective moles.
Consider a reaction: aA + bB --> cC + dD. According to this law:
R α [A]a[B]b
R =K [A] a [B] b. Where ‘K’ is rate constant or velocity constant.
Law of Chemical Equilibrium
At a constant temperature, the rate of a chemical reaction is directly proportional to the
product of the molar concentrations of the reactants each raised to a power equal to the
corresponding stoichiometric coefficients as represented by the balanced chemical
equation. Let us consider the reaction,
• Relationship between Equilibrium constant K, reaction Quotient Q and Gibbs energy G.
A mathematical expression of thermodynamic view of equilibrium can be described by
tine equation.
LAW OF CHEMICAL EQUILIBRIUM

At a given temperature, the product of molar concentration of products divided by that of

the reactants with each concentration terms raised to a power equal to its coefficient in
the balanced chemical equation has a constant value.
This constant is called equilibrium constant when the system is at equilibrium.When the
system is not at equilibrium, this ratio is called concentration quotient and is denoted by
Q.
At equilibrium ;
Q=K
In case of gaseous reactants, equilibrium constant can be expressed in terms of partial
pressure and can be denoted by Kp

Kp=PCc.PDd
PAa.PBb

Where PA,PB,PC and PD are partial pressures of A,B,C,D

RELATION BETWEEN Kp AND Kc

Consider a reaction :
Aa+bB==cC+dD

Kc=[C]c.[D]d
[A]a.[B]b

If the equilibrium involves gaseous species;

Kp=PCc.PDd
PAa.PBb

For ideal gases,

PV=nRT
P=n/V RT
P=CRT;Where C is concentration in Mol/L
PA=[A]RT PB=[B]RT
PC=[C]RT PD=[D]RT

Kp= ([C]RT)c .([D]RT)d

([A]RT)a .([B]RT)b

=[C]c.[D]d . (RT)(c+d)-(a+b)
[A]a.[B]b.

Kp=kc.RTΔn

Where Δn is number of moles of gaseous products -Number of moles of gaseous

reactants
When Δn=0; Kp =Kc

Characteristics of equilibrium constant

1. The equilibrium constant has a definite value for every reaction at a particular
temperature.
 2. The value of equilibrium constant is independent of the original concentration of
reactants.
3. The value of equilibrium constant tells the extent to which a reaction proceeds in the
forward or reverse direction. If the value of K is larger, then the equilibrium concentration
of the components on the right hand side of the reaction will be greater than the
components on the left hand side of the reaction. Hence the reaction proceeds to a
greater extent and vice versa.
4. The equilibrium constant is independent of the presence of catalyst. This is because
the catalyst affects the rate of forward reaction and backward reactions equally.
5. For a reversible reaction, the equilibrium constant for the forward reaction is inverse of
the equilibrium constant for the backward reaction i.e.
Kforward reaction> = 1 / Kbackward reaction>
6. Equilibrium constant is dependent on the temperature .
Application of equilibrium constant

1.It allows us to estimate the extent of a reaction based on its magnitude.

The value of K, the equilibrium constant, denotes how far a reaction can
progress. To put it another way, it’s a criterion for evaluating whether a
reversible reaction is complete.
The composition of the equilibrium mixture and the equilibrium constant K can
be generalized as follows:

I).At equilibrium, products predominate over reactants if K>103. The reaction

goes almost to completion if K is sufficiently large.

II)At equilibrium, reactants predominate over products if K is less than 10−3. The
reaction proceeds to a very small extent if K is very small

III).Appreciable concentrations of both reactants and products are present if K is

in the range of 10−3 to 103.

2.It predicts the direction of the reaction.

The equilibrium constant can also determine which direction an arbitrary
reaction mixture of reactants and products will take. We use the reaction
quotient Q to do this. The reaction quotient is the ratio of product
concentrations (or partial pressures) to the reactant concentrations (or partial
pressures) at any point in the reaction. In other words, the reaction quotient is
calculated in the same way as the equilibrium constant is calculated with molar
concentrations (Qc)or partial pressure (Qp)

aA+bB⇌ cC+dD
Qc = [C]c[D]d (The system may not be at equilibrium)
[A]a[B]b

K c =[C]c[D]d ( The system is at equilibrium)

[A]a[B]b

At equilibrium, Qc=Kc
 Thus,

1.If (Qc) is more than (Kc), the reaction will continue from right to left in the
direction of the reactants (reverse reaction)
2,If (Qc) is less than (Kc), the reaction will proceed from left to right in the
direction of the products (forward reaction)
3.If When (Qc) is equal to (Kc), the reaction mixture is already at equilibrium.
Thus, a reaction tends to form products if Q<Kand reactants if Q>K

3.It helps to calculate the equilibrium concentration.

The equilibrium constant can be calculated if the concentrations of reactants
and products are known at equilibrium in a reaction. On the other hand, the
concentration in the equilibrium mixture may be determined if the equilibrium
constant is known
For example:
. In a one-litre closed glass container, one mole of hydrogen and one mole
of iodine were heated at 490oCuntil equilibrium was established. Find the
final concentrations of H2,l2, and Hl, assuming the equilibrium constant
is 45.9.
Ans: The equation for the given reaction is
H2+I2⇌ 2HI
Suppose the number of moles of H2 reacted at equilibrium = x
Moles of all components at equilibrium are
H2 + I2 ⇌ 2HI
(1-X) (1-X) 2X

Since the volume of the vessel is one litre, the concentrations at equilibrium are
[H2] = 1 – x
[l2] = 1 – x
[HI] = 2x
The equilibrium constant expression becomes

K = [HI]2 =(2X)2 =45.9

[H2][I2] (1-X)(1-X)

Or
4x2 =45.9
1–2x+x2
Or
41.9x2 – 91.8x + 45.9 = 0
On solving we get x=0.79
[H2]=1–0.79=0.21moleperlitre
[I2]=1–0.79=0.21moleperlitre
[HI]=2x=2(0.79)=1.58moles per litre
Le Chatlier’s Principle
Le Chatelier's principle states that if a dynamic equilibrium is disturbed by changing the
conditions, the position of equilibrium shifts to counteract the change to re establish an
equilibrium.
If a chemical reaction is at equilibrium and experiences a change in pressure,
temperature, or concentration of products or reactants, the equilibrium shifts in the
opposite direction to cancel the change.
Effect of Change of Concentration
The increase in the concentration of any of the reactants shifts the equilibrium
towards the forward direction. The increase in the concentration of any of the
products shifts the equilibrium towards the backward direction.

Consider the general reaction, A + B⇌ C + D

If more reactant A or B is added to the reaction in equilibrium, then according to

Le Chatelier’s principle, the effect will decrease the concentration
of A or B Therefore, the equilibrium shifts in the forward direction. Similarly, the
impact of adding more of products C or D to the reaction in equilibrium will shift
the equilibrium in the backward direction; hence the equilibrium is reestablished
after some time.

Example: Consider the reaction

N2(g) + 3H2(g)⇌ 2NH3(g);

If concentration of N2 or H2 is increased,the reaction shifts towards forward direction in

order to counteract the increase.If concentration of NH3 is increased,the reaction
proceeds backward thereby decreasing the concentration of NH3.

Presence of catalyst does not affect the equilibrium because it increases/decreases the
rate of forward and backward reaction to the same extend.Catalyst helps to achieve the
equilibrium quickly.

Addition of inert gas does not affect the equilibrium.

Effect of Change of Temperature

The equilibrium of exothermic and endothermic reactions can be altered by

changing the temperature. Exothermic reactions are favoured by low
temperature, whereas endothermic reactions are favoured by high temperature.
On the altering temperature, if the forward reaction is exothermic, the backward
reaction will be endothermic and vice versa.

In other words, the increase in temperature shifts the equilibrium in the

direction of the endothermic reaction and the decrease in temperature shifts the
equilibrium in the direction of an exothermic reaction.

Example: The formation of ammonia is an exothermic process, while the

reverse is an endothermic process.
N2(g) + 3H2(g)⇌ 2NH3(g);ΔH=-92.5kJmol-1
 Suppose the temperature of the reaction is increased, the equilibrium shifts to
the left to neutralise or undo the effect of an increase in temperature. The
backward reaction is accomplished by decreasing temperature or cooling.
Similarly, if the temperature is increased, then the equilibrium will shift to the
right because heat is evolved in the forward reaction.

Effect of Change of Pressure

Pressure has hardly any effect on the reactions carried in solid and liquid.
However, it does influence the equilibrium of the reactions that are carried in
the gases. The effect of pressure depends upon the number of moles of the
reactants and the product involved in a particular reaction.

Increasing pressure shifts the equilibrium in the direction of a decrease in the

gaseous moles. In contrast, a decrease in pressure shifts the equilibrium in
increasing gaseous moles. However, pressure does not affect an equilibrium
reaction that proceeds with no change in the total number of
moles.Example :PCl3(g) + Cl2(g)⇌ PCl5(g)
In the above reaction, the number of moles of the product is less than the
reactants. Therefore, the increase in pressure will shift the equilibrium to the
right and decrease pressure when shifting the equilibrium to the left.

Applications of Le Chatelier’s Principle

Le Chatelier’s principle has great practical significance in the equilibrium state
in chemical and physical systems.

Application of Le Chatelier’s principle in chemical equilibria

Le Chatelier’s principle is instrumental in predicting the condition of
temperature, pressure, and concentration to get high yields in certain industrial
reactions. A few examples are,

1. Formation of ammonia in Haber’s process: The chemical equilibrium

taking place is
N2(g) + 3H2(g)⇌ 2NH3(g);ΔH=-92.5kJmol-1
This reaction is favoured at optimum temperature 750Kand
pressure 200atmospheres. By increasing the concentration of reactants and
continuous removal of products formation of ammonia is increased. Finely
divided iron is used as a catalyst to achieve equilibrium rapidly, and promoter
molybdenum is used to increase the catalyst’s efficiency.

IONIC EQUILIBRIUM

Ionic equilibrium is the equilibrium established between the unionised

molecules and ions in the solution of a weak electrolyte.

CH 3 COOH+H 2 O⇌ CH3COO-+H3O+

Degree of dissociation or ionisation

The fraction of total number of molecules of an electrolyte which ionises in

solution is called the degree of ionisation or degree of dissociation of electrolyte
Degree of dissociation(α)=Number of molecules of electrolyte that ionise

Total number of molecules of electrolyte

Various concepts of Acids and Bases

1. Arrhenius concept of Acids and bases

According to Arrhenius theory, acids are substances that dissociates in water to give
hydrogen ions H+(aq).

HCl(aq)→H (aq)+Cl (aq)

+ −

Egs of strong acids (which undergo complete dissociation)-

HNO3,HCl,H2SO4

Egs of weak acids(Which undergo partial dissociation)-

CH3COOH,H2CO3,H3PO4

Arrhenius Bases:

Bases are substances that produce OH–(aq) after dissociation in water.

Strong bases- NaOH,KOH,

Weak bases-NH4OH,Al(OH)3,,Ca(OH)2

Bronsted Lowry concept of acids and bases

In 1923, J. N. Bronsted and J. M. Bjerrum in Denmark and T. M. Lowry in England
independently proposed a theory known as ‘the proton theory of acids and bases’.
According to this theory-

An acid is a substance – a molecule or an ion – which can donate a proton.

A base is a substance – a molecule or an ion – which can accept a proton.

A proton is a hydrogen atom which has lost its electron. An acid ‘A’ ionizes as-

A (aq) ↔ H+ (aq) + B (aq) … … … (1)

‘B’ is said to be the conjugate base of the acid, while ‘A’ is the conjugate acid of the base
‘B’. A and B are termed conjugate acid-base pair. The conjugate acid and base differ only
by a proton. Examples of a few conjugate acid-base pairs are:

It may be seen that according to this concept a base or an acid may be a neutral
molecule or an ion. Hydrogen chloride acts as an acid in solution because it can donate a
proton. If the solvent is water H+ ion forms the hydronium ion, H3O+. Water here acts as
a proton acceptor, a base. This can be represented as-
..… …. (2)

Ammonia in water acts as a base because it can accept a proton from water. As a result
an OH– ion is produced,

… … … (3)

Water acts as an acid in this reaction. Following the definition it may be said that in
equation (2) Cl– ion is the conjugate base of the acid HCl, while water is the conjugate
base of the acid H3O+. In equation (3) NH3 is the conjugate base of the acid NH4+,
while OH– is the conjugate base of the acid H2O. It can be clearly seen that conjugate
acid-base pairs differ only by a single proton. In general, we can write,

A1 (Acid1) + B2 (Base2) ↔ B1 (Base1) + A2 (Acid2)

Note that depending on the relative proton donating and proton accepting ability the
same compound, such as water in the two examples given above, can act either as acid
or as a base.

The Bronsted – Lowry concept may also be applied to reaction between HCl and NH3,
both dissolved in benzene. In benzene none of these two compounds are ionized. They
react, however, to form NH4Cl.

Lewis concept of Acids and Bases

In the Lewis theory of acid-base reactions, bases donate pairs of electrons

and acids accept pairs of electrons. A Lewis acid is therefore any substance,
such as the H+ ion, that can accept a pair of nonbonding electrons. In other
words, a Lewis acid is an electron-pair acceptor. A Lewis base is any
substance, such as the OH- ion, that can donate a pair of nonbonding
electrons. A Lewis base is therefore an electron-pair donor.

Eg of Lewis acids:AlCl3,BF3,FeCl3,Ag+,Cu2+

Eg of Lewis bases:NH3,H2O,Cl-’CN-’OH- etc.

IONISATAION CONSTANT OF WEAK ACIDS

Consider the ionisation of a weak acid HX in water.

HX+H 2 O⇌ X-+H3O+

Ka is the dissociation constant of acid given by the expression;

Ka=[X-][H3O+

[HX]

Larger the value of Ka ,higher is the concentration of H3O+and stronger is the acid

Ostwald’s dilution law

Ostwald's dilution law relates the dissociation constant of the weak electrolyte with the degree
of dissociation and the concentration of the weak electrolyte. Consider the dissociation
equilibrium of CH3COOH which is a weak electrolyte in water.
CH3COOH⇌ CH3COO−+ H+
Initial conc C 0 0

Conc. At eqbm C-Cα Cα Cα

Ka=[CH3COO−][H+]
[CH3COOH]
α=degree of dissociation of acetic acid.
∴Ka= Cα×αC
C(1−α)
Ka=Cα2
(1-α)

Ostwald's dilution law

If α is too small, Ka=α2C
α2C=Ka
α2=Ka/C α

α=√Ka/C
Ka=α2C−Ostwald's dilution law for weak acid.
Kb=α2C−Ostwald's dilution law for weak base.

For a weak electrolyte,the degree of disassociation is inversely proportional

to the square root of molar concentration .-this is Ostwald’s dilution law.

Factors affecting acid strength

I. Bond strength: Acid strength increases from HF to HI because bond strength
decreases from HF to HI. When bond strength decreases, H+ ion is easily
liberated,thereby increasing the acidic character
II. Polarity of the molecule: Acidic character increases with increase in polarity.
As the electronegativity difference between the molecule increases in the order

CH4<NH3<H2O<HF

pH Scale

pH of a solution may be defines as negative logarithm of hydronium ion concentration

in mols/L

pH= - log [H3O+]

For pure water [H3O+] =[OH-]=1x 10-7 mol/L

pH of pure water =-log[H3O+]=-log[1x10-7]=7

Buffer solution

A buffer solution is a solution which resists change in its pH value even when small
amounts of acid or base are added to it.

If pH of the buffer solution is less than 7 it is called acidic buffer and pH is greater
than 7 it is called basic buffer.

Acidic buffer is a solution containing a weak acid and a salt of this weak acid with a
strong base.(eg:CH3COOH+CH3COONa)

Basic buffer is a mixture of weak base and a salt of this weak base with a strong
acid.(eg:NH4OH+NH4Cl)

Common ion effect

Common ion effect may be defined as the suppression of dissociation of a weak

electrolyte by addition of some strong electrolyte containing a common ion.

For eg; NH4OH ionises as:

NH4OH⇌ NH4+ +OH-

If NH4Cl is added to the system at equilibrium ,it ionises as

NH4Cl⇌ NH4+ +Cl-

Since NH4+ is a strong electrolyte,it ionises completely and hence concentration of NH4+
ion increases.According to Le Chateliers principle,the reaction proceeds in backward
direction to reduce the concentration of NH4+.Thus addition of NH4Cl suppresses the
ionisation of NH4OH.

Solubility product

Solubility product of a salt is the product of concentration of ions in its saturated solution
raised to a power equal to number of times the ions occur in the equation ,representing
the dissociation of the salt.
For eg, AgCl dissociates as:

AgCl⇌ Ag+ +Cl-

K=[Ag+][Cl-]

[AgCl]

Since [AgCl ] is a constant,Kx[AgCl] will be another constant called solubility

product,denoted as Ksp.

Ksp=[Ag+][Cl-]

Similarly in dissociation of BaSO4,

Ksp=[Ba2+][SO42-]

PbCl2 dissociates as;PbCl2⇌ Pb2+ +2Cl-

Ksp=[Pb2+][Cl-]2

Application of solubility product

1. Solubility can be calculated from solubility product

2. Chances of precipitation of a salt can be predicted if solubility product is known.