EQUILIBRIUM

EQUILIBRIUM IN CHEMICAL PROCESSES – DYNAMIC

EQUILIBRIUM
When the rates of the forward and reverse reactions become equal, the
concentrations of the reactants and the products remain constant. This is the
stage of chemical equilibrium. This equilibrium is dynamic in nature as it
consists of a forward reaction in which the reactants give product(s) and
reverse reaction in which product(s) gives the original reactants.
For a better comprehension, let us consider a general case of a reversible
reaction,
A+B C+D
With passage of time, there is accumulation of the products C and D and
depletion of the reactants A and B .
This leads to a decrease in the rate of forward reaction and an increase in he
rate of the reverse reaction, Eventually, the two reactions occur at the same
rate and the system reaches a state of
equilibrium.
SIMILARLY, THE REACTION CAN REACH THE STATE OF
EQUILIBRIUM EVEN IF WE START WITH ONLY C AND D;
THAT IS, NO A AND B BEING PRESENT INITIALLY, AS THE
EQUILIBRIUM CAN BE REACHED FROM EITHER DIRECTION.
The dynamic nature of chemical equilibrium can be demonstrated in the
synthesis of ammonia by Haber’s process. In a series of experiments,
Haber started with known amounts of dinitrogen and dihydrogen
maintained at high temperature and pressure and at regular intervals
determined the amount of ammonia present. He was successful in
determining also the concentration of unreacted dihydrogen and
dinitrogen. shows that after a certain time the composition of the
mixture remains the same even though some of the reactants are still
present. This constancy in composition indicates that the reaction has
reached equilibrium. In order to understand the dynamic nature of the
reaction, synthesis of ammonia is carried out with exactly the same
starting conditions (of partial pressure and temperature) but using D 2
(deuterium) in place of H2 . The reaction mixtures starting either with
H2or D2 reach equilibrium with the same composition, except that D 2
and ND3 are present instead of H 2and NH 3 . After equilibrium is
attained, these two mixtures (H2 , N2 , NH3and D2 , N2 , ND3) are mixed
together and left for a while. Later, when this mixture is analysed, it is
found that the concentration of ammonia is just the same as before.
However, when this mixture is analysed by a mass spectrometer, it is
found that ammonia and all deuterium containing forms of ammonia
(NH3, NH2D, NHD2and ND3) and dihydrogen and its deutrated
forms (H2, HD and D2) are present. Thus one can conclude that
scrambling of H and D atoms in the molecules must result from a
continuation of the forward and reverse reactions in the mixture. If
the reaction had simply stopped when they reached equilibrium,
then there would have been no mixing of isotopes in this way.
 Equilibrium can be attained from both sides, whether we start
reaction by taking, H2(g) and N2(g) and get NH3(g) or by taking
NH3(g) and decomposing it into N2(g) and H2(g).

N2(g) + 3H2(g) 2NH3(g)

2NH3(g) N2(g) + 3H2(g)
Similarly let us consider the reaction,
H2(g) + I2(g) 2HI(g).
If we start with equal initial concentration of H2and I2, the reaction
proceeds in the forward direction and the concentration of H 2 and I2
decreases while that of HI increases, until all of these become
constant at equilibrium . We can also start with HI alone and make
the reaction to proceed in the reverse direction; the concentration of
HI will decrease and concentration of H2 and I2 will increase until
they all become constant when equilibrium is reached . If total
number of H and I atoms are same in a given volume, the same
equilibrium mixture is obtained whether we start it from pure
reactants or pure product.
 LAW OF CHEMICAL EQUILIBRIUM AND
EQUILIBRIUM CONSTANT
A+ B C+D
Equilibrium equation
LAW OF MASS ACTION

Partial pressures and concentrations of products appear in the

numerator and those of the reactants in the denominator.
Each is raised to a power equal to its coefficient in the
balanced chemical equation.

aA + bB cC + dD
if gases if concentrations
PC  PD 
c d
K C D  K
c d

PA  PB 
a b
A B
a b
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.
aA+ bB cC+dD

Equilibrium constant for the reaction,

4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g) is written as

Equilibrium constant for the reverse reaction is the inverse of

the equilibrium constant for the reaction in the forward
direction.
HOMOGENEOUS EQUILIBRIA
In a homogeneous system, all the reactants and products
are in the same phase. For example, in the gaseous
reaction, N2(g) + 3H2(g) 2NH3(g) reactants and
products are in the homogeneous phase . Similarly, for
the reactions,

Equilibrium Constant in Gaseous Systems

For reaction in equilibrium
where Δn= (number of moles of gaseous products) – (number
of moles of gaseous reactants) in the balanced chemical
equation.
HETEROGENEOUS EQUILIBRIA
Equilibrium in a system having more than one phase is called
heterogeneous equilibrium. The equilibrium between water vapour
and liquid water in a closed container is an example of
heterogeneous equilibrium.
H2O(l) H2O(g)
In this example, there is a gas phase and a liquid phase. In the same
way, equilibrium between a solid and its saturated solution,
Ca(OH)2(s) + (aq) Ca2+(aq) + 2OH–(aq)
is a heterogeneous equilibrium.
For the heterogeneous equilibria involving a pure liquid or a pure
solid, as the molar concentration of a pure solid or liquid is constant
(i.e., independent of the amount present). In other words if a
substance ‘X’ is involved, then [X(s)] and [X(l)] are constant,
whatever the amount of ‘X’ is taken.
EXAMPLE OF HETEROGENEOUS CHEMICAL EQUILIBRIUM.
CaCO3 (s) CaO (s) + CO2 (g)

K´c= [CO2(g)]

Ni (s) + 4 CO (g) Ni(CO)4 (g)

HETEROGENEOUS EQUILIBRIUM

Gases and CaCO3(s) CaO(s) + CO2(g)

Solids
K=PCO2

K is independent of the amounts

of CaCO3(s) or CaO(s)
HETEROGENEOUS EQUILIBRIUM

Liquids H2O(l) H2O(g)

K=PH2O

Solutions I2(s) I2(aq)

K=[I2]
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

 If Kc > 103 , products predominate over reactants, i.e., if K c

is very large, the reaction proceeds nearly to completion.
 If Kc < 10–3, reactants predominate over products, i.e., if K c
is very small, the reaction proceeds rarely.
 If Kc is in the range of 10–3 to 103,appreciable
concentrations of both reactants and products are present.
PREDICTING THE DIRECTION OF THE REACTION

 If Qc > Kc , the reaction will proceed in the direction of

reactants (reverse reaction).
 If Qc < Kc , the reaction will proceed in the direction of
the products (forward reaction).
 If Qc = Kc , the reaction mixture is already at
equilibrium.
The gaseous reaction of H2 with I2,
PREDICTING THE DIRECTION OF THE
REACTION

 If Qc< Kc , net reaction goes from left to right.

 If Qc> Kc, net reaction goes from right to left.

 If Qc= Kc , no net reaction occurs.

Calculating Equilibrium Concentrations

 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. This is applicable to all physical and chemical equilibria.

E Effect of Concentration Change

• The concentration stress of an added reactant/product is relieved by net
reaction in the direction that consumes the added substance.
• The concentration stress of a removed reactant/product is relieved by net
reaction in the direction that replenishes the removed substance. or in other
words,

“When the concentration of any of the reactants or products in a

reaction at equilibrium is changed, the composition of the equilibrium
mixture changes so as to minimize the effect of concentration changes”.
Let us take the reaction,
H2(g) + I2(g) 2HI(g)
If H2 is added to the reaction mixture at equilibrium, then the
equilibrium of the reaction is disturbed. In order to restore it, the
reaction proceeds in a direction wherein H2 is consumed, i.e., more
of H2 and I2 react to form HI and finally the equilibrium shifts in
right (forward) direction. This is in accordance with the Le
Chatelier’s principle which implies that in case of addition of a
reactant/product, a new equilibrium will be set up in which the
concentration of the reactant/product should be less than what it was
after the addition but more than what it was in the original mixture.
The same point can be explained in terms of the reaction quotient, Qc,
Qc= [HI]2/ [H2][I2]
Addition of hydrogen at equilibrium results in value of Qc being
less than Kc. Thus, in order to attain equilibrium again reaction
moves in the forward direction.

Effect of Concentration – An experiment

This can be demonstrated by the following reaction:
A reddish colour appears on adding two drops of 0.002 M potassium thiocynate
solution to 1 mL of 0.2 M iron(III) nitrate solution due to the formation of
[Fe(SCN)] 2+. The intensity of the red colour becomes constant on attaining
equilibrium. This equilibrium can be shifted in either forward or reverse
directions depending on our choice of adding a reactant or a product. The
equilibrium can be shifted in the opposite direction by adding reagents that
remove Fe3+ or SCN – ions. For example, oxalic acid (H2C2O4), reacts with Fe3+
ions to form the stable complex ion [Fe(C2O4)3]3–, thus decreasing the
concentration of free Fe3+(aq). replenish the Fe3+ions. Because the concentration
of [Fe(SCN)]2+ decreases, the intensity of red colour decreases.

Effect of Pressure Change

A pressure change obtained by changing the volume can affect the yield of products
in case of a gaseous reaction where the total number of moles of gaseous reactants
and total number of moles of gaseous products are different. In applying Le
Chatelier’s principle to a heterogeneous equilibrium the effect of
pressure changes on solids and liquids can be ignored because the volume (and
concentration) of a solution/liquid is nearly independent of pressure.
Consider the reaction,
 EFFECT OF TEMPERATURE CHANGE
 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.
Production of ammonia according to the reaction,

is an exothermic process. According to Le Chatelier’s

principle, raising the temperature shifts the equilibrium to
left and decreases the equilibrium concentration of
ammonia. In other words, low temperature is favourable for
high yield of ammonia, but practically very low
temperatures slow down the reaction and thus a catalyst is
used.
EFFECT OF TEMPERATURE – AN EXPERIMENT
Effect of temperature on equilibrium can be demonstrated by taking
NO2 gas (brown in colour) which dimerises into N2O4 gas
(colourless).

NO2gas prepared by addition of Cu turnings to conc. HNO 3 is

collected in two 5 mL test tubes (ensuring same intensity of colour
of gas in each tube) and stopper sealed with araldite. Three 250 mL
beakers 1, 2 and 3 containing freezing mixture, water at room
temperature and hot water (363 K ), respectively, are taken. Both the
test tubes are placed in beaker 2 for 8-10 minutes. After this one is
placed in beaker 1 and the other in beaker 3. The effect of
temperature on direction of reaction is depicted very well in this
experiment. At low temperatures in beaker 1, the forward reaction of
formation of N2O4 is preferred, as reaction is exothermic, and thus,
intensity of brown colour due to NO2 decreases. While in beaker 3,
high temperature favours the reverse reaction of
 formation of NO2 and thus, the brown colour intensifies.
Effect of temperature can also be seen in an endothermic reaction,

At room temperature, the equilibrium mixture is blue due to

[CoCl4]2– .When cooled in a freezing mixture, the colour of the
mixture turns pink due to [Co(H2O)6]3+.
.
 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. It increases the rate
of forward and reverse reactions that pass through the
same transition state and does not affect equilibrium.
Catalyst lowers the activation energy for the forward and
reverse reactions by exactly the same amount. Catalyst
does not affect the equilibrium composition of a reaction
mixture.
It does not appear in the balanced chemical equation or in
the equilibrium constant expression.