CHEMICAL

EQUILIBRIUM
By:P.Anggai
What is equilibrium?

A state of balance, especially between forces or influences that are working in opposite ways.

Importance of Equilibrium

• Equilibria involving O2 molecules and the protein hemoglobin play a crucial role in
the transport and delivery of O2 from our lungs to our muscles.

• Equilibria involving CO molecules and hemoglobin account for the toxicity of CO.

Depiction of Equilibrium

• In a system at equilibrium, both the forward and reverse reactions are running simultaneously.
We write the chemical equation with a double headed arrow:
 Equilibrium mixture
The mixture of reactants and products in the equilibrium state is called an equilibrium mixture.
Types of Equilibrium

Physical Equilibrium Chemical Equilibrium

• Equilibrium which develops between • Chemical equilibrium occurs
different phases or physical when opposing reactions are proceeding
properties. at equal rates.
• No change in chemical composition

• Represents the existence of the same

substance in two different physical
states
 Physical Equilibrium

Solid – liquid
equilibrium • Ice and water kept in a perfectly insulated thermos flask.
• Mass of ice and water do not change with time and the temperature
remains constant.
• Equilibrium is not static but dynamic ( keep on moving without
disturbing the equilibrium).
• Intense activity can be noticed at the boundary between ice and
water.
• Molecules from the liquid water collide against ice and adhere to it and
some molecules of ice escape into liquid phase.
• Rate of melting = Rate of freezing
In dynamic equilibrium,
• Both the opposing processes occur simultaneously.
• Both the processes occur at the same rate so that the amount of ice
and water remains constant.
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

• The number of water molecules from the gaseous For any pure liquid at one atmospheric
state into the liquid state increases until the pressure (1.013 bar), the temperature at
equilibrium is reached. which the liquid and vapours are at
Rate of evaporation =Rate of condensation equilibrium is called normal boiling point of
• Equilibrium water pressure: The pressure at which the the liquid
water molecules remain constant at a given
temperature
• Vapour pressure of water increases with temperature. • Boiling point of the liquid depends on the atmospheric
• The evaporation of liquid depends on, pressure.
• It depends on the altitude of the place; at high
i. The nature of the liquid
ii. The amount of liquid altitude the boiling point decreases
iii. The applied temperature
Solid – vapour
equilibrium

Rate of sublimation = Rate of deposition

Rate of melting = Rate Rate of evaporation = Rate Rate of sublimation =
of freezing of condensation Rate of deposition
 Equilibrium involving dissolution

Dissolution of solids in
liquids

• Initially there were no radioactive sugar molecules in the solution but due to dynamic nature of
equilibrium, there is exchange between the radioactive and non-radioactive sugar molecules between
the two phases.
• The ratio of the radioactive to nonradioactive molecules in the solution increases till it attains a
constant value
For dissolution of solids in liquids, the solubility is constant at a given temperature.
Dissolution of gases in
• When a soda water bottle is opened, some of the carbon dioxide gas
liquids
dissolved in it fizzes out rapidly.
• The phenomenon arises due to difference in solubility of carbon dioxide
at different pressures.
• There is equilibrium between the molecules in the gaseous state and the
molecules dissolved in the liquid under pressure.
CO2 (gas) ⇌CO2 (in solution)

Henry’s law
“The mass of a gas dissolved in a given mass of a solvent at any
temperature is proportional to the pressure of the gas above the
solvent.”

For dissolution of gases in liquids, the concentration of a gas in liquid is proportional to the pressure
General characteristics of physical
equilibrium

(i) Equilibrium is possible only in a closed system at a given temperature.

(ii) Both the opposing processes occur at the same rate and there is a dynamic but stable
condition.

(iii) All measurable properties of the system remain constant.

(iv) When equilibrium is attained for a physical process, it is characterised by constant

value of one of its parameters at a given temperature.

(v) The magnitude of such quantities at any stage indicates the extent to which the
physical process has proceeded before reaching equilibrium.
 Chemical Equilibrium
Consider a general case of a reversible reaction

A+B⇌C+D

With passing time, there is a

• decrease in the concentration of reactants A and B,
• increase in the concentration of products C and D
which leads to a
• decrease in the rate of forward reaction and an
• increase in the rate of backward reaction.

When the two reactions occur at the same rate the

system will reach a state of equilibrium.
 Proof for dynamic nature of chemical equilibrium
Haber’s Process
N2(g) + 3H2(g) ⇌ 2NH3(g)
• Haber started out with known amounts
of dinitrogen and dihydrogen, maintained at high
temperature and pressure, and noted the amount of
ammonia produced at regular intervals.
• As the reaction proceeds, after some time, he noted
that the composition of the mixture remains the same
even though some reactants are still present.
• This shows that the reaction has reached equilibrium.
N2(g) + 3D2(g) ⇌ 2ND3(g)
• Keeping the experimental conditions same as above,
hydrogen (H2) was replaced with deuterium (D2).
• This gives rise to ND3 as the product instead of NH3.
• Both reactions, one involving H2 and one
with D2 were allowed to proceed to equilibrium.
• When these two mixtures (H2, N2, NH3 and D2,
N2, ND3) were mixed and left for a while, it was
observed that the concentration of ammonia was
the same as before.
• Mass spectrometry revealed that along with
ammonia, all forms containing deuterium and
dihydrogen were present (NH2D, NHD2, ND3, H2,
HD and D2).
• This shows that the scrambling of H and
D atoms must be possible due to the continuation
of the forward and reverse reactions.
• There would have been no mixing of isotopes if
the reaction had stopped on reaching equilibrium.
• Chemical reactions reach a state of
dynamic equilibrium.
• Rates of forwarding = Rate of backward reactions
• No net change in composition.
Equilibrium can be achieved from either direction

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

Characteristics of Chemical Equilibrium:

•The concentration of each of the reactants and the products become constant at equilibrium.
•The rate of forward reaction becomes equal to the rate of backward reaction at equilibrium and hence equilibrium
is dynamic in nature.
• None of the products is allowed to escape out or separate out as a solid then only chemical equilibrium can be
established.
 Law of chemical equilibrium

Consider the general reversible reaction,

A+B⇌C+D

At equilibrium, assume the active masses of A, B, C and D are represented as [A], [B], [C], and [D] respectively.

Applying the Law of Mass Action,

Rate of the forward reaction ∝ [A] [B] = kf[A] [B]

Rate of the backward reaction ∝ [C] [D]= kb[C] [D]

At equilibrium,
Rate of forward reaction = Rate of backward reaction
kf[A][B] = kb[C][D]

Kc =

Kc is the equilibrium constant in terms of concentration (active mass).

Example:

Equilibrium Law (or) Law of Chemical Equilibrium.

“At a given temperature, the product of concentrations of the 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.”
 Practice questions

Write the equilibrium expression for Kc for the following reactions:

Solution :

Solution :
Characteristics of Equilibrium Constant:

•The value of the equilibrium constant for a particular reaction is always constant at constant temperature.

•It is independent of the initial concentrations of the reactants.

•The value of the equilibrium constant is inverted when the reaction is reversed.

• The equilibrium constant for the new equation is the square root of K (i.e)) when the equation is divided by 2.

•The equilibrium constant for the new equation is the square of K (i.e) ( when the equation is multiplied by 2.

•Addition of a catalyst do not affect the value of the equilibrium constant.

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 Homogeneous Equilibria

In an equilibrium, all the reactants and the products are present in the same phase, it is called homogeneous
equilibrium.
H2(​g) + I2(​g) ⇋ 2HI(g)

Equilibrium constant in gaseous systems

If the reactants and products of the above reaction are in gas phase, then the equilibrium constant can be written in
terms of partial pressures as indicated below:

Where,
pA, pB, pC,and pD are the partial pressures of the gas A, B, C and D respectively.
Relation between Kp and Kc

where, Δng - difference between the sum of number of moles of products

and the sum of number of moles of reactants in the gas phase.
Case (i):

Case (ii):

Case (iii):
 Heterogeneous Equilibria
• Equilibrium in a system having more than one phase is called heterogeneous equilibrium.

• Molar concentration of a pure solid or liquid is constant (i.e., independent of the amount present).

The equilibrium constant for the above reaction can be written as:

A pure solid always has the same concentration at a given temperature, as it does not expand to fill its container.
i.e. it has same number of moles L-1 of its volume.
Therefore, the concentration of a pure solid is a constant.
The above expression can be modified as follows
• Active mass (concentration) of the pure liquid does not change at a given temperature.
• Consequently, the concentration terms of pure liquids can also be excluded from the expression of the equilibrium
constant.
Practice questions
Solution:
 Unit of equilibrium constant
unit of the equilibrium constant = [Mole L-1]△n
Units of Kp​is (atm)Δn
Case 1: Case 2: Case 3:
When the total number of moles of When the total number of moles Example:
products is equal to the total of products is different than the 2NH3(g) ⇌ N2(g) + 3H2(g)
number of moles of reactants, then total number of moles of
K has no units. reactants, then K has units.
Example: Example:
N2 (g) + O2 (g) ⇌ 2NO (g) N2 (g) + 3 H2 (g) ⇌ 2 NH3
 Applications of equilibrium constant

The knowledge of equilibrium constant helps us to

1. Predict the direction in which the net reaction will take place

2. Predict the extent of the reaction

3. Calculate the equilibrium concentrations of the reactants and products.

Prediction
of extent of
the reaction
Prediction of direction of reaction

Under non-equilibrium conditions, the reaction quotient (Q) can be calculated using the following expression.

• If Q = Kc, the reaction is in equilibrium

state.

• If Q > Kc, the reaction will proceed in the

reverse direction i.e., formation of
reactants.

• If Q < Kc, the reaction will proceed in the

forward direction i.e., formation of
products.
Calculation of equilibrium concentration

If the equilibrium concentrations of reactants and products are known for a reaction, then the equilibrium constant
can be calculated and vice versa.

Step 1. Write the balanced equation for the reaction.

Step 2. Under the balanced equation, make a table that lists for each substance involved in the reaction:
(a) the initial concentration,
(b) the change in concentration on going to equilibrium, and
(c) the equilibrium concentration.
In constructing the table, define x as the concentration (mol/L) of one of the substances that reacts on going to
equilibrium, then use the stoichiometry of the reaction to determine the concentrations of the other substances in terms
of x.

Step 3. Substitute the equilibrium concentrations into the equilibrium equation for the reaction and solve for x. If you are
to solve a quadratic equation choose the mathematical solution that makes chemical sense.

Step 4. Calculate the equilibrium concentrations from the calculated value of x.

Step 5. Check your results by substituting them into the equilibrium equation.
Example:
Let us consider the formation of HI in which, ‘a’ moles of hydrogen and ‘b’ moles of iodine gas are allowed to react in a
container of volume V. Let ‘x’ moles of each of H2 and I2 react together to form 2x moles of HI.
Applying law of mass action,

The equilibrium constant Kp can also be calculated as follows:

 Relationship between equilibrium constant (K),
Reaction quotient (Q) & Gibbs energy (G)
• Kc for a reaction does not depend on the rate of Case (1):
the reaction.

which implies a spontaneous reaction or the reaction which

proceeds in the forward direction to such an extent that the
products are present predominantly.
Case (2):

(At equilibrium)

(Taking antilog) 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.
 Le Chatelier’s Principle

It states that “If a system at equilibrium is disturbed, then the system shifts itself in a direction that nullifies the
effect of that disturbance.”

“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
• At equilibrium, the concentration of the reactants and the products does not change.
• The addition of more reactants or products to the reacting system at equilibrium causes an increase in their respective
concentrations.
• According to Le Chatelier’s principle, the effect of increase in concentration of a substance is to shift the equilibrium in
a direction that consumes the added substance.
Example 1:

• The addition of H2 or I2 to the equilibrium mixture, disturbs the equilibrium.

• In order to minimize the stress, the system shifts the reaction in a direction
where H2 and I2 are consumed.
• i.e., the formation of additional HI would balance the effect of added
reactant.
• Hence, the equilibrium shifts to the right (forward direction) i.e. the forward
reaction takes place until the equilibrium is re-established.
• Similarly, removal of HI (product) also favours the forward reaction.
• At equilibrium, the concentrations of HI, H2 and I2 are 1 M, 0.2M and
0.1M respectively.

• The equilibrium was disturbed by adding 0.1 M iodine to the reaction

mixture.
• After sometime, the concentration of HI is found to be 1.092 M.
• Let us verify whether the system proceeds to re-establish the equilibrium
according to Le Chatelier’s principle.

The reaction quotient Q at this stage,

So, we can conclude that the system

has re-established the equilibrium at
this stage and the addition of iodine
results in the increase in the HI
concentration.
Example 2: • Oxalic acid (H2C2O4 ), reacts with Fe3+ ions to form
the stable complex ion [Fe(C2O 4 ) 3 ] 3 – , thus
decreasing the concentration of free Fe3+ (aq).

• In accordance with the Le Chatelier’s principle, the

concentration stress of removed Fe3+ is relieved by
dissociation of [Fe(SCN)]2+ to replenish the Fe 3+
ions.

• The equilibrium can be shifted in the • Because the concentration of [Fe(SCN)]2+

opposite direction by adding reagents that decreases, the intensity of red colour decreases.
remove Fe3+ or SCN – ions.
• Addition of aq. HgCl2 decreases red colour because Hg2+
reacts with SCN – ions to form stable complex ion
[Hg(SCN)4] 2–.

• Removal of free SCN – (aq) shifts the equilibrium from right

to left to replenish SCN – ions.

• Addition of potassium thiocyanate on the other hand

increases the colour intensity of the solution as it shift the
equilibrium to right.
 Effect of pressure
change
• The change in pressure has significant effect only on
equilibrium systems with gaseous components.

• When the pressure on the system is increased, the

volume decreases proportionately and the system
responds by shifting the equilibrium in a direction that
has fewer moles of gaseous molecules.

• Let the system be allowed to attain equilibrium in a cylinder

with a piston.
• If we press the piston down to increase the pressure, the
volume decreases.
• The system responds to this effect by reducing the number
of gas molecules. i.e. it favours the formation of ammonia.
• If we pull the piston upwards to reduce the pressure, the
volume increases.
• It favours the decomposition of ammonia.
• However, when the total number of the
moles of the gaseous reactants and the
gaseous products are equal, the change
in pressure has no effect on system at
equilibrium.
 Effect of temperature
changeconstant for an exothermic reaction
• The equilibrium
(negative ∆H) decreases as the temperature increases.
• The equilibrium constant for an endothermic reaction
(positive ∆H) increases as the temperature increases.
• Temperature changes affect the equilibrium constant
and rates of reactions.
Effect of temperature on equilibrium can be demonstrated by
taking NO2 gas (brown in colour) which dimerises into N2O4 gas
(colourless).
• NO2 gas prepared by addition of Cu turnings to
conc. HNO3 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 (36 3K ), 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 addition of
• Additioncatalyst
of a catalyst does not affect the state of the equilibrium.

• The catalyst increases the rate of both the forward and the reverse reactions to the same extent.

• Hence, it does not change the equilibrium composition of the reaction mixture.

• However, it speeds up the attainment of equilibrium by providing a new pathway having a lower activation
energy.

• For example, in the synthesis of NH3 by the Haber's process iron is used as a catalyst.

• Similarly, in the contact process of manufacturing SO3, platinum or V2O5 is used as a catalyst.
 Effect of addition of inert
gas
• When an inert gas (i.e, a gas which does not react with any other species involved in equilibrium) is added to an
equilibrium system at constant volume, the total number of moles of gases present in the container increases, that
is, the total pressure of gases increases.

• The partial pressure of the reactants and the products are unchanged.

• Hence at constant volume, addition of inert gas has no effect on equilibrium.

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