Chemical Equilibria

Syllabus
Concept and laws of chemical equilibrium
 Reversible reactions: Explanation of reversible reactions with examples.
 Equilibria involving physical changes: Examples of physical changes in equilibrium,
general characteristics of equilibria involving Physical Processes.
 Equilibria in chemical process:
 Dynamic equilibrium: Explanation of dynamic nature of chemical reaction in
equilibrium, Concept of chemical equilibrium: Explanation of concept of chemical
equilibrium using graph and examples, main features of chemical equilibrium.
 Law of chemical equilibrium from law of mass action: Deduction of expression for
law of chemical equilibrium from law of mass action.
 Deduction of expressions for equilibrium constant ‘KC’ and ‘Kp’ for homogenous and
heterogeneous reactions, relation between KC and Kp, units and calculations of KC and
Kp,
 Le Chatelier’s principle: Effects of change in concentration, pressure and temperature
on the position of equilibrium in homogeneous reactions and applications.

Objectives
 Explain reversible reactions by designing the simulation / video.
 Explore examples and characteristics of physical changes in equilibrium by observing the
natural phenomena in the surrounding.
 Demonstrate the features of chemical equilibrium by designing a simulation/video.
 Deduce mathematical expression for law of chemical equilibrium and equilibrium
constant from law of mass action.
 Solve numerical problems by applying the expression of equilibrium constant or law of
equilibrium.
 Design and carryout an experiment to verify Le Chatelier’s principle.
 Design a model of a chemical process for an industry to optimise the product and save
time using the knowledge of chemical equilibrium.
 Analyse the biological significance of chemical equilibrium.

Chemical equilibrium is defined as the state of a chemical reaction at which the rates of
forward and backward reactions are equal and the concentration of reactants and products reach
constant value.
Chemical equilibrium point changes with the change of temperature, pressure and
concentration.
Chemical reaction is a process in which one or more reactants react to produce one or more
products.
Type of Chemical reaction
(a) Reversible reactions (b) Irreversible Reactions

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(a) Reversible reactions
Reversible reactions occur in both forward and backward directions and therefore never go on to
completion.
For any reversible reaction, container should be closed
Examples:
N2 (g) + O2 (g) 2NO (g)
3Fe (s) + 4H2O (g) Fe3O4 (s) + 4H2 (g)
CaCO3 (s) CaO (s) + CO2 (g)
PCl5 (g) PCl3 (g) + Cl2 (g)
H2 (g) + I2 (g) 2HI (g)
N2O4 (g) 2NO2 (g)

(b) Irreversible Reaction:

Unidirectional reactions are known as irreversible reactions. i.e. reactants convert to produce
products and where products cannot convert back to the reactants.
Examples:
AgNO3 (aq) + NaCl (aq) → AgCl (s) + NaNO3 (aq)
BaCl2 (aq) + Na2SO4 (aq) → BaSO4 (s) + NaCl (aq)
2Mg (s) + O2 (g) → 2MgO (s)

Equilibria involving physical changes

The type of equilibrium which develops between different phases and there is no change in
chemical composition. In physical equilibrium, there is the existence of same substance in
different physical states.
In all processes which attain equilibrium, the two opposing processes (forward and backward
processes) are involved. Equilibrium is attained when the rates of the two opposing processes
becomes equal.
If the opposing processes involve only physical changes, the equilibrium is called physical
equilibrium.
The most familiar examples involve changes of state are:
(i) Solid-liquid equilibrium, example; ice liquid water
(ii) Liquid – gas equilibrium; example, water water vapour
(iii)Equilibrium of solute in two phases of solution, example;
(a) Sugar (s) Sugar in saturated solution in water (Solid−liquid equilibrium)
(b) CO2 (g) CO2 (solution), i.e., dissolved in water. (Gas−liquid equilibrium)
(i) Solid-Liquid Equilibrium: The equilibrium is represented as
H2O(s) H2O (l)
Rate of melting of ice = Rate of freezing of water.
The system here is in dynamic equilibriums 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.

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(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) (a) Equilibrium involving Dissolution of Solid in Liquid
Solution: When a limited amount of salt or sugar or any solute dissolves in a given amount of
water solution is formed.
At a given temperature state is reached when no more solute can be dissolved then the solution is
called saturated solution.
The equilibrium between a solid and its solution is indicated by the saturated solution and may
be represented as

Here, dissolution and precipitation takes place with the same speed.
On adding a small amount of radioactive sugar to the saturated solution it will be found that the
sugar present in the solution as well as in the solid state is radioactive.

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.
Mathematically, m∝ p
m = kp [k = Henry’s constant]
m
k= ,
p

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Where ‘m’ is the mass of a gas dissolved in a given volume of the liquid at pressure ‘p’ and at
constant temperature ‘T’
It implies that, smaller the pressure, smaller would be the amount of a gas dissolved in a given
quantity of solvent. The bubbles of gas (CO2) from soda water bottle start coming out briskly as
the cork is open. The reason is that solubility of the gas dissolved at high pressure in the bottle
becomes less on lowering the pressure and excess of it bubbles out on opening.
Solubility of gas of the gas in a liquid depends on:
(a) pressure
(b) nature of gas
(c) nature of liquid (solvent)
(d) other components present in the solution.
Problems
(i) The solubility of a substance ‘A’ (M = 120 g mol−1) at 300 K at equilibrium is equals to 0.002
mol dm3. How much ‘A’ will remain undissolved?
(a) If 0.5 g of it were taken with 200 cm3 of water till the equilibrium is reached?
(b) Hoe much of ‘A’ will be dissolved if another 200 cm3 of water is added to the above
mixture?
Answer:
At equilibrium the amount of ‘A’ dissolved per dm3 or 1000 cm3 of water = 0.002 mol.
Molecular mass of ‘A’ = 120 g mol−1
Mass of ‘A’ dissolved in 1000 mL of water = 0.002 × 120 = 0.24 g
(a) Volume of water = 200 mL
200 ×0.24
Therefore mass of ‘A’ dissolved in 200 cm3 = 1000 = 0.048 g
Total mass of ‘A’ taken = 0.5 g
Hence, mass of ‘A’ left undissolved = 0.5 – 0.048 = 0.452 g.
(b) Total volume of water = 200 + 200 = 400 cm3
400 ×0.24
Therefore the mass of ‘A’ dissolved = 1000 = 0.096 g

(ii) 0.20 g of solid iodine was treated with 100 cm3 water at 298 K till equilibrium was
established. The solubility of iodine = 0.0011 mol/litre at 298 K.
Calculate:
(a) How much iodine remained undissolved?
(b) How much iodine could remain undissolved if another 150 cm3 of water is added to the
solution?
Answer:
Molecular mass of I2 = 254 g mol−1
(a) Amount of dissolved iodine = solubility × volume of water
Amount of dissolved iodine = 0.0011 × 0.1 L = 0.00011 mol
Mass of iodine dissolved = 0.00011 × 254 = 0.02792 g
Amount of undissolved iodine = 0.20 − 0.02792 = 0.17208 g.
(b) Total volume of water = 250 cm3 = 0.25 L
Amount of dissolved iodine = 0.0011 × 0.25 L = 0.000275 mol.
Mass of iodine dissolved = 0.000275 × 254 = 0.0698 g

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 Mass of undissolved iodine = 0.20 − 0.0698 = 0.1302 g.
(iii) 425 g of sugar was treated with 100 cm3 water at 293 K till equilibrium was established. The
solubility of sugar = 5.9 mol/litre at 293 K.
Calculate:
(a) How much sugar remains undissolved at equilibrium?
(b) How much sugar will remain undissolved when solution is diluted to make a volume 200
cm3 ?
Answer:
(a) Amount of dissolved sugar = solubility × volume of water
Amount of dissolved sugar = 5.9 × 0.1 L = 0.59 mol
Mass of sugar dissolved = 0.59 × 342 = 201.78 g
Amount of undissolved sugar = 425 – 201.78 = 223.22 g.
(b) Volume of water = 200 cm3 = 0.200 L
Amount of dissolved sugar = 5.9 × 0.2 L = 1.18 mol.
Mass of sugar dissolved = 1.18 × 342 = 403.56 g
Mass of undissolved sugar = 425 – 403.56 = 21.44 g.
General characteristics of equilibria involving physical processes
Following factors have come to light from the discussion of various processes involving physical
equilibrium:
(i) In the case of liquid gas equilibrium, the pressure of gas above the liquid was found to
be constant at a given temperature.
(ii) In the case of solid liquid equilibrium, there is only one temperature called melting
point, at which the system does not lose matter to surroundings or gain matter from the
surroundings. So, the mass of the two phases remains constant.
(iii) In case of dissolution of solids in liquids, the solubility is constant at a given temperature.
(iv) In case of dissolution of gases in liquids, the concentration of a gas in a liquid is proportional
to the pressure of the gas over the liquid or the concentration of a gas in the space above the
liquid.
Characteristics of Equilibria Involving Physical Processes
(i) The equilibrium can be attained only in closed systems at a given temperature. (Exchange of
matter from the surrounding to the system and vice-versa is not allowed)
(ii) At the equilibrium the measurable properties of the system remain constant.
(iii) The rate of forward reaction or process = Rate of backward reaction or process.
(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.
Equilibria in chemical process: Dynamic equilibrium:
Equilibrium in Chemical Processes
In chemical equilibrium, concentration of the reactants and products do not change with time
and the system does not show any further change in properties.
In case of chemical equilibrium, rate of forward reaction becomes equal to the rate of backward
reaction. i.e., Rate (forward reaction) = Rate (backward reaction)

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The stage at which the rate of the forward reaction is equal to the rate of the backward reaction is
called an equilibrium stage. At this point, the number of reactant molecules converting into
products and product molecules into reactants is the same. The same equilibrium can be carried
out with the same reactants anywhere with similar conditions with continuous interchanging of
molecules, and hence chemical equilibrium is dynamic.
Forward reaction (In an open glass container)
∆
3Fe (s) + 4H2O (g) → Fe3O4 (s) + 4H2 (g)
If the container tube is closed, both the reactions take place simultaneously and hence reaction
becomes reversible.
3Fe (s) + 4H2O (g) Fe3O4 (s) + 4H2 (g)
Characteristics of Chemical Equilibrium
 A reaction (or a process) is said to be in chemical equilibrium when the rate of forward
reaction (process) becomes equal to the rate of backward reaction (process).
 An equilibrium is dynamic in nature and not static i.e., even after equilibrium is attained, the
forward as well as the backward reaction take place but at equal speeds.
 A chemical equilibrium can be established only if none of the products is allowed to escape
out.
 At equilibrium, the amounts of each of the reactants and products become constant so long as
the factor like concentration, temperature, pressure etc. remains unchanged.
 When reaction attains equilibrium at certain temperature and pressure, ∆G = 0
 Chemical equilibrium can be achieved from either direction. The nature and the properties of
equilibrium state are same, regardless of the direction from which is reached.

Law of chemical equilibrium from law of mass action

Law of Mass Action: 1n 1867, Guldberg and Waage enunciated the generalization, known as
the law of mass action. It expresses quantitatively the effect of mass or concentration on the rate
of a chemical reaction.
The rate of a reaction is proportional to the product of the active masses of the reactants The rate
of a reaction is proportional to the product of the active masses of the reactants.
Let us consider a reaction between the reactants ‘A’ and ‘B’ to form products
A+B Products
According to the law of mass action,
Rate of reaction ∝ [A] [B] = k[A] [B]

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Where [A] and [B] are the molar concentration (active masses) of reactants ‘A’ and ‘B’ and ‘k’
stand for the velocity constant or rate constant
If [A] = [B] = 1
Therefore, rate of reaction = k
Rate constant or velocity constant is equals to rate of reaction when molar concentrations of
the reactants are unity each.
Consider a reaction: aA + bB + cC Products
Rate of reaction is directly proportional to [A] a [B]b [C]c
Thus, the law of mass action may be restates as:
The rate of a reaction is proportional to the product of the active masses of the reactants; the rate
of a reaction is proportional to the product of the active masses of the reactants.
By applying the law of mass action to a reversible reaction, it is possible to derive a
mathematical expression known as law of chemical equilibrium.
Consider a homogeneous reversible reaction taking place in a gas or liquid phase, at a constant
temperature
A+B C+D
According to the law of mass action,
Rate of the forward reaction ∝ [A] [B]
= k1 [A] [B]
Rate of the backward reaction ∝ [C] [D]
= k 2 [C] [D]
[A], [B], [C], and [D] represent the active masses or molar concentrations of A, B, C and D
respectively and k1 and k 2 are the velocity constants of the forward and backward reactions
respectively.
At equilibrium, Rate of forward reaction = Rate of backward reaction
k1 [A] [B] = k 2 [C] [D]
k1 [C][D]
= K c = [A][B]
K2
k
At constant temperature, k1 and k 2 are constant, therefore, K1 = K c is also constant at constant
2
temperature and is called ‘Equilibrium constant’ (K c ).
The product of the molar concentrations of the products, each raised to the power equal to its
stoichiometric coefficient divided by the product of the molar concentrations of the reactants,
each raised to the power equal to its stoichiometric coefficient is constant at constant temperature
and is called Equilibrium constant (𝐊 𝐜 ).
Equilibrium constant in terms of pressure (K p )
For gaseous reactions, the partial pressure of a substance is proportional to its concentration in
the gaseous phase.
Consider the formation of hydrogen iodide from H 2 and I2
H2 (g) + H2 (g) 2HI (g)
According to the law of mass action,
Rate of the forward reaction ∝ [H2] [I2]
= k1 [H2] [I2]

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 Rate of the backward reaction ∝ [HI]2
= k 2 [HI]2
[HI], [H2] and [I2] represent the active masses or molar concentrations of HI, H 2 and I2
respectively and k1 and k 2 are the velocity constants of the forward and backward reactions
respectively.
At equilibrium, Rate of forward reaction = Rate of backward reaction
k1 [H2][I2] = k 2 [HI]2
k1 [HI]2
= Kc =
K2 [H2 ][I2 ]
[HI]2
Kc =
[H2 ][I2 ]
K p for the reaction can be written as:
[PHI ]2
Kp =
[PH2 ] × [PI2 ]
K p related to K c as K p = K c (RT)∆n, where ‘∆n’ is the difference in number of moles of products
and reactants taking part in the reaction. ‘R’ is a gas constant (0.0821 L atm K−1 mol−1) and ‘T’
is the temperature in Kelvin.
Relationship between 𝐊 𝐩 and 𝐊 𝐜
Consider a general reversible reaction
aA + bB xX + yY
The equilibrium constant (K c ) for the reaction in terms of molar concentration written as:
[X]x [Y]y
Kc =
[A]a [B]b
Or
CX x CY Y
Kc =
CA a CB b
CA, CB, CX and CY represents the molar concentration of A, B, X and Y respectively.
If A, B, X and Y are gaseous, the equilibrium in terms of pressure written as:
PX x PY
Kp =
PA a PB b
If the gas behave ideally, according to ideal gas equation,
PV = nRT
n n
P = V RT [V = number of moles per litre = C (molar concentration)]
P = CRT
Therefore, the gases A, B, X and Y are expressed as:
PA = CA RT, PB = CB RT
PX = CX RT, PY = CY RT
Substitute the values in K p equation:
(CX RT)x (CY RT)y CX x CY Y (RT)x+y
Kp = =
(CA RT)A (CB RT)b CA a CB b (RT)a+b
CX CY Y
x
(x + y) – (a + b)
= = (RT) = K c (RT)∆n
CA a CB b
CX x C Y Y
Where, K c =
CA a C B b
∆n = Number of moles of products (gases) – Number of moles of reactants (gases)

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∆n = (x + y) – (a + b) = change in number of moles.
Hence, K p = K c (RT)∆n
[Value of R = 0.0821 L atm. K−1 mol−1 (if the partial pressure in atm. unit), R = 8.314 J K−1
mol−1 (if the partial pressure in k Pa).]
1 atm = 101325 Pa = 101.3 k Pa.
Predicting the direction of the reaction
The equilibrium constant is also used to find in which direction the reaction will proceed for
a given concentration of reactants and products. For this purpose, we calculate the Reaction
Quotient (Q). The reaction quotient is defined in the same way as the equilibrium constant (with
molar concentrations to give Qc , or with partial pressure to give Q P) at any stage of reaction.
For a general reaction: aA + bB cC + dD
[C]c [D]d
QC = [A]a [B]b
(i) If QC > KC, the reaction will proceed in the backward direction (QC will tends to decrease so
as to become equals to KC. As a result the reaction will proceed in the backward direction)
(ii) If Qc < Kc, the reaction will move in the forward direction (QC will tends to increase. As a
result the reaction will proceed in the forward direction)
(iii) If Qc = KC then reaction will be in equilibrium.

Problems related to Kc and Kp

(i) The following concentrations were obtained for the formation of NH 3 from N2 and H2 at
equilibrium at 500K. [N2 ] = 1.5 × 10–2 M, [H2 ] = 3.0 × 10–2 M, and [NH3] = 1.2 × 10–2 M.
Calculate the equilibrium constant.
Answer:
The equilibrium constant for the reaction, N2 (g) + 3H2 (g) 2NH3 (g) can be written as
[NH3(g) ]2 (1.2 ×10−2 )2
Kc = 3
= = 3.55 × 102 mol−1 L
[N2 (g)][H2 (g)] (1.5 ×10−2 )×(3.0 ×10−2 )2

(ii) For the equilibrium, 2NOCl (g) 2NO (g) + Cl2 (g) Kc is 3.75 × 10–6 at 1069K.
Calculate the Kp for this reaction at this temperature.

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Answer:
K p = K c (RT)∆n
∆n = 3 − 2 = 1
K p = 3.75 × 10–6 × (0.0821 × 1069)1
K p = 3.291 × 10−4
(iii) At 700 K, the equilibrium constant Kp for the reaction
2SO3 (g) 2SO2 (g) + O2 (g)
–3
is 1.80 × 10 kPa. What is the numerical value of Kc in moles per litre for this reaction at the
same temperature?
Answer:
Given: 2SO3 (g) 2SO2 (g) + O2 (g)
1atm = 10 Pa, ∆n = 3 − 2 = 1
5

K p = 1.80 × 10–3 kPa = 1.8 Pa = 1.8 × 10−5 atm

K p = K c (RT)∆n
Kp 1.8 ×10−5
Kc = = = 3.132× 10−7 mol L−1
(RT)∆n (0.0821 × 700)

(iv) For the reaction, N2 (g) + 3H2 (g) 2NH3 (g), the partial pressure of N2 and H2 are
0.80 and 0.40 atmosphere respectively at equilibrium. The total pressure of the system is 2.80
atmospheres. What is Kp for above reaction.
Answer:
Given: N2 (g) + 3H2 (g) 2NH3 (g)
At equilibrium:

(v) Calculate the equilibrium constants Kp and Kc for the reaction

CO (g) + ½O2 (g) CO2 (g)
Given that the partial pressures at equilibrium in a vessel at 3000 K are:

Answer:
(a) Calculate Kp
PCO2 0.6 0.6
Kp = 1/2 = = = 3.356
PCO × PO 0.4 ×(0.2)1/2 0.4 × 0.447
2
(b) Calculate Kc
K p = K c (RT)∆n

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 Kp = K c (0.0821 × 3000)−½
1 1
= Kc × (246.3)1/2
= Kc =
15.7
Kc = Kp × 15.7
Kc = 3.36 × 15.7 = 52.75
(vi) For a system, A + 2B C, the equilibrium concentration are [A] = 0.06, [B] = 0.12,
and [C] = 0.216. Calculate the Kc for the reaction.
Answer:
Given: A + 2B C
[C] 0.216
Kc = = = 250
[A]×[B]2 0.06 × (0.12)2

(vii) For the reaction, N2O4 (g) 2NO2 (g), the concentration of an equilibrium mixture of
298 K are N2O4 = 4.50 × 10 moles L and NO2 = 1.61 × 10−2 moles L−1. What is the value of
−2 −1

equilibrium constant?
Answer:
[NO2 ]2 (1.61 ×10−2 )2
Kc = 2
= = 5.76 × 10−3 mol L−1
[N2 O4 ] (4.50 ×10−2 )2

Types of Chemical Equilibria

There are two types of chemical Equilibria, depending upon the phases (physical states) of the
reactants and the products.
(i) Homogeneous Equilibria
(ii) Heterogeneous Equilibria
(i) Homogeneous Equilibrium
When all the reactant and the products are present in the same phase (gaseous or liquid) in a
reaction at equilibrium, it is called a homogenous equilibrium.
Homogeneous Equilibria is further sub-divided into two types
Type I: The number of moles products equals to the number of moles of reactants.
For example:
N2 (g) + O2 (g) 2NO (g)
2CO (g) + 2H2O (g) 2CO2 (g) + 2H2 (g)
In the above reaction all reactants and products are in gaseous phase.
Type II: The number of moles products not equals to the number of moles of reactants.
(i) N2 (g) 3H2 (g) 2NH3 (g)
(ii) 2SO2 (g) + O2 (g) 2SO3 (g)
(iii) PCl5 (g) PCl3 (g) + Cl2 (g)
(iv) CH3COOC2H5 (aq) + H2O (l) CH3COOH (aq) + CH3COOH (aq)
3+ − 2+
(v) Fe (aq) + SCN (aq) FeSCN (aq)
In the above reaction (iv) and (v), all reactants and products are homogeneous solution phase.
(ii) Heterogeneous Equilibrium
When the reactants and products are present in two or more than two phases at equilibrium, it is
called heterogeneous equilibrium.
For example,
CaCO3 (s) CaO (s) + CO2 (g)

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 Ca(OH)2 (s) Ca2+ (aq) + 2OH− (aq)
3Fe (s) + 4H2O (g) Fe3O4 (s) + 4H2 (g)

Equilibrium Constant Expressions

In writing the equilibrium constant expressions the following two conventions must be followed.
The active mass of every solid is taken as 1.i.e., [Solid] = 1
If a pure liquid is present in excess (example, a solvent), its concentration remains almost
constant and this constant is included into the equilibrium constant, i.e., for liquid present in
excess, [Liquid] = 1.
Equilibrium Constant Expressions for Homogeneous Equilibrium
N2 (g) 3H2 (g) 2NH3 (g)
[NH3(g) ]2 P2NH3
Kc = , Kp =
[N2 (g)][H2 (g)] 3 PN2 × P3H2
PCl5 (g) PCl3 (g) + Cl2 (g)
[PCl3 (g)]×[Cl2 (g)] PCl3 × PCl2
Kc = , Kp =
[PCl5 (g)] PPCl5
CH3COOC2H5 (l) + H2O (l) CH3COOH (l) + C2H5OH (l)
Here liquids present in excess, hence
[CH3 COOH (𝑙)][C2 H5 OH(𝑙)]
Kc =
[CH3 COOC2 H5 (𝑙)][H2 O (𝑙)]
Water present in excess (being the solvent) therefore, by convention [H 2O] is a constant and
equal to 1. Hence the K c equation written as
[CH3 COOH (𝑙)][C2 H5 OH(𝑙)]
Kc =
[CH3 COOC2 H5 (𝑙)]
CH3COOH (l) + C2H5OH (l) CH3COOC2H5 (l) + H2O (l)
Here no liquids present in excess, hence
[CH3 COOC2 H5 (𝑙)][H2 O(𝑙)]
Kc =
[CH3 COOH(𝑙)][C2 H5 OH (𝑙)]
NH3 (aq) + H2O (l) NH4+ (aq) + OH− (aq)
[NH+ −
4 (𝑙)][OH (𝑙)]
Kc =
[NH3 (𝑙)] [H2 O (𝑙)]

Equilibrium Constant Expressions for Heterogeneous Equilibrium

(i) 3Fe(s) + 4H2O (g) Fe3O4 (s) + 4H2 (g)
[Fe3 O4 (s)][H2 (g)]4
Kc =
[Fe (s]3 [H2 O (g)]4
By convention, [Fe3O4] = 1 and [Fe] = 1
[H2 (g)]4 P4H2
Hence, K c = or in terms of pressure, K p =
[H2 O (g)] 4 P4H O
2
PH2
Kp = [Taking the 4th root of both the sides]
PH2 O

(ii) CaCO3 (s) CaO (s) + CO2 (g)

[CaO (s)] [CO2 (g)]
Kc =
[CaCO3 (s)]
By convention, [CaO] = 1 and [CaCO3] = 1

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Hence, K c = [CO2 (g)]

Unit of ‘Kc’ vary from reaction to reaction.

Write the expressions for equilibrium constant for the following reactions. If the
concentrations are expressed in mol L–1, give the units in each case.
(1) N2O 4 (g) 2NO2 (g)
(2) 4NH3 (g) + 5O2 (g) 4NO (g) + 6H2O
(3) N2 (g) + 3H2 (g) 2NH3 (g)
(4) 2HI (g) H2 (g) + I2 (g)
(5) 2N2O 5 (g) 4NO2 (g) + O2 (g)

Factors affecting the state of equilibrium

Le Chatelier’s principle: A chemical equilibrium is governed by the following factors:
(i) Concentration
(ii) Temperature
(iii) Pressure.
The combined effect of all the three factors studied by one principle known as Le Chatelier’s
principle It is state as:
If a system at equilibrium is subjected to a change in concentration, pressure or
temperature, the equilibrium shifts in such a direction so as to minimize or undo the effect
of the change imposed.
Le Chatelier’s principle helps to predict qualitatively the effect of change in the concentration
of the reactants or products, temperature and pressure on any reversible reaction in equilibrium.
(i) Effect of change in concentration:
As per Le Chatelier’s principles, the only way for equilibrium to accept more reactants is to
increase product formation. The forward reaction is favoured when the concentration of the
reactant is increased. The equilibrium of the reaction shift towards the use of reactants in the
reaction, which decreases the concentration of the reactants.
Similarly, the addition of product (concentration/pressure) shall increase the backward reaction
to decrease the product concentration. The backward reaction is favoured when the concentration
of the reactant decreases, the equilibrium of the reaction shift towards the production of
reactants, and the concentration of the reactants is more.
Example:
Consider a reaction between oxygen and sulfur dioxide to produce sulfur trioxide.
2SO2 (g) + O2 (g) 2SO3(g)
If the concentration of the reactant increases, then
Equilibrium will shift towards the decrease in the concentration of the reactants.
More favoured for the forward reaction.
Some of the SO2 or O2 form SO3.
Equilibrium of the reaction shift towards the right.
If the concentration of the reactant decreases, then
Equilibrium will shift towards the increase in the concentration of the reactants.

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 More favoured for the backward reaction.
Some of the SO3 would change to SO2 or O2.
Equilibrium of the reaction shift towards the left.
If the product decreases, then
The equilibrium of the reaction shift to increase the concentration of the sulfur trioxide.
Increase in the forward reaction rate.
Some of the SO2 or O2 form SO3.
Equilibrium of the reaction shift towards the right.
If the product increases, then
The equilibrium of the reaction shifts to decrease the concentration of the sulfur trioxide.
Increase in the reverse reaction rate.
Some of the SO3 would change to SO2 or O2.
Equilibrium of the reaction shift towards the left.
Some examples from everyday life
If the concentration in any one part of a system in equilibrium is disturbed, it no longer remains
in equilibrium and re-adjusts its concentration to re-establish the equilibrium. The following
illustrate this point.
(a) We sweat more on a humid day it evaporates when we sit under a fan: More sweating
takes place because the surrounding air has large amount of water vapour and our skin cannot
lose more to it. The fan removes the humid air and evaporation starts from the skin.
(b) Clothes dry quicker when there is a breeze or we keep on shaking: This is because water
vapour of the nearby air is removed and the cloth loses more water vapour to re-establish the
equilibrium with the surrounding air.
(c) Transport of oxygen by haemoglobin by blood: Oxygen breathed in combines with the
haemoglobin in the lungs according to the equilibrium
Hb (s) + O2 (g) HbO2 (s)
When it reaches the tissue, the pressure of oxygen there is low. To re-adjust the equilibrium,
oxyhaemoglobin gives up oxygen. When it returns to lungs where the pressure of oxygen there is
high, more oxyhaemoglobin is formed.
(d) Tooth decay by sweets: Our teeth are coated with an enamel of an insoluble substance
known as hydroxypatite (Ca5(PO4)3OH). It exists in equilibrium with its ions as follows:
Ca5(PO4)3OH (s) 2Ca2+ (aq) + 3PO43− (aq) + OH− (aq)
The forward reaction involving dissociation is called demineralization and the backward reaction
involving formation is called remineralisation. If we do not brush our teeth after eating sweets,
the sugar gets fermented on the teeth to produce H+ ions which combine with the OH− ions
shifting the equilibrium in the forward direction thereby causing tooth decay.
(ii) Effect of change in temperature:
There are two opposing reactions in a chemical equilibrium in which one favours the formation
of products and the other reactants. One of these reactions, heat is evolved (exothermic reaction)
and the other reaction, heat is absorbed (endothermic reaction).
The individual reaction in the equilibrium can be either endothermic or exothermic. Likewise,
at equilibrium, the net energy involved may make the reversible reactions either endothermic or
exothermic.

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According to Le Chatelier’s Principles,
 In exothermic Effect of change in temperature, an increase in temperature decreases
product formation, and a decrease in temperature increases product formation.
 In endothermic reactions, an increase in temperature increases the product formation, and
a decrease in temperature decreases the product formation
Example:
Consider a reaction
N2(g) + 3H2(g) 2NH3(g) ΔH = − 92kJ
Increase in temperature
This prefers an endothermic reaction because it takes energy.
An endothermic reaction is a reverse reaction, and it is favoured.
The yield of the product (NH3) decreases.
Decrease in temperature
This prefers an exothermic reaction because it gives energy.
An exothermic reaction is a forward reaction, and it is favoured.
The yield of the product (NH3) increases.
In endothermic reactions, the forward reaction is favoured by high temperature and in
exothermic reactions; forward reaction is favoured by low temperature.
(iii) Effect of change in pressure: If a system in equilibrium involves only solids or only
liquids, then pressure has no significant effect on equilibrium.
If a system in equilibrium involves gases then pressure plays an important role and concentration
all components can be altered by changing the pressure. If the number of gas molecules is the
same on either side, then changing of pressure will have no effect.
Example
Consider a reaction
N2(g) + 3H2(g) 2NH3(g) ΔH = − 92kJ
1 mole 3 mole 2 mole
The effect of changing the pressure on a gas-phase reaction depends on the stoichiometry of the
reaction. The formation NH3 (forward reaction) is accompanied by a decrease in number of
moles,
A reaction at equilibrium was subjected to a stress an increase in the total pressure on the
system. The reaction then shifted in the direction that minimized the effect of this stress. The
reaction shifted toward the products because this reduces the number of particles in the gas,
thereby decreasing the total pressure on the system. Thus high pressure will favour the formation
of ammonia.
Low pressure always favours those reactions which occur with increase in total number of moles
but high pressure favours those reactions which occur with decrease in total number of moles.
Pressure has no effect on equilibrium reactions which takes place with no change in total number
of moles.
Applications of Le Chatelier’s Principle
We can use Le Chatelier’s principle to increase the profits and yields of many industrial
reversible reactions by looking at the effect of changing conditions on the position of
equilibrium. For example, the reaction’s equation might tell you that increasing the pressure
increases the equilibrium yield. We can therefore apply this to the reaction in industry in order to
maximise profit.
Chemical Equilibria XI @ Haridas. V. Sukumaran 2024 Yhss Page 15 of 17
(i) Effect of change in concentration:

 Increasing concentration of one side favours the other.

(ii) Effect of change in temperature:

 If the forward reaction exothermic then backward reaction will be endothermic and vice-
versa.

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(iii) Effect of change in pressure:

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