Chemical Equilibrium

In a chemical reaction, chemical equilibrium is the state in which

both reactants and products are present in concentrations which
have no further tendency to change with time. Usually, this state
results when the forward reaction proceeds at the same rate as the
reverse reaction. The reaction rates of the forward and backward
reactions are generally not zero, but equal. Thus, there are no net
changes in the concentrations of the reactant and product. Such a
state is known as dynamic equilibrium.
Law of Mass Action
The rate of a chemical reaction at a given temperature is proportional to the
active mass of each of the reactants present in the system. Active mass meant
the molar concentration, i.e., the number of gram molecules per litre, or of any
term proportional to this, such as partial pressure in case of gases.

Mathematical Expression of the Law of Mass Action

Let us consider a simple reversible reaction of the type
A + B = C + D
Let [A], [B], [C] and [D] represent the molar concentration of A, B, C and D
respectively at any instant. According to the law of mass action the rate of the
forward reaction at any instant is proportional to the concentrations of A and B.
Then
Rateforward = k1 [A] [B]
where k1 is a constant, called the velocity constant or specific rate constant.
The speed of the reverse reaction, i.e., the one in which A and B are formed
from C and D at any instant is proportional to [C] and [D]. Hence
Ratereverse = k2 [C] [D]
where k2 is the velocity constant of the reverse reaction. At equilibrium the rate
of the forward reaction is equal to the rate of the reverse reaction. That is,
k1 [A]e [B]e = k2 [C]e [D]e
where the subscript indicates concentrations at equilibrium position. Hence
[C]e [D]e k1
= = K
[A]e [B]e k2

where K is called the equilibrium constant for the above reaction. K is equal to
the ratio of the velocity constants for the forward and the reverse reaction.
For a general reversible reaction represented by
aA + bB + ••••• = lL + mM + •••••
the equilibrium constant is given by

[L]l [M]m • • •
Kc =
[A]a [B]b • • •
where the concentrations (mol/l) are those at equilibrium.

Gaseous Equilibria
The concentrations of gases in a mixture usually are expressed in terms of the
partial pressure of the gases. Since the partial pressure of an ideal gas is
proportional to its concentration, c, the expression for the equilibrium constant
for the reaction
aA + bB + ••••• = lL + mM + •••••
may be written in the form pLl pMm • • •
Kp =
pAa pBb • • •
where Kp is the mass law constant. Kp and Kc are not always identical. This is
because the partial pressure are proportional to but not equal to gas
concentration expressed in mol/l.
A relation between Kp and Kc can be easily deduced for ideal gas, so that if Kp is
known Kc may be evaluated and vice versa. For n moles of a gas in a mixture of
volume V litres and temperature T, the partial pressure is p = (n/V)RT; but (n/V)
is equal to c, the molar concentration, so that p = cRT. Substituting this value of
p for each species at equilibrium
[L]l [M]m • • • (RT)l+m+ • • •
Kp = = Kc (RT) (l+m+ • • •) − (a+b+ • • •) = Kc (RT) Δn
[A]a [B]b • • • (RT)a+b+ • • •
where Δn is the change in the number of moles of the gas during the reaction.
When there is no change in the number of moles of the gas during the reaction,
i.e., Δn = 0, Kp = Kc.
Calculation of Equilibrium Constants
In determining the equilibrium constants the concentrations of the various
species at equilibrium are to be known. This has to be done in a manner so that
the equilibrium is not disturbed by the method of analysis used for the purpose.
The dissociation of nitrogen tetraoxide is represented by the equation
N2O4 (g) = 2NO2 (g)
Initial 1 0
Equilibrium (1-α) 2α
If α represents the degree of dissociation, (1-α) is proportional to the number of
moles of undissociated N2O4 and 2α is proportional to the number of moles of
NO2 so that (1-α+2α) or 1+α is proportional to the total number of moles. If P is
the total pressure, the partial pressures are given by 2 2α 2
(p ) P 4α2
2α 1-α NO2 1 + α
pNO2 = P pN2O4 = P Kp = = = P
1+α 1+α pN2O4 1-α 1–α 2
P
1+α
Dissociation of Phosphorous Pentachloride
The dissociation reaction is represented by the following equation:
PCl5 = PCl3 + Cl2
Initial 1 0 0
Equilibrium (1-α) α α
Let α be the degree of dissociation at equilibrium under the given conditions. If
one starts with 1 mole of PCl5 then at equilibrium there will be (1-α) moles of
undissociated PCl5 and α moles of each PCl3 and Cl2. If the reaction is carried
out in a vessel of capacity V litres, then the concentrations of the gases are
1-α α α
[PCl5] = ; [PCl3] = and [Cl2] =
V V V
The equilibrium constant (Kc) in terms of moles per litre is represented by
α α
[PCl3] [Cl2] V V α 2

Kc = = =
[PCl5] 1-α (1 – α)V
V
The expression for Kp may be determining the partial pressures of the gases
and substituting in the relation
pPCl3 pCl2
Kp =
pPCl5
The total number of moles at equilibrium is (1 - α + α + α) = (1 + α). If P is the
total pressure, the partial pressures of the gases are

1-α ; α α
pPCl5 = P pPCl3 = P and pCl2 = P
1+α 1+α 1+α

α α
P P
1+α 1+α α2
Then Kp = = P
1-α (1 – α )
2
P
1+α
Formation and Decomposition of Hydrogen Iodide Gas
An example of gaseous homogeneous equilibrium is the reaction:
2HI = H2 + I2
The expression for the equilibrium constant for the decomposition reaction may
be arrived by considering the volume of the vessel to be V litres and the
amounts in moles as follows:
Initial Equilibrium
[HI] a a - 2x
[H2] 0 x
[I2] 0 x
x x
[H2] [I2] V V x2

Then Kc = = =
[HI]2 a – 2x 2 (a – 2x)2
V
For the combination reaction, let the concentration in mole per litre of hydrogen,
iodine and hydrogen iodide be as follows:
Initial Equilibrium
[H2] a a-x
[I2] b b-x
[HI] 0 2x
2x 2
[HI]2 V 4x2
Then Kʹc = = =
[H2] [I2] a-x b-x (a – 2x)2
V V

Note that Kʹc is the reciprocal of Kc. Since Δn = 0, Kp = Kc. It may be seen that
the values of the equilibrium constant when the equilibrium is approached from
the opposite direction is the same. This proves the reversibility of reactions as
well as the validity of the law of mass action.
Le Chatelier Principle
The principle states that when a system is at equilibrium a change in any one of
the factors upon which the equilibrium depends will cause the equilibrium to shift
in a direction such that the effect of the change is diminished.
The resulting system will, however, be still in equilibrium unless the change is
very large and except in the case of change in temperature the equilibrium
constant will remain the same. This principle is, also known as the principle of
mobile equilibrium, clearly indicating that the equilibrium position can be easily
shifted by changing conditions of the reaction.
The equilibrium may be shifted to the right or to the left, the direction of the
change depending on the nature of the change brought into the system by
altering the conditions that govern the equilibrium.
Effect of Temperature Change
Chemical reactions are classified as exothermic or endothermic, depending on
whether heat is evolved or absorbed as a result of the reaction. The synthesis of
ammonia by the Haber-Bosch process is exothermic:
N2 + 3H2 = 2NH3 ΔH = - 22.0 Kcal
As heat is evolved in this reaction, according to the principle of Le Chatelier, an
increase of temperature will cause the equilibrium to move in the direction in
which the effect of the temperature rise may be diminished. This is possible if
some ammonia decomposes into nitrogen and hydrogen, the process being
endothermic. So, the equilibrium will shift to the left, i.e., the yield of ammonia will
be decreased on increasing the temperature. Conversely, if an exothermic
reaction is cooled more of the products will be formed and the equilibrium shifts
to the right.
The production of nitric oxide by the Birkeland and Eyde process is endothermic:
N2 + O2 = 2NO ΔH = + 43.2 Kcal
an increase in temperature increases the amount of the product while cooling
decreases the amount of product, i.e., shifts the equilibrium towards the left.
The change of equilibrium constant with temperature may be expressed
quantitatively in the form of the equation

ln(K) and therefore K change with temperature unless ΔH° = 0.

An alternative form of the van’t Hoff equation is:

This is a very important equation and may be used to determine heats of

reaction from measurements of equilibrium constant of reactions. For this
purpose more convenient forms are the integrated forms:
ΔHº
ln K = − + constant
RT

K2 ΔHº 1 1
ln = − −
K1 R T2 T1
Heterogeneous Equilibria
Heterogeneous equilibrium involves substances in different states. The position
of heterogeneous equilibrium does not depend on the amount of pure solid and
liquid present.
Consider the decomposition of calcium carbonate when heated to a high
temperature:
CaCO3 (s) = CaO (s) + CO2(g)
The equilibrium constant in terms of partial pressures may be written as
pCaO pCO2
Kp =
pCaCO3
At any given temperature pCaO and pCaCO3 are constant. Hence the correct
expression for the equilibrium constant, Kp, is
Kp = pCO2
The value of the equilibrium constant at any temperature is determined soley by
the equilibrium pressure of carbon dioxide evolved.
 Electrochemistry

What are Electrolytes?

• Substances whose aqueous solution or molten state conduct electricity.
• Conduction takes place by the movement of ions.
Examples: salts, acids and bases.

• Substances whose aqueous solution does not conduct

electricity are called non electrolytes.
Examples: solutions of cane sugar, glucose, urea etc.
 Types of Electrolytes

• Strong electrolytes are highly

Strong ionized in the solution at all
concentration.
Electrolytes • Examples are HCl, H2SO4, NaOH,
KOH etc

• Weak electrolytes are only feebly

Weak ionized in the solution.
• Examples are H2CO3, CH3COOH,
Electrolytes NH4OH etc
 Metallic Vs Electrolytic
Conductors
Metallic
• Flow of electricity takes place
without the decomposition of
substance i.e. no chemical
change
• Conduction is due to the flow
of electrons
• Conduction decreases with
increase in temperature
Electrolytic
• Ions are oxidized or reduced at
electrodes i.e. chemical
reaction takes place
• Flow of electricity is because
of movement of ions
• Conduction increase with
increase in temperature
 Resistance
• Resistance refers to the obstruction to the flow of
current.
• For a conductor of uniform cross section(a) and
length(l); resistance R is given by,
l l a
R l and R  R  
a a
l
where “ρ” is called resistivity or specific resistance.
 Conductance
• The reciprocal of the resistance is called conductance. It is
denoted by C.
C=1/R

• Conductors allow electric current to pass through them.

Examples are metals, aqueous solution of acids, bases and salts
etc.
• Unit of conductance is ohm-1 or mho or Siemen(S)
• Insulators do not allow the electric current to pass through
them. Examples are pure water, urea, sugar etc.
 Specific conductance
• Specific conductance or conductivity is defined as the
conductance of unit volume of a cell. It is reciprocal of
resistivity.
κ = 1/ρ and
Therefore,

or κ = (l/a) x Conductance
The quantity “l/a” is called cell constant .
Specific conductance has units ohm–1cm–1. SI Unit of specific
conductance is Sm–1 where S is Siemen.
 Equivalent Conductance
• It is the conductance of all ions furnished when one gram equivalent of an electrolyte is
dissolved in V cc of the solution. Equivalent conductance is represented by λeq

Mathematically, λeq= κ x V

Where, κ = Specific conductivity

V = Volume of solution in “cc” containing one gram equivalent of the electrolyte.
 Molar Conductance
• It is the conductance of all ions furnished when one mole of the electrolyte is dissolved in V
cc of the solution. Molar conductance is represented by λm
Mathematically, λm= κ x V

Where, κ = Specific conductivity

V = Volume of solution in “cc” containing one gram equivalent of the electrolyte.
 Factors affecting electrolytic
conduction
• Nature of electrolyte: Strong electrolytes ionize almost
completely in the solution whereas weak electrolytes ionize
to a small extent.
• Size of ions: larger the ion, smaller will be its conductance.
• Nature of solvent and viscosity: Greater the polarity of the
solvent, greater is the conductance. Greater the viscosity,
lesser will be the conductance.
• Concentration of solution: Higher the concentration of the
solution, less is the conduction.
• Temperature: On increasing the T, the dissociation increases
and the conduction increases.
 Variation of Conductance with
dilution
• Specific conductivity
decreases on dilution.

• Equivalent and molar

conductance both increase
with dilution and reaches a
maximum value.

• The conductance of all

electrolytes increases with
temperature.
 Strong Vs weak electrolytes
Strong electrolytes:
• The molar and equivalent conductance at infinite
dilution can be obtained by extrapolating the line.
• It is denoted by λ∞
• Increase in the Molar and equivalent conductance is
due to weakening of intermolecular forces upon
dilution.
• Follow Debye Hückel Theory (λcm = λ∞m – A √C)
Weak electrolytes:
• The molar and equivalent conductance at infinite
dilution can be obtained by Kohlrausch’s Law
• Increase in the Molar and equivalent conductance is
due to increase in the number of ions upon dilution.
 Kohlrausch’s Law
Statement: “At time infinite dilution, the molar conductance of an electrolyte can be expressed as the
sum of the contributions from its individual ions” i.e. Λ∞m = v+ λ∞+ + v- λ∞-

where, v+ and v- are the number of cations and anions per formula unit of electrolyte respectively

and, λ∞+ and λ∞- are the molar conductivities of the cation and anion at infinite dilution respectively.

For e.g. The molar conductivity of HCl at infinite dilution can be expressed as,

Λ∞HCI = vH+λ∞H+ + vCI-λ∞CI-; For HCI, vH+ = 1 and vCI- = 1.

So, Λ∞HCI = (1 x λ∞H+) + (1 x λ∞H-); Hence,

Λ∞HCI = λ∞H+ + λ∞CI-