Chemical Equilibrium

Definition of reversible reaction:

The reaction which have forward and backward rate is known as
reversible reaction.
For example:

Definition of chemical equilibrium:

The state of a reversible reaction where the rate of the forward
reaction equals the rate of the reverse reaction is known as Chemical
Equilibrium.
 Chemical Equilibrium
Graphical presentation of chemical equilibrium:
If the rate of a chemical reaction plotted along the Y-axis & time of the reversible
reaction plotted along the X-axis, then chemical equilibrium can be shown as
follows.

Forward reaction

Rate of backward reaction

 Chemical Equilibrium
Law of mass action:
At a fixed temperature and time rate of a chemical reaction is proportional to the active masses of the reactants (molar concentration or partial
pressure) present at that time.
Explanation:
To explain the law of mass action, let us consider the following reversible reaction-
A + B ⇌ C + D
Rate of forward reaction rf ∝ [A].[B]
rf = Kf.[A].[B] ………….(i)

Rate of backward reaction rb∝ [C].[D]

rb = Kb.[C].[D] …………..(ii)

At equilibrium, rf = rb
Kf.[A].[B]=Kb.[C].[D]
or, Kf/Kb = [C].[D]/[A].[B]
or, Kc = [C].[D]/[A].[B]
Where, Kc is the equilibrium constant in terms of molar constant, which can be defined as followed,
The ratio of the product of molar concentration of the products and the reactants is known as K c .
 Chemical Equilibrium
Rate of forward reaction r f ∝ PA.PB
rf = Kf. PA.Pb ………….(iii)

Rate of backward reaction r b∝ PC.PD

rb = Kb. PC.PD …………..(iv)

At equilibrium, rf = rb
Kf.PA.Pb = Kb.PC.PD
or, Kf /Kb = PC.PD / PA.PB
or, Kp = PC.PD / PA.Pb
Where, Kp is the equilibrium constant in terms of partial pressure, which can be defined as followed,
The ratio of the product of partial pressure of the products and the reactants is known as K p .
 Chemical Equilibrium
Establish the relation between Kp & Kc :
To establish the relation between Kp & Kc ,let us consider the following reversible reaction-
xA + yB ⇌ mC + nD
According to the law of mass action,
Kc = [C]m.[D]n/[A]x.[B]y ………….(i)
Kp = PCm.PDn / PAx.Pby ………….(ii)

From the Ideal Gas Equation we know that,

PV=nRT
or, P=(RT)n/V
or, P= [ ]RT
So, PA = [A]RT
PB = [B]RT
PC= [C]RT
PD= [D]RT
 Chemical Equilibrium
Using these values in equation number (ii) we get,
Kp = [C]m(RT)m.[D]n(RT)n/[A]x(RT)x.[B]y(RT)y
Or, Kp = [C]m.[D]n /[A]x.[B]y . (RT)(m+n)-(x+y)
Or, Kp = Kc. (RT) n

Where, Δn = number of product molecules/moles – number of reactant

molecules/moles.