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CHEMICAL EQUILIBRIUM
Synopsis:
• Based on the direction of their occurrence Chemical reactions are two types.
• Irreversible reactions: in these reactions reactants are converted into products and products cannot be
converted into reactants.
• There are unidirectional as they occur in one direction. i.e. Reactants → products.
• These are denoted by single arrow mark.
• These reactions almost go for completion i.e. reactants are almost completely convert into products.
• Precipitation – ionic reactions, explosive reactions, strong acid – strong base neutralisation reactions,
combustion- reactions are irreversible.
Eg :1) 2KClO3(s)→2KCl(s) + 3O2(g)
2) NH4NO2(s) → N2(g) + 2H2O(g)
3) C2H5OH(l) → 3O2(g) → 2CO2(g) + 3H2O(g)
4) 2Mg(s) + O2(g) → 2MgO (s)
5) HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l)
6) H2(g) + F2(g) → 2HF(g)
7) H2(g) + Cl2(g) → 2HCl(g)
Reversible reactions :
• A reaction is said to be reversible, if both the forward and the backward reactions are taking place
simultaneously under the given experimental conditions.
• Reactants giving rise to products is known as forward reaction.
• Products giving rise to reactants is known as reverse reaction (or) backward reaction.
• Reversible reactions are represented by writing a pair of half headed – arrows pointing in opposite directions
in between the reactants and products.
Reactants products
• A reverse reaction does not go to completion.
• Most of the reversible reactions are carried in the closed vessels.
Eg : 1) H2(g) + I2(g) ⇔ 2HI(g)
2) PCl5(g) ⇔ PCl3(g) + Cl2(g)
3) 2NO2(g) ⇔ N2O4(g)-
4) N2(g) + O2(g) ⇔ 2NO(g)
5) 2SO2(g) + O2(g) ⇔ 2SO3(g)
6) CaCO3(s) ⇔ CaO(s) + CO2(g)
7) CH3COOH(l) + C2H5OH(l) ⇔ CH3COOC2H5(l) H2O(l)
Equilibrium State :
• The stage or state at which the rate of forward reaction is equal to the rate of the reverse reaction in a
reversible reaction is known as the equilibrium stage or state.
• The chemical equilibrium is considered as dynamic equilibrium because the forward and the reverse reactions
1
Chemical Equilibrium
2
Chemical Equilibrium
kc =
kf
=
[C] c [D] d
k b [A ] a [B] b
kc =
[HI ] 2
[ H2 ] [I2 ]
No unit for Kc
2
PHI
kp =
p H2 × p I2
No unit for Kp
ii) 2SO2(g) + O2(g) 2SO3(g)
kc =
[SO3 ] ; k = PSO
2 2
3
4
Chemical Equilibrium
equilibrium towards the reactant side and rate of backward reaction is increased.
Effect of pressure :
• Pressure has no effect on equilibrium if Δv or Δn=0, (np= nr).
Eg : H2(g) + I2(g) ⇔ 2HI(g)
• Pressure has effect on equilibrium if Δv≠0 or Δn≠0, (np≠ nr). When pressure increases, equilibrium shifts in a
direction of decrease of volume or towards less mole number and vice vessa.
Eg: N2(g) + 3H2(g) ⇔ 2NH3(g)
When pressure increases, equilibrium shifts towards right and forward reaction rate increases.
• Pressure does not show any marked effect on equilibrium reactions taking place in the solution phase or in the
solid phase.
• Effect of temperature : increase of temperature of the equilibrium system favours endothermic reactions, and
decrease of temperature of the equilibrium system favours exothermic reactions.
• Effect of Catalyst : Catalyst has no net effect on equilibrium. It helps the system to attain equilibrium at a
faster rate by increasing the rate of forward as well as backward reaction to the same extent.
Eg:(1) Synthesis of ammonia by Haber’s process:
N2(g) + 3H2(g) ⇔ 2NH3(g) + heat ΔH = – 92.0 K.J
Favourable conditions for high yield of NH3:
High pressure:200atm, Catalyst : Fe as catalyst
Low temperature : 773 K, Promoter: small amount of molybdenum or Al2O3 and K2O.
(2) Manufacture of H2SO4 by the contact process.
2SO2(g) + O2(g) ⇔ 2SO3(g) + Heat; ΔH = –189 K.j
• Favourable conditions for higher yield of SO3.
I) High pressure : 1.5 – 1.7 atm.
ii) Low temperature : 673 k
iii) Catalyst : V2O5 or platinised asbestos
N2(g) + O2(g) 2NO(g) – heat
i) High temperature ii) No effect of pressure
Melting of ice :
H2O(s)+ heat H2O
I) high temperature ii) high pressure