CH 7 EQUILIBRIUM

#) EQUILIBRIUM. IT Represents the state of a process in which the property like

temperature, pressure and concentration do not change with time. In
equilibrium, two opposing processes are involved. If these are physical
changes. It is called physical equilibrium and if these are chemical reactions, it is
called chemical equilibrium. At equilibrium, the two opposing processes take
place at equal rate.
#)Physical equilibrium :
(I) Solid - liquid equilibrium, e.g., melting of ice ----> water. At equilibrium, rate
of melting of ice = rate of freezing of water.
(ii) Liquid - vapour equilibrium, e.g., evaporation of water in a closed vessel,
water ---> vapour. At equilibrium, rate of evaporation = rate of condesation.
(iii) Solid-vapour equilibrium, e.g., sublimation of 12 ,12 (s) ---> I2 (vapour).
(iv) Solid-solution equilibrium, e.g., Saturated solution of sugar containing some
undissolved sugar, Sugar (solid)---> Sugar (solution). At equilibrium, rate of
dissolution= rate of precipitation.
#)Chemical equilibria
(I)Reversible and irreversible reactions. A reaction which takes place in the
forward direction as well as backward direction is called a reversible reaction. It
represented by putting double arrows between reactants and products.If a
reaction cannot take place in the reverse direction, it is called an irreversible
reactions.
(ii) Concept of equilibrium and its dynamic nature. When equilibrium is
attained, rate of forward reaction and backward reaction become equal.
Hence, concentration of each reactant and product remains constant, I.e., does
not change with time. It appears that the reaction has stopped. This is actually
not so. Reaction is still going on in forward as well as backward direction at
equal rate. Thus, equilibrium is dynamic and not static in nature.

#) Characteristics of chemical equilibrium. (I) At equilibrium, concentration of

each reactant and product remains constant.
(ii)At equilibrium, rate of forward reaction = rate of backward reaction and
equilibrium is dynamic in nature.
(iii) A chemical equilibrium is attained only if none of the products is allowed to
escape.
(iv) Chemical equilibrium can be attained from either direction.
(v) A catalyst does not alter the st of equilibrium. It simply helps to attain the
equilibrium quickly.
#)Law of masss action. It states, " Rate at which a substance reacts is directly
proportional to its active mass and hence the rate of a chemical reaction is
directly proportional to the product of the active masses the reactants."Active
mass of a substance means its molar concentration. Active mass of A is
represented as [A].
#)Law of chemical equilibrium. Applying law of mass action to a reversible
reaction in equilibrium. We have rate of forward reaction (R f ) = k f [ A] a [B]b and
rate of backward reaction ( R b ) = k b [X]x [Y]y where k f and k b are rate constants
for forward and backward reaction.
#)Relationship between K p and K c : K p =K c (RT)n where n = (n p -n r ) gaseous
#)Characteristics of equilibrium constant. (I) Equilibrium constant of a reaction
is constant at constant temperatures and does not depend upon the
concentration of reactants.
(II) If the equation with equilibrium constant K is divided by 2, new equilibrium
constant is K.
(III) If equation with equilibrium constant K is multiplied by 2, equilibrium
constant for the new equation will be K2.
(III) If equation with equilibrium constant K takes place in two steps having
equilibrium constants K1 and K2 , then K=K1 * K2 .
(IV) Value of equilibrium constant is not affected by catalyst.

#)Effect of temperature on equilibrium constant.K= k f / k b . In endothermic

reactions, with increase of temperature k f increases more than k b . In
exothermic reactions, with increase of temperature, k b increases more than k f.
Hence, K decreases. Quantitatively, the effect of temp. On K p is given by van't
Hoff eqn.
#)Types of chemical equilibria: (I) Homogenous equilibria., i.e.,when all the
reactants and product are present in the same phase.
(II)Heterogeneous equilibria. I.e., when all the reactants and products are not
in the same phase.
#)Expressions for equilibrium constant. Products are written in the numerator
and reactants in the denominator. For pure solids or pure liquid present in
excess, active mass is taken as 1.
#)Applications of equilibrium constant
(I) Predicting extend of reaction. If K is large (> 103), forward reaction is
favoured. If K is small ( < 10-3) ,backward reaction is favoured.
(II) Predicting direction of reaction. For a state other than equilibrium state,
concentration quotient (Q) = [X]x [Y]y / [A]a [B]b . If Q = K, reaction is in
equilibrium. If Q > K ,Q tends to decrease, I.e., reaction proceeds in backward
direction. If Q < K , Q tends to increase, I.e., reaction proceeds in forward
direction.
#)Effect of adding inert gas on equilibrium. There is no effect when (

n p = n r )gaseous. Effect is observed when (n p = n r )gaseous and reaction

takes place at constant pressure. At constant volume, there is no
effect because adding inert gas at constant volume does not change
molar concentrations.
#) Le Chatelier's principle (Effect of concentration, temp. and
pressure on equilibrium). It states, "If a system in equilibrium is
subjected to a change of concentration , temperature or pressure,
equilibrium shifts in the direction that tends to undo the effect of the
change imposed."

#) Effect of concentration. At equilibrium, if concentration of any

reactant is increased, the equilibrium shifts in the forward direction
and if the concentration of any product is increased,equilibrium shifts
in the backward direction.
(II) Effect of temperature. Exothermic reactions are favoured by low
temperature whereas endothermic reactions are favoured by high
temperature.