Chemical

Equilibrium

STATE OF NO CHANGE
Reaction Rate and kinetics
The rate of a reaction means the speed with which the reaction takes place. This
is expressed either in terms of decrease in the concentration of a reactant per unit
time or increase in the concentration of a product per unit time.
Rate of reaction = Decrease in the concentration of a reactant
Time interval

Increase in the concentration of a product

Time interval
It may be emphasized that the rate of reaction is always positive. The minus
sign alongwith the first term is used simply to show that the concentration of
the reactant is decreasing while plus sign along with the other two terms is used
to show that the concentration of the products and is increasing.
In general, for any reaction of the type
A+B C+D
[A ] [B] [C] [D]
Rate of reaction = 
t

t

t

t
Types of Rates
Relation Between the Rate of Reactions of Different Species Taking Part in a
Chemical Reaction
N2 + 3H2 2NH3

d[N 2 ]
rate of reaction of N2 =
dt
rate of reaction of H2 = d[H 2 ]
dt
d[NH3 ]
rate of reaction of NH3 =
dt
From above we can have the following relation between the rate of reactions of different
species d[N ] 1 d[H ] 1 d[NH ]
2 2 3
 
dt 3 dt 2 dt
The value of above expressions is also written as rate of the given reaction.

Remember that “Rate of Reaction” phrase has no meaning if a balanced equation is not given. Hence rate of reaction phrase is always
used with a balanced chemical equation,

And for balanced chemical equation as given below,

aA + bB cC + dD

rate of reaction means

1 d[A] 1 d[B] 1 d[C] 1 d[D]
Rate of reaction =   
a dt b dt c dt d dt
 Unit of Rate and Rate Law
Since concentration is usually expressed in moles/litre and the time is taken in seconds or
minutes, the unit of the rate of reaction is moles litre–1 sec–1 (mol L–1 s–1) or moles litre–1
min–1
(mol L–1 min–1).
Order or reaction
Order of reaction is the sum of the exponents of all the concentration terms
appearing in the rate law expression
Remember that order is always experimentally calculated.
Unit of Rate Constant
Molecularity
Reaction Mechanism
There are three main factors for a reaction to occur
1. Collision among molecules- Bonds are broken mainly due to collision of
molecules. On increasing concentration , no of molecules in unit volume will
increase and therefore more collisions will occur in unit time .
2. Energy – The kinetic energy of all the molecules are not same. A specific energy
is required to break the molecules( Called as activation energy ). On increasing more
molecules become capable to break the bonds so reaction occur fast
3. Orientation- Bonds are formed in particular direction and this is specific
property of each molecule or species to form
Transition Step and Activated Complex
Steady State Approximation
Chemical Equilibrium
At
Equilibrium…..
At equilibrium net free energy
change becomes zero so reaction
does not move in any direction.
But because this is dynamic
equilibrium, so we say that
reaction is free to move in both
the directions, rate of forward
reaction becomes equal to rate of
backward reaction and change in
concentration of reactants and
products becomes zero with time.
Relationship between Kp and Kc
THE LE-
CHATELIER’S
PRINCIPLE
“When a chemical reaction at
equilibrium is subjected to
any stress, then the
equilibrium shifts in that
direction in which the effect
of the stress is reduced”.
Now, let us examine the effect of change in certain parameters such as number of moles, pressure,
temperature etc.
If we increase a or b, the left-hand side expression becomes QP ( as it is disturbed from
equilibrium) and we can see that QP > KP
The reaction therefore moves backward to make QP = KP.
If we increase c, QP < KP and the reaction has to move forward to revert
back to equilibrium.
If we increase the volume of the container (which amounts to decreasing the pressure), QP < KP
and the reaction moves forward to attain equilibrium.
If we increase the pressure of the reaction, then equilibrium shifts towards backward direction
since in reactant side we have got 2 moles and on product side we have got 4 moles. So pressure is
reduced in backward direction.