CHEMICAL EQUILIBRIUM: Those reactions which proceeds in forward direction and

reaches almost to completion are called irreversible reactions.

Those reactions which proceed in forward and backward directions both and never
reach completion are called reversible reactions. These reactions can be initiated in
any direction.
Reactions with explosive nature, reactions in which one of the products was expelled
out as gas or as precipitate are irreversible. Gaseous reactions takes place in open
vessel also acts as irreversible. Except these all reactions are reversible in nature.

State of chemical equilibrium can be defined as the state when the rate of forward
reaction becomes equal to rate of reverse reaction and the concentration of all the
species becomes constant”.
  Equilibrium 
Forward 
reaction 
Rate of reaction
Concentration

State of equilibrium 
Backward 
reaction 
Reactant 

Time  Time 
At equilibrium concentration of reactants and products may or may not equal but
they must remains constant but the rate of forward and back word reaction must
remains same.

Characteristics of Equilibrium State:

1. Can be recognized by the constancy of certain measurable properties such as

pressure, density, intensity of colour, concentration etc.
2. Can only be achieved in case of reversible reaction carried out in a closed
container.
3. Is dynamic in nature. i.e., Rate of forward reaction = Rate of backward reaction.
4. G = 0, so that H = TS. and can be achieved from both the directions.
5. Unaffected by catalyst, however time to come to equilibrium decreases with
+ve catalyst.
LAW OF MASS ACTION
For a chemical reversible reaction aA  bB cC  dD , At equilibrium, R f  Rb ,by
applying law of mass action
Rate of forward reaction, Rf = kf[A]a[B]b

Rate of reverse reaction Rr = kr[C]c [D]d

So kf[A]a [B]b = kr[C]c[D]d

kf [C]c [D]d
 Kc 
kr [A]a [B]b

[C ]c [ D]d pCc pDd  ng

Kc  ; Kp  ; K p  K c  RT  : K p  K x ( P ) n
[ A]a [ B]b p Aa pBb

Characteristics of equilibrium constant:

1. Independent of the original concentration of reactants.
2. For a reversible reaction, the equilibrium constant for the forward reaction is
inverse of the equilibrium constant for the backward reaction.
3. The value of equilibrium constant tells the extent to which a reaction proceeds
in the forward or reverse direction.
4. The equilibrium constant is independent of the presence of catalyst.
5. The value of the equilibrium constant depends upon the stoichiometry of the
chemical equation.
6. Equilibrium constant value is dependent on temperature and representation of
reaction only. (But remember equilibrium constant in terms of mole fraction
is dependent on external pressure also.)
7. If the enthalpy of a reaction is defined in terms of activation energies as
K2 H  T2  T1 
H  Ea f  Ea b log   
K1 2.303R  T1T2 

Significance of the Magnitude of on Equilibrium Constant:

A very large value of KC or KP signifies that the forward reaction goes to
completion or very nearly so.
A very small value of KC or KP signifies that the forward reaction does not occur to
any significant extent.
A reaction is most likely to reach a state of equilibrium in which both reactants and
products are present if the numerical value of Kc or KP is neither very large nor very
small.

Reaction Quotient Q:

To compare the position of reaction with equilibrium state we can use reaction
quotient which is the same expression as that of equilibrium constant but at any
concentration.
1. If Q > K, the reaction will proceed in the direction of reactants (reverse
reaction).
2. If Q < K, the reaction will proceed in the direction of the products (forward
reaction).
3. If Q = K, the reaction mixture is already at equilibrium.

Gibb’s Free energy vs. Equilibrium Constant:

1. For a chemical reversible reaction G  G o  RT ln Q
2. G  0 for a reaction at equilibrium but G o  0 ; hence at equilibrium

G o   RT ln K

3. For a given reaction free energy of system is minimum at equilibrium position

and entropy of universe (not system) is maximum at that position.
4. In the equation G 0   RT ln K , if one puts K  K P he takes standard state as 1 at

m pressure. But if someone puts K  KC , he takes standard as 1 mole litre 1

concentration. Since the two standards are different, values may also be
different.
5.

Because

To determine Ho and So, plot ln Keq vs 1/T. The resulting straight line will have
a slope equal to - Ho/R and an intercept equal to So/R.

Note: 1.in the reaction, where all gaseous reactants and products; K represents Kp
2. In the reaction, where all solution reactants and products; K represents Kc
3. A mixture of solution and gaseous reactants; Kx represents the
thermodynamic equilibrium constant and we do not make the
distinction between Kp and Kc.
When G 0 = –ve or K > 1: forward reaction is feasible
G 0 = +ve or K < 1: reverse reaction is feasible
G 0 = 0 or K = 1: reaction is at equilibrium (very rare)
4. in hetero generous equilibrium

G 0  G 0 products  G 0 rectents
 PV
Le-Chatelier's Principle
Shifts the equilibrium
    
1. Increase in temperature in the direction of
Endothermic reaction
Shifts the equilibrium
    
2. Decrease in temperature in the direction of
Exothermic reaction
Shifts the equilibrium
    
3. Increase in pressure in the direction of
Decreasing gaseous moles
 Shifts the equilibrium
    
4. Decrease in pressure in the direction of
Increasing gaseous moles
Shifts the equilibrium
    
5. Increase in volume in the direction of
Increasing gaseous moles
Shifts the equilibrium
    
6. Decrease in volume in the direction of
Decreasing gaseous mole
V  cons tan t
  
7. Addition of an inert gases No effect on the equilibrium.
P  cons tan t
  
Shifts the equilibriu m
8. Addition of an inert gas in the direction of
Increasing gaseous moles.

Graphical representation for Lechatelier principle for habors process

1. At point 1 nitrogen gas was added to equilibrium mixture

2. At point 2 concentrations of all components increases which means that

pressure increased or volume decreased?

3. At point 3 without any sudden change in concentration of components

ammonia decomposition increases which means that temperature of system
increases.

Note: if the reaction is decomposition then that reaction is endothermic

generally.
4. Effect of temperature in graphical form is
 Effect of temperature on rate of reaction in equilibrium reactions:

Endothermic reaction

In exothermic reactions also both rates increases but backward rate increases
more readily than forward reactions i.e. in such case blue line represents
backward rate and red line represents forward rate .

Heterogeneous equilibrium: if all components are not of same phase (remember not
physical state) then that reaction is heterogeneous equilibrium. For example
diamond and graphite are different phases that’s why allotropic conversion also
heterogeneous reaction.

Application of Lechatelier principle for heterogeneous equilibrium:

Le Chatelier’s principle, as already stated, is applicable to all types of equilibria
involving not only chemical but physical changes as well. A few examples of its
application to physical equilibria are discussed below.

1. Effect of pressure on the boiling point of a liquid: The conversion of liquid

into vapour, as represented by the above equilibrium, is accompanied by
increase of pressure (vapour pressure). Therefore, if pressure on the system is
increased, some of the vapours will change into liquid so as to lower the
pressure. Thus, the application of pressure on the system tends to condense
the vapour into liquid state at a given temperature. In order to counteract it, a
higher temperature is needed. This explains the rise of boiling point of a liquid
on the application of pressure.

2. Effect of pressure on the freezing point of a liquid (or melting point of a

solid): At the melting point, solid and liquid are in equilibrium:
Solid   Liquid
Now, when a solid melts, there is usually a change, either increase or
decrease, of volume. For example, when ice melts, there is decrease in
volume, or at constant volume, there is decrease in pressure. Thus, increase of
pressure on ice water system at a constant temperature will cause the
equilibrium to shift towards the right, i.e., it will cause the ice to melt. Hence,
in order to retain ice in equilibrium with water at the higher pressure it will be
 necessary to lower the temperature. Thus, the application of pressure will
lower the melting point of ice.
When sulphur melts, there is increase in volume or at constant volume, there
is increase in pressure. From similar considerations, it follows that if the
pressure on the system, sulphur (solid)    sulphur (liquid) is increased, the
melting point is raised.

3. Effect of temperature on solubility: In most cases, when a solute passes into

solution, heat is absorbed, i.e., cooling results. Therefore according to Le
Chatelier’s principle, when heat is applied to a saturated solution in contact
with solute, the change will take place in that direction which absorbed heat
(i.e., which tends to produce cooling). Therefore, some more of the solute will
dissolve. In other words, the solubility of the substance increases with rise in
temperature.
Dissociation of a few salts (e.g., calcium salts of organic acids) is accompanied
by evolution of heat. In such cases, evidently, the solubility decreases with rise
in temperature.
4. Allotropic modification: in case of allotropic modification increase in pressure
favours denser component and increase in temperature favours more
energetic component. For example among graphite and diamond ,diamond is
more denser so high pressure favours conversion of graphite to diamond, and
among these two diamond is more energetic so high temperature favours
formation diamond.
Note: to compare energy we can use thermodynamically stability, we know
that graphite is thermodynamically more stable diamond so graphite is low
energetic.

Relation between vapour density and degree of dissociation:

D0  Dt
1.  Where D0 is vapour density at t = 0 and Dt at time t; n is the
Dt ( n  1)

number of moles of products formed per mole of reactant. (Instead of density you
can use molecular weight or vapour density or pressure at initial stage as well as at
equilibrium stage, if volume is constant)
2. This expression is not applicable if n = 1.
Ex: H 2  I 2 2 HI ; 2NO N 2  O2

Note: n is the number of moles of products from one mole of reactant. ”n” is also
called Van’t Hoff factor if the compound undergoes total decomposition.
Thus for the equilibria
 I: PCl5(g)  PCl3(g)  Cl2(g) ,  n = 2

II: N 2 O 4(g)  2NO 2(g) ,  n = 2

1
III: 2NO 2  N 2O 4 ,  n= 
2

Also D0 × 2 = Molecular weight (theoretical value)

Dt × 2 = Molecular weight (abnormal value) of the mixture
PM
You can use D  to calculate initial density.
RT

Simultaneous equilibrium:
If any one component (not solid component) is same in two equilibrium reactions
which occurs in same vessel then that phenomenon is known as simultaneous
equilibrium.
In case of simultaneous equilibrium the common component must have same
concentration in both equilibrium. For example if decomposition of ammonia and
hydrazine takes place in same vessel then that is simultaneous equilibrium.
1 3
NH 3  N2  H 2 N 2 H 4  N2  2H 2
2 2
If initial no of moles of ammonia and hydrazine are “a” and “b” and “x” and “y” are
extent of decomposition respectively then at equilibrium concentration of
components are as follows

No of moles ammonia  a  x
No of moles hydrazine  a  y
3
No of moles hydrozen  x  2 y
2
1
No of moles nytrozen  x  y
2

And you can write equilibrium constant expressions just like normal.

EQUILIBRIUM REACTIONS CORRESPONDING TO HYDRATED SALTS:

In case of hydrated salts there is equilibrium between hydrated salts and partially or
totally dehydrated salts as like below.
CuSO4 .5 H 2O  s   CuSO4  s   5 H 2O g 
So on the surface of any hydrated salt we can observe some water vapour pressure
due to equilibrium between hydrated and (partially) dehydrated salt and depending
on this equilibrium vapour pressure the salt may be involved in efflorescence or
delinquency.
 1. If equilibrium water vapour pressure is less than atmospheric water vapour
pressure then water vapour molecules moves from atmosphere onto the solid
or in other words solid absorbs moisture from surroundings and acts as
desiccant or drying agent and weight of substance increases and this
phenomenon is known as hygroscopic nature (if solid absorbs limited no of
water molecules) or delinquency if solid absorbs water until it converts into
solution.
2. If equilibrium water vapour pressure is more than the atmospheric water
vapour pressure then solid looses water molecules to the atmosphere and
solid loses its weight and solid undergoes efflorescence.
3. If equilibrium water vapour pressure is equal to the atmospheric water vapour
pressure substance won’t lose water or absorbs water so weight of substance
remains constant.

Relative Humidity (RH). Is a ratio, expressed in percent, of the amount of

atmospheric moisture present relative to the amount that would be present if the air
were saturated i.e. aqueous tension. Since the latter amount is dependent on
temperature, relative humidity is a function of both moisture content and
temperature.
actual vapour density
Relative Humidity =  100
saturation vapour density
To know the nature of substance we have to calculate actual vapour pressure from
relative humidity and by comparing this with equilibrium water vapour pressure we
can decide the nature of substance.

equilibrium vapour pressure over the solid

Equilibrium relative humidity =  100
saturated water vapour pressure (or )aqueous tention
If relative humidity is less than equilibrium relative humidity then substance
undergoes efflorescence.
If relative humidity is more than equilibrium relative humidity then substance acts as
drying agent.
If relative humidity is equal to equilibrium relative humidity then substance never
exhibits efflorescence or hygroscopic nature.