Equilibria:[ Equilibrium ]

Equilibrium :
Introduction :
Equilibrium is the state of any process in which the
observable parameters like concentration , temperature ,
Pressure, colour etc. does not change with time. When a
reaction has reached the equilibrium the concentration of
reactants and products do not change with time. i.e.
concentrations of reactants and products become constant ,
(the properties of the system like temperature, pressure,
concentration etc. of the system remains constant).
At equilibrium, the concentration of reactants and
products may or may not be equal but must remains
unchanged with time. It is because the rate of forward
reaction is equal to the rate of back ward reaction.
 Reversible and irreversible reactions :
reversible reactions :
⚫ A reaction in which reactants react together to form the
products & at the same time the products also react to form
reactants under the same conditions is called reversible
reactions. During reversible reaction, there is occurance of
both forward and backward reaction.It occurs only in
closed container. The reactants and products is separated by
double headed arrow.( arrow) . This reaction is also known
as opposing reaction.
⚫ In general, A + B (⇄) C + D

⚫ E.g. N2(g) + 3 H 2 (g) ( ⇄) 2 NH3 (g)

H2 (g) + I2 (g) <--------- 2 HI (g)

 Irreversible reactions :

⚫ A reaction in which reactants react together to form products

and at the same time the products can not react to form reactants
under the same conditions is called irreversible reactions. During
irreversible reaction, there is occurance of only forward reaction.This
reaction occurs in closed as well as open container. The single headed
arrow( ) always pointed towards product side to represent the
reaction. The concentration of reactant always decrease and
concentration of product always increase.
⚫ In general, A + B ------------ C + D
Zn (s) + 2HCl (aq) ---------- ZnCl2 (aq ) + H2 (g)
( heat)
2 KClO3 (s) ---------- > 2 KCl (s) + 3O2 (g)

2Na + 2H2O ------------- 2NaOH + H2

NaCl + AgNO3 ----------- AgCl + NaNO3
 Forward reaction : The reaction in which , reactants react
together to form products .

Backward reaction : The reaction in which , products react

together to form reactants.

Types of equilibrium:

1) Physical equilibrium

2) Chemical equilibrium

Note : If the equilibrium is involved in ionization reaction , then it

is called ionic equilibrium.
 Physical equilibrium :
The equilibrium which exists in physical process is called
physical equilibrium. In this equilibrium only change in their
physical state but chemical properties remains same.The various
types of physical equilibrium are discussed below:

1 ) Solid – liquid equilibrium : The equilibrium in which solid and

liquid phase of a substance exist in equilibrium to each other is
called solid- liquid equilibrium . The two process involved are
melting and freezing.

Melting
For e. g. H2O ( solid/ Ice ) ---------- H2O (liquid)
Freezing

Here, rate of melting of ice = rate of freezing of H2O.

 2) Liquid – vapour equilibrium: The equilibrium in which liquid and vapour phase of a
substance exist in equilibrium to each other is called Liquid – vapour equilibrium . The two
process involved are evaporation (vapourization) and condensation.

Vapourization
For e. g. H 2O ( l ) ------------ H2O ( g )
Condesation

Here, rate of vapourization of H2O = rate of condensation of H2O vapour.

3) Solid- Vapour equilibrium : The equilibrium in which solid and Vapour(gas) phase of a
substance exist in equilibrium to each other is called solid- vapour equilibrium . The two
process involved are vapourization (evaporation) and condensation.

Vapourization
For e. g. Camphor ( s ) ----------- Camphor ( g )
Condensation

Here, rate of vapourization of camphor = rate of condensation of camphor vapour.

 4) Solid – solution equilibrium : The equilibrium in which there is existence of equilibrium
between solid phase and it’s saturated solution is called solid – solution equilibrium. The
two process involved are dissolution and precipitation.

dissolution
For e. g. NaCl ( s ) ----------- NaCl ( aq )
precipitation

Here, rate of dissolution of NaCl = rate of precipitation of NaCl from the solution .
 Chemical equilibrium :
The equilibrium between different chemical species present in the
same or different phases is called chemical equilibrium or When a
reversible reaction is carried out in a closed vessel, a stage is reached
in which forward and backward reactions proceed with the same
rate called chemical equilibrium. It is dynamic in nature.

During chemical reaction , the concentration of reactant

is maximum and that of product is minimum initially. Hence, the rate
of forward reaction is faster and that of backward reaction is slower
initially. As time passes the concentration of reactant decreases and
that of product increases.Hence, the rate of forward reaction
becomes slower and that of backward reaction becomes faster.
 During this process, a stage comes in which rate of forward
reaction becomes equal to the rate of backward reaction . This stage
in a process is called equilibrium. At equilibrium state , reaction
seems to be stopped but actually that is not so. It is because the
rate of forward reaction is equal to the rate of back ward reaction.
So , chemical equilibrium is dynamic in nature which can be
represented as graphically as below:

Graph :
 Types of chemical equilibrium :
I ) Homogeneous equilibrium ii) Heterogeneous eqilibrium
Homogeneous equilibrium : A chemical equilibrium in which
the reactants and products are in same phases is known as homog-
eneous equilibrium.
For e.g. i) N2 (g) + 3 H2 (g) ------- 2NH3 (g) + heat

ii) H2 (g) + I2 (g) ------ 2 HI (g)

iii) PCl5 (g) ------------ PCl3 (g) + Cl2 (g)
Hydrolysis of ester in acidic medium :
H+
iv) CH3COOC2H5 (l) + H2O (l) ----- CH3COOH (aq) + C2H5OH (aq)
(ethyl acetate) (acetic acid) (ethyl
alcohol)
 Heterogeneous equilibrium : The equilibrium in which
reactants and products are in different phases is called
heterogeneous equilibrium. iv) 2 Pb3O4(s) - 6PbO(s) + O2(g)
For e. g. i) CaCO3 (s) -------- CaO(s) + CO2 (g)
ii) FeO (s) + CO (g) ------ Fe (s) + CO2 (g)
iii) 2 Cu (NO3)2(s) --------- 2 CuO (s) + 4NO2 (g) + O2 (g)
Characteristics of chemical equilibrium:
1) It is dynamic in nature.
2) The state of equilibrium can be approached from both sides of
the reaction.
3) The state of equilibrium is dependent only upon the
temperature.
4) The factors like concentration , catalyst etc. has no effect in the
state of equilibrium.
5) The state of equilibrium is obtained only in closed vessel.
6) A chemical equilibrium is characterized by a constant called
equilibrium constant ‘ K ‘.
 Le-Chatelier’s principle

The factors like temperature , pressure , concentration etc.affects

the state of equilibrium , the effect of this factors in equilibrium
was studied by Henry Le-chatelier’s in 1884 and he gave a law which
is called as Le-chatelier’s principle.

It states that”when a systam in equilibrium is subjected to stress by

changing temperature,pressure,concentration etc,then the

equilibrium shifts in that direction which nullifies the effect of stress

imposed.”
It means that;
1) If the temperature of system is increased then the equilibrium
shifts in that direction which absorbs the heat(i.e. towards
endothermic direction) and vice–versa.
2) If the pressure of system is increased then the equilibrium shifts
 3) If the concentration of system is increased then the equilibrium
shifts in that direction where added concentration is consumed i. e.
increase in concentration of reactant shifts the reaction towards
product(i. e. favours forward reaction) and increase in concentration
of product shifts the reaction towards reactant (i. e. favours
backward reaction).

4) If the catalyst is used then the state of equilibrium remains

same.
 5) Effect of addition of inert gas:
An inert gas does not participate in the reaction . However it does affect the
equilibrium condition depending on how the inert gas is introduced. Effect of
inert gas can be studied at constant volume and at constant pressure .

i) At constant volume : when an inert gas is introduced into the equilibrium

system at constant volume . The total gas pressure will increase but the
concentration or partial pressure of gaseous substance in the equilibrium mixture
remains constant. As a result , inert gas has no effect on the equilibrium condition
at constant volume. (the partial pressure of each species remain constant .
Hence, there will be no effect on the equilibrium system. )
ii) At constant pressure : if the reaction takes place at constant pressure with
the addition of inert gas, it will increase the total volume of the system and
causes decrease in partial pressure of individual gas. It means when volume is
increased partial pressure decreases and the equilibrium shifts in the direction
that increases pressure. Pressure increases in the direction that involves larger
number of moles (volume) of gas. Hence, the equilibrium will shift towards the
direction that increases the number of moles of gas.
 Application’s of Le-Chatelier’s principle:

1) Application in chemical equilibrium:

a) In the manufacture of ammonia by Habers process: Ammonia

can be manufactured by Haber’s process from the reaction
between nitrogen and hydrogen gas, the reaction occurs as follows:
N 2 (g) + 3H 2(g) 2NH3(g) , H = - 22.04 Kcal

i) Effect of temperature: The reaction is exothermic in forward

direction and endothermic in backward direction. When
temperature is increased then the equilibrium shifts in that direction
which absorbs the heat ( i. e. endothermic reaction). Hence, high
temperature favours backward direction.
 When temperature is decreased, forward reaction is favourable because it is
exothermic which releases the heat to the system. Thus, low temperature is
favourable for high yield of ammonia .

Note: Exothermic: Endothermic :

A + B <=======>C + D + Heat A + B <=======> C + D - Heat
A + B - Heat <=======> C + D A + B + Heat <=======> C + D
A + B <=======> C + D , H = - ve A + B <=======> C + D, H =+
ve

Note : i) In exothermic reaction, low temperature is favourable for the forward

reaction.

ii ) In endothermic reaction , high temperature is favourable for the forward

reaction.

ii) Effect of pressure: One volume of nitrogen reacts with three volumes of
hydrogen to form two volumes of ammonia. Since, the forward reaction occurs with
decrease in volume ,high pressure favours this reaction. If the pressure is
decreased, it favours backward reaction because it occurs with increase in volume.
There fore, high pressure is favourable for high yield of ammonia .
Note :

i) If total no. of moles of reactants are more than that of total no .of moles of
products , high pressure is favourable for forward reaction. In this case, the low pressure
is applied in the system , the equilibrium shifts to the backward reaction.

ii) If total no. of moles of products are more than that of total no .of moles of
reactants , low pressure is favourable for forward reaction. In this case , the high pressure
is applied in the system , the equilibrium shifts to the backward reaction.

iii) If total no. of moles (or volumes) of gaseous reactants and products are equal ,
pressure has no effect in the equilibrium .
iii) Effect of concentration : If the concentration of at least one
reactant is increased, it favours forward reaction and if the
concentration of product is increased , it favours backward
reaction. There fore,for the maximum yield of ammonia,high
concentration of N2 and H2 should be used.

2) Application of physical equilibrium:

a) In melting of ice : The melting of ice can be represented as

follows,
H2O (s) + Heat <=======> H2O(l)
Ice (more volume) (less volume)
a) Effect of temperature : The reaction is endothermic in forward
derection and exothermic in backward direction. When the
temperature is increased, it favours forward reaction because it is
endothermic.When temperature is decreased, it favours backward
reaction(direction) because it is exothermic. There fore on
increasing temperature , more ice will melt.

b) Effect of pressure: Since, the forward reaction occurs with

decrease in volume , high pressure favours this reaction. When the
pressure is decreased,backward reaction is favourable because it
occurs with increase in volume. There fore on increasing pressure,
more ice will melt.
### Mention proper conditions for maximum yield of NO in the following equilibrium
reaction.
N 2(g) + O2(g) ================= 2 NO(g) () H = + 180 Kj

Ans : The proper conditions for maximum yield of NO in the following equilibrium reaction
are:

i) Effect of temperature : The reaction is endothermic in forward direction and

exothermic in backward direction. When temperature is increased, it favours forward
reaction because it is endothermic and when temperature is decreased, it favours
backward reaction because it is exothermic . Therefore, high yield of nitric oxide high
temperature is favourable .

ii) Effect of pressure : One volume of nitrogen reacts with one volume of oxygen to form
two volumes of nitric oxide. Since there is no change in volume , pressure has no effect in
equilibrium.

iii) Effect of concentration : If the concentration of at least one reactant is increased, it

favours forward reaction and if the concentration of product is increased, it favours
backward reaction. There fore , high yield of nitric oxide high concentration of N 2 and O2
should be used.
 ### what is the effect of temperature and pressure in the following equilibrium

H2O (l) + Heat ----------- H2O (g)

Solution:

H2O (l) + Heat ----------- H2O (g)

(less volume) ( more volume )

The effects of temperature and pressure in the following equilibrium are :

i) Effect of temperature : The reaction is endothermic in forward direction and

exothermic in backward direction. When temperature is increased , forward reaction is
favourable because it is endothermic and when temperature is decreased , backward
reaction is favourable because it is exothermic.

ii) Effect of pressure : Since the forward reaction occurs with increase in volume, low
pressure favours this reaction. If the pressure is increased backward reaction is favourable
because it occurs with decrease in volume.
 Law of mass action:
Rate of reaction is dependent upon concentration. The
dependency of reaction rate with concentration was studied by
two Norweigian chemists C.M. Guldberg and P. Waage in 1867.
They put Forward a law which is called as law of mass action.
`It states that at constant temperature and pressure “the rate
at which a substance reacts is directly proportional to it’s active
mass and the rate of a chemical reaction is directly proportional to
the product of active masses of the reacting substances , each
raised to the powers equal to their stoichiometric coefficients
present in the balanced chemical equation ‘’.
The term” active mass”indicates molar concentration of the
Species which is expressed in terms of molarity i.e. no. of moles of
the substance dissolved per litre of the solution . The active mass of
any species is represented by enclosing the species inside the
square brackets or by placing the name of species as subscript of C.
 For example, the active mass of species “A” is represented by
[ A ] or CA .

Let us consider a general reversible chemical reaction in which A

reacts with B to give the products C and D.

i. e. a A + b B <=======> c C + d D

Where a , b , c and d are the stoichiometric coefficients of

chemical species A , B , C and D respectively.

According to law of mass action, the rate of forward reaction is

directly proportional to the product of active masses of A and B.
 i. e. Rate of forward reaction ∞ [ A ] a * [ B] b

Rf ∞ [A] a
* [ B] b

Rf = Kf [ A ] a * [ B] b ………………..( 1 )

Where Kf is the proportionality constant known as rate constant

for forward reaction.

Again, from law of mass action , the rate of backward reaction is

directly proportional to the product of active masses of C and D.

i. e. Rate of backward reaction ∞ [ C ] c * [ D ] d

Rb ∞ [C] c
* [D]d
 Rb = Kb [C ] c
* [ D ] d …………………… ( 2 )

Where Kb is the proportionality constant known as rate constant

for backward reaction.
At equilibrium, the rate of forward reaction becomes equal to the
rate of backward reaction .
i. e. Rf = R b
Or , Kf [ A ] a * [ B ] b = Kb [ C ] c * [ D ] d

Kf / Kb = [ C ] c [ D ] d / [ A ] a [ B ] b

Keq or K = Kf / Kb = [C] c
[D] d/[A]a [B]b

Or, Kc = [ C ]C [ D ]d / [ A ]a [ B ]b

Where, Kc is equilibrium constant in terms of molar concentration.

 Where Keq or K is known as equilibrium constant. It is defined as the
ratio of product of active masses of product to the product of active
masses of reactant , each raised to the powers equal to their stoichio-
metric coefficients present in the balanced chemical equation. [Or it is
the ratio of rate constat for forward reaction to the rate constant for
backward reaction].

In case of gaseous rection , the molar concentration of substance

is proportional to it’s partial pressure.If the active mass is expressed in
terms of partial pressure then the equilibrium constant (Keq)isdenoted
by Kp and it is expressed as,

K p = PC c * PD d / PA a * PB b

where , PA , PB , PC and PD are the partial pressures of gases A , B ,C

and D respectively.
 Characteristics of equilibrium constant:

1. The equilibrium constant has a definite value for every reaction

at a particular temperature.

2. It is independent upon the factors like concentration , catalyst

of chemical species.

3. Greater the value of equilibrium constant more favoured is the

forward reaction and vice- versa .

4. The equilibrium constant value depends upon the temperature.

5. For a reversible reaction, the equilibrium constant for the

forward reaction is reciprocal (inverse) to the equilibrium
constant for the backward reaction .
 For example,

H2 (g) + I2 (g) <=======> 2HI (g)

For forward reaction , Keq = [ HI (g) ] 2 / [ H2(g) ] [ I2 (g)]

If the reaction is reversible, 2HI (g) <=======> H2(g) + I2(g)

For backward reaction, Keq ‘ = [ H2(g) ] [ I2 (g) ] / [ HI(g) ] 2

Hence, Keq = 1 / Keq’

6) Different reactions have different values for equilibrium

constant.
 Significance of equilibrium constant :

1) The equilibrium constant value has a great significance. If the value of equilibrium
constant is high, then it indicates that the reaction goes to almost completion in forward
direction. If the value of equilibrium constant is low , it shows that the reaction does not
go to completion and the yield will be low.
If Keq > 1 ,then the reaction goes to almost completion in forward direction, more
products is present in the system.
If Keq < 1 , it shows that the reaction does not go to completion , more reactants is
present in the system.

if Keq = 1 ,it shows that the concentration of reactants and products are equal in the
system.
If Keq = ∞ , it shows that the completion of the forward reaction .
If Keq = 0 , it shows that reactants do not react to each other.

2 ) Greater the value of equilibrium constant, greater will be the stability of the products
and unstability of the reactants .

3) Equilibrium constant is required for the calculation of concentration of reactants and

products .
 Writing expression for equilibrium constant :

1) If the reaction involves only gaseous reactant and product then

the name of all the species must be included in the expression for
equilibrium constant and the coefficient present in balanced
chemical equation must be raised to the power.

N2 (g) + 3H2(g) ------------- 2NH3 (g)

Keq = [ NH3(g) ]2 / [ N2(g) ] [ H2(g) ]3

2) If the reaction contains pure solid or pure liquid or both then it’s
concentration is taken as unity ( 1 mole per litre ) and the name of
such species must not be included in the expression.

CaCO3 (s) -------- CaO (s) + CO2 (g)

 Keq = [ CaO (s) ] [ CO2 (g) ] / [ CaCO3 (s) ]

But, [CaCO3 (s) ] = 1 mol / lit = [ CaO (s) ]

Keq = [ CO2 (g) ]

Note : If the pressure is applied to the reactant the volume of species does not change the
concentration becomes 1.

3) The concentration of pure liquid in the reactant is taken as unity

but not in the product side.

For e.g. a) NH3 (aq) + H2O ( l ) ----- NH4 + (aq) + OH – (aq)

K c = [NH4 + (aq) ] [OH – (aq)] / [NH3 (aq)]

b) CH4 (g) + 2O2(g) -------- CO2 (g) + 2 H2O (l)

K c = [CO2 (g) ] [H2O (l) ] 2 / [CH4 (g) ] [O2(g)] 2

 4 ) If one of the reactants is large excess in the reaction then, it’s concentration remains
same .
For e.g. H+
CH3COOC2H5 (aq) + H2O (l) ------- C2 H5 OH (aq) + CH3COOH (aq)
( Ethyl acetate) (excess) (Ethyl alcohol ) (acetic acid )

Keq = [ C2 H5 OH ] [ CH3COOH ] / [ CH3COOC2H5 ] [ H2 O ]

Or , Keq * [ H2O] = [ C2 H5 OH ] [ CH3COOH ] / [ CH3COOC2H5 ]

Or , Keq’ = [ C2 H5 OH ] [ CH3COOH ] / [ CH3COOC2H5 ]

1. Define equilibrium constant. What would be the expression for Kc in the following
reaction.
CaCO3(s) ========== CaO(s) + CO2(g) [ NEB]

It is defined as the ratio of product of active masses of product to the product of active
masses of reactant , each raised to the powers equal to their stoichiometric coefficients
present in the balanced chemical equation. It is denoted by Keq or Kc . Or It is defined as
the ratio of rate constant for forward reaction to the rate constant for backward reaction.
( Keq = Kf= / Kb )
 We have, Kc = [ CaO (s)] [ CO 2 (g)] / [ CaCO3 (s)]
Since, CaO(s) and CaCO3(s) are pure solids, their molar concentration’s are taken
as unity.
Now, Kc = [ CO2 (g) ] .

2 ) Write the expression for equilibrium constant Kc for the following reactions :

i) 2 Cu (NO3)2(s) --------- 2 CuO (s) + 4NO2 (g) + O2 (g)

ii) FeO (s) + CO (g) --------- Fe (s) + CO2(g)

Ans : I ) Kc = [ CuO (s) ] 2 [ NO2(g) ]4 [ O2(g)] / [Cu (NO3)2(s) ] 2

= [ NO2(g) ]4 [ O2(g)]

Scnce , Cu (NO3)2(s) and CuO (s) are pure solids, their molar concentration’s are
taken as unity.

ii) Kc = [ Fe (s) ] * [ CO2(g) ] / [FeO (s) ] * [ CO (g)]

= [ CO (g) ] / [ CO (g)] [ Fe (s) ] = 1 mol/ L = [ FeO(s) ]

### Write the equilibrium constant [ Kp and Kc ] for the following chemical reactions :

I) PCl5 (g) ------------ PCl3(g) + Cl2 (g)

ii) 2 Fe (s) + 3H2O (g) ------------ Fe2O3 (s) + 3 H2 (g)

Solution : i) Kc = [ PCl3(g) ] [Cl2 (g) ] / [PCl5 (g) ]

Again, Kp = P PCl3 * PCl2 / P PCl 5

ii) Kc = [ Fe2O3 (s) ] * [ H2(g) ] 3 / [ Fe (s) ]2 [H2O (g)] 3

Since, Fe2O3 (s) and Fe (s) are pure solid’s , there molar concentrations are taken as unity.

Kc = [ H2(g) ] 3/[ H2O (g) ] 3

 Relationship between Kp and Kc:

Let us consider the following reversible chemical reaction ,

i. e. a A + b B <=======> c C + d D

If the active mass is expressed in terms of molar concentration

then the equilibrium constant (Keq) is denoted by Kc .

i.e. KC = [ C ] C [ D ] d / [ A ] a [ B ] b ………….( 1 )

Where, [A] ,[B] ,[C] and [D] are molar concentration of chemical
species A, B, C and D respectively.

If the active mass is expressed in terms of partial pressure then the

equilibrium constant (Keq) is denoted by Kp .
 i.e. K p = PC c * PD d / PA a * PB b …………..( 2 )

Where, PA, PB, PC and PD are the partial pressures of gases A , B ,C

and D respectively.
From ideal gas equation,
P * V = n R * T
Or, P = n R * T/V

Where, n / V = Molarity Or molar concentration.

i.e. P A = nA / V * R T = [A] *R T

PB = nB / V * R T = [B] *R T

P c = nC / V * R T = [C] *RT
Substituting the values of PA , PB , PC and PD in equation (2) we get,

K P = { [ C ] R T } c * { [ D ] R T } d/ { [ A ] R T } a * { [ B ] R T } b

KP = [ C ] c * ( R T) c * [ D ] d* ( R T) d / [ A ]a * ( R T)a * [B]b *(R T )b

KP = [ C ] c * [ D ] d * ( R T ) c + d / [ A ] a * [ B ] b * ( R T ) a + b

KP = [ C ] c * [ D ] d / [ A ] a * [ B ] b * ( R T ) c + d / ( R T ) a+b

KP = KC * { R T } ( c + d ) - ( a + b )

KP = KC * ( R T) n

Where n = no. of moles of gaseous products – no. of moles of

gaseous reactants
 Special cases : 1) If n = 0 , then KP = KC .
For e. g, H 2(g) + I 2(g) <=======> 2HI(g)
Here, n = { 2 – ( 1 + 1)} = 0
Now, KP = KC * ( R T ) n = KC ( R T) 0
KP = KC
2) If n > 0 , then KP > KC.
For e.g, PCl 5(g) <=======> PCl3(g) + Cl2 (g)
Now , KP = KC * ( R T) n { Here, n = ( 1 + 1 ) - 1 } ,
Or n = 1
KP = KC * ( R T ) 1
KP > KC
3) If n < 0 , then, KP < KC.
For e.g. N 2(g) + 3H 2(g) <=======> 2NH 3(g)

Here, n = { 2 – ( 1+ 3 )} = - 2
Now, KP = KC ( R T ) n = KC ( R T) -2 = KC / (RT) 2
 Unit of Kp and Kc :

The unit of Kc is ( mol L-1 )()n and that of Kp is (atm) () n .

I ) If () n = 0 , then Kc and Kp are unitless.

ii) If ()n greater than 0 , then unit of Kc is mol L- 1 or mol2 L- 2 or mol 3 L- 3 etc. and that of
Kp is atm or atm 2 or atm3 etc.

III) If ()n less than 0 , then unit of Kc is L mol- 1 or L2 mol -2 or L 3 mol -3 etc. and that of Kp
is atm-1 or atm -2 or atm-3 etc .

# Find the unit of Kp and Kc in the following reaction :

i) N2 (g) + 3H2 (g) --------- 2NH3 (g)

Hint : i) ()n = { 2 – (1+3) } = - 2

Unit of Kp is (atm) () n = (atm) – 2 = atm- 2

Unit of Kc is ( mol L-1 ) ()n = ( mol L-1 ) -2 = L2 mol- 2

Alternatively :

Or , Kp = PNH3 2 / PN2 * PH2 3 = (atm) 2 / (atm) (atm)3

= (atm) -2 = atm-2

Or , Kc = [NH3]2 / [ N2 ] * [ H2 ] 3

= (mol L- 1 ) 2 / (mol L-1 ) (mol L-1)3

= ( mol L-1 ) -2 = L2 mol- 2

1) Write the expression for equilibrium constant( Kc ) for,

4NO(g) + 6H 2O(g) <=========> 4 NH3 (g) + 5O 2(g). What is the relationship

between Kcand Kp for the above relation. [ NEB]

Ans: We have Kc = [ NH3 (g) ]4 [ O2 (g) ]5/ [ NO (g) ]4 [ H2O (g) ]6

For the relation between Kp and Kc,
() n = Total no. of moles of gaseous products – total no. of moles gaseous reactants

= { (4+5) - ( 4+ 6 )} = -1

Now , Kp = Kc ( R T ) ( ) n
, Or Kp = Kc (RT) - 1= Kc / RT , KpKc

2) Write the relationship between Kp and Kc for the following reaction:

CH4(g) + 2O2 (g) ---------- CO2(g) + 2H2O ( l )

() n = { 1 - (1 + 2 ) } = - 2

Now, Kp = Kc (RT) ()n , Or Kp = Kc (RT) –2

KpKc
 Effect of addition of inert gas:
Effect of inert gas can be studied at constant volume and at
constant pressure.
i) At constant volume : when an inert gas is inroduced into the
equilibrium system at constant volume the partial pressure of each
species remain constant . Hence, there will be no effect on the
equilibrium system.
ii) At constant pressure : if the reaction takes place at constant
pressure with the addition of inert gas, it will increase the total
volume of the system and causes decrease in partial pressure of
individual gas. It means when volume is increased partial pressure
decreases and the equilibrium shifts in the direction that increases
pressure. Pressure increases in the direction that involves larger
number of moles (volume) of gas. Hence, the equilibrium will shift
towards the direction that increases the number of moles of gas.
 1) What would be the effect on the position of equilibrium of the reaction ?

PCl5 (g) < ------------------ PCl3 (g) + Cl2 (g) + Heat()

On : a) adding Cl2 b) adding PCl3 c) decreasing the pressure by increasing the volume of
system d) increasing the temperature ( the reaction is endothermic in forward direction)
e) adding a catalyst.

2 ) Write short notes on :

i) Le – Chatelier’s principle and it’s applications .

ii) Relationship between Kp and Kc .

iii ) Law of mass action and chemical equilibrium

3) State and explain Le – Chatelier’s pinciple . How does the change in temperature and
pressure affect the equilibrium of the follwing reaction?

N2 (g) + 3 H2 (g) <------------- 2NH3 (g) + 22.4 K Cal.

# What do you mean by equilibrium state of a chemical reaction ?

 # State law of mass action . Write a chemical equilibrium in which Kc becomes equal to
Kp.

# Define equilibrium constant . What are the characterictics of equilibrium constant.

# what are the significances of equilibrium constant ?

# Define the following terms :

a) Active mass b) Homogeneous equilibrium c) Chemical equilibrium d) Physical

equilibrium .

# Difference between reversible and irreversible reaction .

# Chemical equilibrium is dynamic in nature . Explain it with suitable reason .

# What are the characteristics of chemical equilibrium ?

# Why does chilled soda water bottle fizz out when opened ?

# Why is forward reaction favoured when Kc

# Why is backward reaction favoured when Kc< 1 ?

 # Mention proper conditions for maximum yield of SO3 in the following equilibrium
reaction.
2 SO2(g) + O2(g) ================= 2 SO3(g) + Heat

# Predict the favourable condition’s for forward reaction in the following case.

i) 4NH3(g) + 5 O2(g) =============== 4 NO(g) + 6H2O (g) + Heat

ii) H2(g) + I2(g) ------------- 2HI (g) - Heat

# What happens when the pressure is increased in the following equilibrium

reactions.
a) N 2(g) + 3 H2(g) ============ 2NH3 (g)
b) N 2(g) + O 2(g) ============= 2 NO (g)
# Write the equilibrium constant [ Kp and Kc ] for the following chemical reactions :

ii) CH4(g) + 2O2 (g) ---------- CO2(g) + 2H2O ( l )

ii ) 4 NO (g) + 6H2O (g) --------------- 4 NH3( g) + 5 O2(g )

iii) CuCO3 (s) --------------- CuO (s) + CO2(g)

iv) 2HI (g) -------- H2 (g) + I2 (g)

 ## Find the unit of Kp and Kc in the following reactions :

i) 2SO2 (g) + O2(g) ----- 2SO3 (g)

ii) H2(g) + I2(g) ---------- 2HI (g)

# Write the effects on equilibrium of following reaction ,

2CO (g) + O2(g) -------- 2CO2 (g) + Heat

when,
a) Pressure is increased .
b) Temperature is increased.
c) CO is added .
d) CO2 is removed .
e) Inert gas is added .
f) Catalyst is used .
g ) NaOH solution is injected.

# Caustic soda (NaOH) dissolves more when the beaker containing it’s solution is cooled
under water . Why?

# Ice melt slowly at higher altitude . Give reason.