Escolar Documentos
Profissional Documentos
Cultura Documentos
Aditya vardhan
CHEMICAL EQUILIBRIUM 1 adichemadi @ gmail.com
CHEMICAL EQUILIBRIUM
Reversible reaction : A reaction which proceeds through forward and backward directions is called
reversible reaction. In a reversible reaction, reactants are converted into products and vice versa.
Eg.,
N
Irreversible reaction: A reaction that occur only in direction is called irreversible reaction i.e., only
HA
reactants are converted to products and conversion of products to reactants is not possible.
Eg.,
E
RD
1) CH4 (g) + 2O2 (g)
EG
CO2 (g) + 2 H2O (l)
by
LL
ed
G C
ep
AN IOR
Pr
Chemical equilibrium: The state at which the rate of forward reaction becomes equal to the rate of
YA
backward reaction.
AR N
W JU
AG T
VI
I
DE
AD
state of equilibrium
N
equilibrium are not in the same phase.
HA
Eg.,
E
RD
EG
by
2) NH4HS (s) NH3(g) + H2S(g)
LL
ed
VA
AL O
ar
G C
ep
The rate of a reaction at an instant of time is proportional to the product of active masses of the
Pr
YA
i) For dilute solutions, the molar concentrations are taken as active masses.
AG T
VI
ii) For gases at low pressures, the partial pressures are taken as active masses.
I
DE
AD
where [A], [B], [C] and [D] are the equilibrium concentrations of A,B,C and D respectively.
Kf and Kb are the rate constants of forward and backward reactions respectively.
But at equilibrium,
rate of forward reaction (vf) = rate of backward reaction (vb)
i.e., K f [A]a [B]b K b [C]c [D]d
Prepared by V. Aditya vardhan
CHEMICAL EQUILIBRIUM 3 adichemadi @ gmail.com
K f [C]c [D]d
or =
K b [A]a [B]b
[C]c [D]d
or Kc =
[A]a [B]b
Kf
where K c = and is known as equilibrium constant.
Kb
product of concentrations of products at equilibrium
In general, Kc =
product of concentrations of reactants at equilibrium
N
Units of K c (mole.L-1 ) n
HA
Where n = (c+d)-(a+b) = no. of moles of products - no. of moles of reactants
E
RD
EG
Kp is the equilibrium constant in terms of partial pressures. If A, B, C and D are gases then for
by
above reaction, Kp can be written as
LL
ed
VA
PC c PD d
AL O
ar
KP = G C
ep
PA a PB b
AN IOR
Pr
where PA, PB, PC and PD are the partial pressures of A, B, C and D at equilibrium.
YA
AR N
nRT
AG T
V
I
DE
AD
[C]c [D]d
Therefore K P = a b
x[ RT ](c d )( a b)
[A] [B]
VA
V.
or K P =K c [RT]Δn
where Δn=(c+d)-(a+b) = no. of moles of gaseous products - no.of moles of gaseous reactants
If Δn=0 then K p =K c
and if Δn>0 then K p >K c
and if Δn<0 then K p <K c
Illustrations
[HI]2
Kc =
[H 2 ] [I2 ]
PHI2
Kp =
PH . PI 2
2
K P =K c [RT]Δn
Prepared by V. Aditya vardhan
CHEMICAL EQUILIBRIUM 4 adichemadi @ gmail.com
Δn=(2)-(1+1)=0
Kp = Kc
[PCl3 ][Cl 2 ]
Kc =
[PCl5 ]
PPCl3 .PCl2
Kp =
PPCl 5
Δn = (1+1)-(1) = +1
Kp > Kc
N
HA
3) N2(g) + 3H2(g) 2NH3(g)
E
[NH 3 ]2
RD
EG
Kc =
by
[N 2 ][H 2 ]3
LL
ed
VA
PNH3 2
AL O
ar
Kp = G C
ep
PN2 .PH2 3
AN IOR
Pr
YA
K P =K c [RT]Δn
AR N
W JU
Δn = (2) - (1+3) = -2
AG T
VI
K p <K c
I
DE
AD
[N 2 ][H 2 ]3
V.
Kc =
[NH3 ]2
PN2 .PH2 3
Kp =
PNH3 2
Δn = (1+3) - (2) = +1
Kp > Kc
K c =[CO 2 ]
K p =PCO2
Δn=(1)-(0)=+1
Kp > Kc
Problems :
1) The molar concentrations of A, B & C at equilibrium for the reaction 2A + B 3C are 1,2
& 3 moles / litre respectively calculate Kc
Prepared by V. Aditya vardhan
CHEMICAL EQUILIBRIUM 5 adichemadi @ gmail.com
2) Kc value of the following reaction is 0.4
H 2(g) + I2(g) 2HI(g)
if the equilibrium concentrations of H2 & HI are 0.2 and 0.8 moles/litre respectively. What is the
concentration of I2 at equilibrium.
3) The Kc of a reversible reaction is 5. if the rate constant of forward reaction is 2.5 what is the rate
constant for backward reaction.
4) Give the relations between Kc and Kp for the following reactions .
CH 3COONa
(i) CH 3COOC 2 H 5(aq) + NaOH (aq) (aq) + C 2 H 5OH (aq)
N
Calculate the Kp value at 270C.
HA
Le Chatelier's principle
When external stress is applied on a system at equilibrium, the system shifts the position of
E
RD
EG
by
equilibrium so as to nullify the effect of stress.
Stress can be applied by changing the concentration or pressure or temperature. The effects of
LL
ed
G C
ep
AN IOR
Effect of concentration:
Pr
YA
Effect of pressure:
I
DE
1) When pressure is increased, the system tries to decrease the pressure by favoring the reaction in
AD
Effect of temperature:
1) When the temperature is increased, the endothermic reaction is favored.
2) When the temperature is decreased, the exothermic reaction is favored.
Industrial applications
Effect of temperature: Forward reaction is exothermic. Hence increase in temperature favors the
dissociation of ammonia. But at low temperatures the reaction does not occur. Hence the reaction is
carried out at moderate temperatures (725 - 775 K).
To increase the rate of reaction, finely powdered iron is used as catalyst and Mo is used as promoter.
Prepared by V. Aditya vardhan
CHEMICAL EQUILIBRIUM 6 adichemadi @ gmail.com
Favourable conditions:
Pressure 200 atm
Temperature 725 to 775 K
Catalyst Fe
Promoter Mo
N
towers used in the reaction are corroded. To avoid this moderate pressures (10 atm) are employed.
HA
Effect of temperature: Forward reaction is exothermic. Hence low temperatures favor the synthesis of
E
sulfur trioxide. But at low temperatures the reaction does not occur. Hence the reaction is carried out at
RD
EG
by
moderate temperatures (673 K).
LL
ed
VA
To increase the rate of reaction, platinized asbestos or V2O5 are used as catalysts.
AL O
ar
Favorable conditions
G C
ep
AN IOR
Pr
Pressure 10 atm
YA
Temperature 673 K
AR N
W JU
Catalyst Pt or V2O5
AG T
VI
I
DE
AD
2) The forward reaction is favoured when pressure is increased on the following reaction system at
equilibrium.
2C( g )
A( g ) B( g )
3) The synthesis of ammonia is favoured by removing ammonia formed, in Haber's process, by liquefy-
ing it.
4) The value of equilibrium constant Kc can be changed by changing the temperature.
5) Kc > Kp for the following reaction.
CaCO3( s ) H 2O( aq )
Ca (OH ) 2 CO2( g )