CHEMICAL EQUILIBRIUM

Chemical reaction :- Symbolis representation of any chemical

change interms of realtants and Products is called
chemical reaction Based on direction of reaction taking
Place Chemical reactions are two types
i Irreversible reactions Iiil Reversible reactions
1.Ir-reversible reaction :-
The chemicalreaction which cantakes
place in one direction i e Reactants products till
one for all the reactants are completely converted into products

Eg i Precipitation reactions
Agel Nano
Agnospa Nacka aa
ii Combustion reaitions
iiiRed on reactions
iv Neutralisation reactions S.A Vs S B only
v Most of the thermal decomposition reactions

Cacogs Cao 04g In openVessel

Characteristils
Generally proceeds in one direction
Possible in open container
Donot attain equilibrium
Reactants one on all completely converted into products
2. Reversible reaction :- The chemical realtion which Ian
takes place in bothdirections i e Reactants Products
under similar Conditions of temperature
Reactants Products
Reactants Products is Forward reactions
Products Reactants is Backward reaction
 Characteristics
Generallyproceeds in both direction i e forward backward
Possible in closed Container very few are in open vessel

Eg Caco Cag 02,9 In Closed Vessel

Eg 2H50 C 3900675 42911
CHzCOOHq a

even in openvessel
Can attain equilibrium
Reactants never Completely Converts into products
Neutralisation reactions ex lept S.A vs S B
Equilibrium state :-
when reactants of a reversible reaction placed in
closed
are a

container at a particular temperature to give produits the

Coni of reactants gradually decreases and conc of products
gradually increases
After a certain time there is no significant change in
conc of either reactants or products
The state of a reversible reaction at which the conc
of reactants ion products donot alter with time is
Called equilibrium state
The state in which measurable properties of the system
like pressure density Coni and colour donot undergo
any significant change with time under given set of
conditions is called equilibrium state
Note In the beginning re Vb as time progress rate of
forward reaction rf delreases and rate of backward
reaction increases rb
 In the beginning rate of backward reaction is zero rb 0
as time progress r increases
The state at which rf Vs is called equilibriumstate
Equilibrium state can be attained in both physical
and chemical process

Equilibrium state is established

1 In a reversible process only
in at constant temperature
11171
mostly in a closed Vessel If the rean takesplace
in lid phase fool as so stale on solid state then it is
possible in even in open vessel

Chemical equilibrium state

Equilibrium state
Physiial equilibrium state

Equilibrium in chemical process :-

Eg In Closed Vessel
1 Hey Is 2H11
2N 3,9
2
2,9 3H49
3 PC 5,9 PC13,9 512,9

4 N2 g 02,9 2H49
51 2502,9 02,9 2503,9

6 1420419 21499
7 NHyHS s NH 299
 8 3Feis 4H20 Fesoys 4712,9

a
Cacog say 904g
In open vessel
CH 900Cottage Hey
CHzCooHq 2H50 g
Ionisation of weak acids weak bases

CHzCOOH CHzCo5 Ht
NHL OH NHI OH

Dynamic equilibrium :- In a reversible chemical reaction

initially Vb o but as time progress rate of forward
reaition decreases and rate of backward reaction increases
At equilibrium of Vb
The reversible chemical rean in whith both F R and B R
are continue to take place with equal rates is called
Dynamic equilibrium
Chemical equilibrium is important in numerous
biological Environmental process
Eg Equibrium of Haemoglobin Hb in the transportation
of 02 and toxicity of CO
Dynamic nature of Chemical equilibria Can be demonstrated
by Haber's process by the reaction b w Nz Az
NZ 3H49 2MHz Proless I
N2 3D 2ND proless I
After mixing abolle two Mixtures the final mixture contains
MHz NH2D NHDz ND Hz HD Dz Hence dynami nature
is prooved
Characteristics of chemical equilibrium :-
At equilibrium state of Vb
It is always dynamic in nature but not static
The properties such as pressure Cons density colour etc
remains unchanged with time
A catalyst donot alter the state of equilibrium
Ve catalyst helps to attain equilibrium Quickly
Ve Catalyst delay retard to attain equilibrium

rate equilibrium state

ye ye

time
At equilibrium DG 0 P.T Const
Chemical equilibria Can be established from either
side of the reversible reaction
The Cons of reactants and Products remains Constant
unchanged with time
Note At equilibrium rf r but it is not necessary that
Coni of reactants and cons of products equal
At equilibrium Vf Vb
But I 7 or

T2 7 Cor

To
 R R P
Coni Coni
Conc
R
P calmstate P calmstate calmstate
time time
72 a a

Types of chemical equilibrium :-

1.Homogenous equilibrium:-
In a reversible chemical reaation if all the realtants
and prodults are in same phase then Suth equilibrium
is called Homogeneous equilibrium
Eg H2 g 2H Ipg
Igg
CHz100Hag 1 C2 sofa CHzsoo fatttag 29,1

Feta Scalia Fe San

yellow colourless deepred
Homogeneous equilibrium realtions are further classified into
i o H2 g Igg 2H Ipg
Ang
2,9 02,9 2H49
ii Dng the PC 5,9 PC3,9 219
204,9 21499
iii Dng e
Nz 2
3H49 391
2502,9 02,9 2503,9
2. Heterogeneous equilibrium :- In a reversible chemical reaction
if a reactant for product is are in different phase than
other reactant product s then such equilibrium is known as
Heterogeneous equilibrium
Caco Cage CO2
NHyHS NH 25,9

Nigs 4 Ni coly Mond's process

A92 24h03m 2491403 29,1
Law of chemical equilibrium :- ( Law of mass action )
Law of mass action proposed by Guldberg Waage
It gives the relation b w the rate of a chemical reaction

and cons of reactants

The rate of a chemical reaction at a given temperature
is directly proportional to the product of active masses
of the reactants at that instant
Law of mass action applicable to all the reactions taking
place in gas phase and as.su state
Active mass molar Contentuation it Lmw lit
Active mass of solids and Pure lionids is always unity
because mass is an intensive property
1000 91mL
For gases hw 1mW 9 lit w

Lawof mass action applicable to both Homogeneous

Heterogeneous equilibrium reactions
Chemical equilibrium follows 1 Law of mass altion
21 Lechatelier principle
 Equilibrium constant :- defined as
Equilibrium constant is

the ratio between the product of molar lone of products

to the product of molar Concentrations ofreactants with
each cons term raised to a power equal to stoichiometric
Co efficient in balanced chemilal equation denoted with K

The Equilibrium Constant is defined as the ratio of the

rate constants of forward and backward reans at a
given temperature

Kf
Kb

Equilibrium Constant has a definite value for every chemical

reaction at a particular temperature

Product of Conc terms of Products

EquilibriumConstant K
product of cons terms of reactants

Forms of equilibrium constant :-

Equilibrium constant (K)

EquilibriumCont Equilibrium Equilibrium

Constant partial pressure molefraction Constant
Ka Constant Kp Kx
1.Equilibrium concentration constant (Kc) :-
Consider a reversible homogeneous chemical reaction

A y B MC nD
BR

Act.to Law of massation

9
rate of forward rean rf α A B

Vf Kf A B Kf F R rate constant

rate of backward rean vs α C D

Vb Kb C D Kb B R rate constant

at equilibrium state of b

i Kf A B Kb C D

C D
Kc unitsof K moles it_
9
A B

Kc known as equilibrium Cont Constant It has

is
Constant value for a given rean at a given temperature
2. Equilibrium partial pressure constant (Kp) :-

For a general reversible homogeneous reaction

Agg 9 Big Mfg Pg
 rate of F R rf Kf Pa Piz

rate of B R vsKb PC Pj
But at equilibrium if Vb

KpPa P K PC P
Pam PD atmp
Kp Kp units
Pa pay

Kp is Equilibrium partial pressure constant

3. Equilibrium constant in terms of mole fraction :-
For a general reversible homogeneous reaction
nA YB MC ND
rate of F R Vf Kf Xñ
rate of B R r Ks Xi XD

But at equilibrium f b

ke X X Ks Xi

XP xp Kx
a By

Kx Equilibrium molefration Constant

Relation between Kc & Kp :-

For a general reversible reaction

nA YB MC MD
 C D Pim P
Kc Kp
A B
9 Pa P Y

For gases P V NRT

P F RT

P CRT where Concentration

i PA ART PB BRT
Pc C RT PD DRT

CRT GRT
Kp
CART CBRT

C RT c RT
Kp
RT C RT
Ca

CD Raylan
Kp
a C 12 16 7

4 G Inty
RT
Kp
Ca c

Kp Kc CRT

Ang g products
9
Reactants
Case i If Ang 0 then kp k
Kp and K both are unit less
9 Dng o Kp K
49 Egg e 2411g
Eg
2,9 02,9 2H09 i Ang o Kp Kc

Case ii If Ang Ye then Kpsk

Eg PC PC 91219
5g 3,9

ng 1 1 1
RT 9
Kp K

Kp Ke RT

Kp Ke RT 101 RT I Ke

k Kp RT

1
moles lit moles Lit
Units of Ke
Kp Catmp
Case iii If ng ve then Kpck
Eg Nz g 2N
342,9 3g
ng 2 1 3 2

Kp K RT
2 04 kp 1k con Kp RT Kc

Kc Kp
Units of K moles it mole Lit 2
RT
Units ofKp tmp at'mp
Relation between Kp , Kc & Kx :-

i x
Kx
i
Acc to Dalton's law of partial pressures
Pgas Pt gas

Pa XA.PT PB XB.PT Pc X Pt PD XD.PT

Pam P X Pt x p
Kp Pan p y Pt
APT

Kp i XD Pt
Xa XB PT
mtn atg
Kp Kx p

Kp Kx Pt

But Kp Kc RT 2

from 1 and eats

K RT Kx Pt
Ke Kx II
for I mole of ideal gas PV RT
IF
9
i Ke Kx
Volume of System containing 1 mole of ideal gas
Factors e ect Equilibrium constant :-

The value of Equilibrium constant is independent on

i Initial of reactants
Conc
Presente of catalyst
ii Direction from which the equilibrium state attained
iv Presence of inert gases material
v Pressure volume
The value of Equilibrium Constant depends on
i mode of representationof rea
ii Stoichiometry of rean
iii No of steps involved in the rean multi step rean
iv Temperature
1.Mode of representation of reaction :-
For a general reaction for the reaction
A B C D C D A B
C D A B
K ki
A B C D

the relation b w Kc Ki is ke
Eg
2 I
Hag Igg 2 I
g g Haig Igg
I
H2 Iz
K K
He Iz HI

i Ka on ke
2. Stoichiometry of reaction :-

when a reversible reaction Can be written with the help of two

foot more stoichiometric equation then the value of equilibrium
Constant will be numerically different
If the rea is multiplied for divided with n then
equilibrium Constant relation is Ke Kd
Eg 2 NO
219 02,9
g

2 02
Kc
No

If the reaction is multiplied with then the reanberom

Nog 039 9g 7s
then Nz 02
y
NO

then the relation bw K Ki is ke Kc

ie Ki K Kc
If the reaction is multiplied with 2 then the rea becomes

2
4k9g 2,9 2049
2 2
Kc 2 02

NO 4

the relation b w Kc Kc is given by

Ke Kc son Ke ki Ke
3. In case of multi step reaction :-

Eg 502,9 02,9 503 991

The above reaction takes plate in two steps
02
i N NOg 02,9 K
2,9
NO

ii 502g 049 503 K 503

502 02

N NYg K K K
502,9 2,9 503,9

503
14 2
Noc 50 102
NO 503
K
NO 502
Eg 2 Nzpg 02,9 14g 2H00
g
The above reaction takes plate in two steps
2 No
I 2,9 04g 0,91 K
Nz 02
ii 2 99 42,9 214011191
K

2,970491 9149 214091,9

NOC
K K 411
Nz 02 12
2
NOC
K
Nz 02 12
4. E ect of Temperature :-
The value of Equilibrium Constant depends only on Temperature
The relation b w K and T is given by Arrhenius equation
Ea RT
K A e

K rate constant
A Arrheniusfreouenlyfactor
Ea Activation energy
For forward reaction Kf Af e Eat RT

Eab RT
For backward reaction K Age
Eap RT
i Keg Af e

Ab e Ecs RT

9b af
keg e

Let k is equilibrium Constant at T Temperature

K2 is equilibrium Constant at T2 Temperature then
Eab Eaf
Rtf
K re RTI K
f e

In Eab Eat
R
DH
In DH Eaf Eog
R

In
1
 It
log 2 303 R

log 2 I Van't Hoffeat

then the reaction is endothermic

Case i If T2 T
DH the endothermic realtion
iK2 K
In such cases K α I

K increases with increase in Temp

DH
Eaf Eap Eaf Eab

Case ii If T2 4Tthen the reaction is exothermi

H ve Exothermic rea
i K2 K K α
in
In Such Cases k decreases with increase Temp
DH Eaf Eas Eaf Eab
Case iii If T Tz then the rear is neither Exothermic
Endothermit hence DH O
nor
i K2 K
K remains Constant at all temperatures
Applications of Equilibrium constant :-
1.Stability of reactant (or) Product :-

In a reversible chemical reaction

stability of product α k
stability of reactant α

Eg In the following reaction

Ii 2 0,9 04g i K 1.0 102

4g
2.5 1010
ii 2
02,9 2,9 204g Kz

As k K2 the stability of 04g

2. Predicting the direction of reaction :-

Reaction Quotient Q The ratio of product of molar

Concentrations of products to the product of molar conc
of reactants with each Coni term raised to power equal
to it's stoichiometric co efficient at any stage during
the progress of rean
Note Q can be Callulated at any stage of real in a
reversible rean but K Can be Calculated after attaining
equilibrium state only
For a general reversible rea A yB me nd
the values of Qc Kc Con Qp Kp help to predict thedirection
of rea
C D
QC a y
at any stage of rean
a B

C D
only at eq m stage
ke 9
A B
Case i If Qc Ke for Qp Kp then the reaction is
at equilibrium of 85
Case ii If Qc 2k on Qp Kp then the reaction is
not at equilibrium The rean proceeds in the
direction of Products i e forward direction
Vf Vb
Case iii If Q k Coo Qp Kp then the reaction will
proceed in the direction of reaitants
i e Backward direction of 85

K B Rfavours

Q K m
state
Q eq

Q CK F R favours

time
3. Predicting the extent of reaction :-
The numerical value of the equilibrium Constant for a

reversible rean indicates the extent of rean

Products
a fool Kp α reactants

Kc 410 3 Kc 153to 103 k 103

R P R P RICEP
Realtants Predominate Appreciable conc product predominate
Ke is small of both R P Kc is large

Vean proceeds slowly rea at eat rear proceedsnearly lompletio

Calculation of degree of dissociation :-

Degree of dissociation is denoted with α

No of moles of reactant dissociated

α
No of moles initially taken

1α α 100

It is the ratio b w number moles of reactant dissociated

to the no of moles of reactant initially taken
1.Calculation of equilibrium concentration
and equilibrium constant :-

If initial Conc is known but donot know equilibrium Cons

then it write the balanced ean
11 Under the balanced een mention the following
for each substance
a initial cone
b The change in Cont on going to equilibrium
c The equilibrium Conc

n Consider a is the Small change in the Conc of one

of the substance that reacts ongoing to equilibrium Use
stoichiometry of the reaction to determine the Conc of other
Substances interms of x

v7 Substitute the equilibrium cont into the equilibrium

eqn for the rean and solve fora Use Quadratic
equation if redaired
Iv Calculatethe equilibrium Cont from the value of a
Eg A B C
7 0 0

t calm n 1 a a

C
Ke
A B

If the rean takes place in 1 lit Vessel then

Kc In
Eg 2 At 2B 3C rean taking Place in 1 lit vessel
A 2B 3C
0 I 1 0

calm 1 A 1 22 32
3
I 1
2,1 I
C 3
K 3913 9
2 1 4 2
I 1 76 2,2 1 a

Eg in Ilit vessel
Nyg 3H49 2MHz
t o I 1 0

t eqlm 1 n 1 34 2n
1 2 1 3k 22

2 2
K 3 2272 4
3 1 a 1 2273 1 a 1 8 3
7
 For a general equation
A NB
0 I 0

t eqlm 1 a nn

Total no of moles at equilibrium 1 a na

Ith n n

Nt 7 n 1 n

Volume at equilibrium N XV
I n 1 a

2. Calculation of equilibrium partial pressure :-

For a general reversible rean Big Gg

Aig Big Cig

t 0 I 1 0

t eq m 1 a 1 a a

Total no of moles at equilibrium I n 1 a a

Nt 2 X
PA XAP SIP IIP
PB B
XBP P I P

Ps XP
I P In P

Kp Pc
PA x PB

2
P

IIP CLIP
 In a 2 2
1 a up
1
2 a
Kp 1 a P

3. Calculation of degree of dissociation from vapour density :-

For the reaction Aq n Big

Let d is the observed vapourdensity at Particular T
when degree of dissociation n and D bethe Vapour
density when there is no dissociation
α d α
I n t x x

G DIY
7

1 n 1 a Van'tHofffactor

n 1 a 1
d

D d
d n 1

D Initial vapourdensity
d Vapourdensity at calm
degree of dissociation
n Total no of moles of gaseous products from one moleof R
 But Molar mass M 2 V D

M m
i
m n 1

M Initial molar mass

m
m Molar mass at eq
n Total no of moles of gaseous products formedfrom
one mole of reactant

Applications of Law of mass action :-

Relation b w degree of dissociation α n equilibrium pressure
P and volume x
Ii In Case of Homogeneous reactions
Case i Reactions ng o
Es Hagg 14g 2H19
2,9 0491 2499

Degree of dissociation is independent on Pel V

a n α

Case ii Reaction Dng 0 71

Eg PC 1219
Palsy
4204,9 2140219

degreeof dissociation a depends on V P

K α a α
P
Addition of inert gas :-
Relation between Kp , X and equilibrium pressure (P) :-
Le-Chatelier’s Principle :-

1.Chemical Equilibrium :-

I). E ect of Concentration :-

II). E ect of Temperature:-
III). E ect of Pressure :-
IV). E ect of catalyst :-

Industrial applications of Lechatelier’s principle :-

1.Formation of HI :-
4. Formation of SO3 ( contact process ) :-
5.Dissociation of PCl5 :-
Physical Equilibrium :-

1.Solid - Liquid equilibrium :-

E ect of Temperature :-

E ect of Pressure :-
E ect of Pressure on M.P. :-
2. Liquid - Vapour (gas) equilibrium :-
3. Solid - Vapour equilibrium :-
4. Phase transition :-

Equilibrium in Dissolution of solid in liquid :-

Equilibrium of gases in liquids :-
Thermodynamics - Equilibrium constant :-
Calculation of K from graph :-
Van’t Ho iso-chore equation :-

Simultaneous equilibria :-