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Chemical
Equilibrium
Chemistry | Class 11
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 Chemical
Equilibrium
solid
← liquid
Gas
liquid
Gas ←
Solution
a A- t bB
# xx tyy chemical
Egg
A, B are reactants and X, Y are
products representation

b/w the and

The double arrow
left hand
part
hand
right part shows that
changes
is
taking
both directions
place in the .

basis
On the
of
extent
of
reaction ,
before equilibrium
attained chemical
classified
is reactions be into
may
three
categories
+

to
⑨ Those reactions which
proceeds almost
completion .

(b) Those reactions which

proceeds only upto little

extent .

④ Those reactions
proceed to such
which extent an ,

concentration
that the
of reactants and products
at
equilibrium comparable
are .
 Equilibrium in Physical Process : .

Solid
liquid Equilibrium
-
: -

The
equilibrium existing b/w ice and water is an

eye of solid liquid equilibrium

In a close at
system
-

,
.

attain this
Oc ice and water
equilibrium .
At
point
rate
of melting af ice is equal to rate of freezing
of water The equilibrium is represented
. as -

H2O Cs) # Haole)

(b) liquid Gas Equilibrium t

- -

Evaporation of water in closed vessel is

egg
a an .

where rate
of liquid gas equilibrium af
-
.

to rate
evaporation is
equal of
condensation The .

equilibrium is represented as -

Ha Oct ) Hao
f- Cg)

(c) Solid -

solution
Equilibrium : .

add in
If you more and more salt a
glass of
stirred rod ,
water and with a glass after dissolving
some amount ,
you
will
find out
. no
further salt
is to the son and it settles down at the
going
bottom .
The sun is now said to be saturated and
in a state
of equilibrium .
At this
stage many
molecule the undissolved salt into
of
salt
from go
( dissolution) and amount
the sun same
of dissolved

salt are
deposited back ( Precipitation ) .

Thus ,
equilibrium rate dissolution is to
at
of equal
rate
of precipitation .

Salt ( solid) ⇐ salt ( in Sol

"
)

d) Gas -
San
equilibrium :
.

Dissolution
of liquid under pressure
a
gas
in a

closed
gas liquid equilibrium
in vessel established a -

The best
egg af
this
type of equilibrium te cold
drinks bottle The
equilibrium that exists with
.

in the bottle is -

way) Coal in Sol )

 Equilibrium in chemical Process :
.
-

4) Reversible Reaction ? -
A reaction in which not

react to
only the reactants
form the
products under

certain conditions but also the

products react to

reactants under the conditions is called

form
same

a Reversible Reaction .

Eg . Ci ) 3 fees ) t 4420cg) f- Persons) t

442cg)
Caches ) F Ca Ocs) t CO2

Ciii) Nag) t 3
Hugs ← 2N Hug)

② Irreversible Reaction : If a reaction cannot take

-

the
place in the reverse direction , i.e .

products formed do

not react to back the reactants under the same

fire
condition it is called an Irreversible selection .

Need
Cgi Ci ) Ag Noscaqjt Coop
→
Ag Ucs) t Ng
Nosy,
Cii ) 2mg 't 02cg ) →
2mg Ocs)

**
of the
If anyreversible product will be removed
from
the reaction will become irreversible
system ,

one
 Concept of chemical
Equilibrium : .

A t B ← C t D

at time -1=0 ao bo O O

time will A and B will be converted to

as
pass ,

As
C and D . soon as C and D will be
formed ,

reaction will start in back direction also .

A time
and B
of decomposition of A
will come when rate

to the A & B
of formation af
be rate
will
equal ,
to
forward reaction will be
equal
the rate
i.e .

of
reaction At this
the rate
of reverse .

stage the

reaction is said to be state chemical

in a
of
Equilibrium .

...
forward Reaction
n

I librium
point
¥
or
Reverse Reaction
>

Time →
 Characteristics
of chemical
Equilibrium : -

4) The equilibrium is
dynamic i the -
e .
reaction
continues in both
forward and reverse directions .

to the rate
② The rate
forward
of reaction
reaction
equals
of reverse .

③ The observable
properties of the
system such

concentration , invariant
as
pressure ,
density remains

with time .

④ The chemical
equilibrium can be
approached from
either side .

⑤ A the
catalystbut candoeshasten approach of
equilibrium not
ayer the state
of
equilibrium .

Types of Equilibria : -

(9) is said to
Homogeneous 8- Equilibrium be

homogeneous tf reactants and

products are in
same
phase .
 Hay ) t
12cg ) f- 2
HI
Cg )
N t 2N
2cg) Hag ) # 3
Hug )
Nally Cg) # 2 NO 2cg)
CH zero H CI) t Cana OH LI
) # CHS COO canst) t HIC

(b)Heterogeneous in Equilibrium is said to be

heterogeneous tf reactants and products are in

different phases
↳ coz ( s) Cao Cs) t Co2 Cg )
#

Nhu Hscs) #
Nb Cg) t Has
Cg)
N Hawa N Hy Cs ) # 2MHz
Cg)
t
Cong)
# Note and
pure liquid
the concentration
of
e
.
-

to the
pure solid assumed be
unity ,
as concentration
such substances remain constant i. e.
ofconcentration ,

motel like a
density
=
.
 law Mass Action
of BB
: -

AA t → cc t DD

rate reaction CAT CBTB

of reaction
a .

' 's
rate KEAT LBJ
af k is rate
=

where constant or
velocity constant

of the reaction at that temperature .

Unit rate constant Ck) [ moles hittin time -2

of
=

( where is order reaction )

n
of .

Concentration
Rate forward
day Reactant
←
of

÷:÷i:i
I

'
¥
I
E
l
i
Reaction
.

←Is
Equilibrium n.me
A →
Concentration Time at which Time

Product
of equilibrium is established

Eg : . Calculate the
partial pressure of each

component in the
following equilibria
Nag)
t
342cg ) #
2MHz
Eg)
Saks Nag ) t
3h29) #
2MHz eg)
at 7=0 a b O

b
at
equilibrium a x 3x 2x
- -

n
total = A -
Xt b -

3×+2 x = Cat b - 2x )
Partial
pressure
C9
Pma
ANNI Pt x Pt
=
=
x
( atb -
2x )

nnnf-xpt-ca.ba#gxPiPnns=nnNnsxA=ca+fIqxPt
Pna =

AA t b B cc t DD
#
then , Action
from law of
mass

( B2b
"
reaction CAT
of forward
rate ng a
"
ka CAT CBP and rate severs exaction
or
of
r, =

Loyd
'
nad Ccj
be ka CCJ [
'
DID
at
equilibrium ,
r, or

[ DID
'
→ K ,
CAN [ BJb= Kz [ CJ
 KIWI
the =

EAT
'
[ By
b

ke Kalka , in terms
an
equilibrium constant af
of reacting species
actin masses .

for the reaction

SO a U2 # SO , t Iz
at t -
- O a O O

at
equilibrium a- x x x

( vis
at
v
Iu ¥ volume
af
container)
So , CS0aUaT= ; Good = = Cuz]

=ca¥v kEa¥xu
so ,
Kc -
-

# Characteristics constant ( Kc ) in
of Equilibrium
C) Kc
for a
particular reaction at given temperature
has a constant value .

E) Value
of Kc
always depends on the nature
of
reactants and the
temperature ,
but independent
 of presence of catalyst
or ,
of inert material .

③ As value is
initial concentration
always independent of
reactants
the

of as well as the

products .

① The value Kc indicates the

proportion of
of
products formed equilibrium large
as .
ke value

means
large proportions of product .

⑤ when reaction reversed ,

the is
equilibrium
constant reaction also
for reverse will be

in versed .

He =
I
Kc

let us hare
At B Ct D

Kc = CcTLD)
TATTBJ
the
By reversing reaction ,
CTD
←
At D
A/B =
419
(6)
If the
coefficients of
reactants , products are

hatred doubled then value

according by
or ,

K' o
of
will
change .

At B CTD

Kc =
Cote
[AT EBT

for 2A t 2B act 2 D
←

"
=EaEY#r=f%ii=k :

⑦ when
equilibrium reactions added
ofconstant
a no .
are
,

the
equilibrium overall reaction is
for constants ,

the
product of equilibrium of respective
reactions .

02cg)
=CN0I[
t
Nay) #
2 NO; K,

NISHI
H2O
Cg) # Nagy t 2/202 egg; ka -
-
ENTITY
[ Nz
Na Oeg) t
21202cg ) -#
2N
0cg ); Ks = EMOJI
( Magog 't
÷=cnI:Y¥axck:T* u¥%÷↳
' -

i e Ks
-
.
=
kg
I

Equilibrium constant in terms

of partial
pressures :
-

let consider
us a
generalDDreaction
AA t BB cc t
#
PA PB Pc PD

from law action

of mass
' ' b
rza ( Pg ) (
9
PB ) r
,
= k, CPAP & PB)
d
PDT
'
Kz ( Pc ) ( p D)
'

ra 2 ( Pc ) ( be =

at
equilibrium
kg ( Pa ) ( PB )b= ka ( Pe ) ( pp )d
" '
r, =
rz or

Cppjd
¥ ,
=

( Pa ) 9 ( PB ) b

=(PcYCP b
Kp =

Kay , ( Pa ) 9 ( PB )
 Relation between Kp and Kc : -

for
"
a
general Eq ,

att t bB ect DD
←
the
where , a ,
b, c and d are
coefficients of
reacting substance

Kp =CPc5CPp)d_ b
( Pa )9 ( PB )
from
"
Gas Eg -

PV =
n RT P RT

[ AT RT
'

So ,
PA = PB = ( BIRT

Pc =
(c) RT; Pp -
[ D) RT

( I RT ) ( [ DIRT )d
'

Hence , Kp =
-
.

( IAI RT) 9 ( CBT RT)b .

Utd ) Cathy
Ccj ( DID
-

M ,
Kp =
X ( RT )
TAY
where
Ang =
{ cetd ) -

Cat b) } =

change in the nos .

of gaseous moles .

Hence , Kp =
Kc .
( Rt) Ang
 when An = O;
Kp = Kc
Dn s O; Kp 7 Kc
An L O;
Kp S Kc

EgCao Cs)
: - At 27°C Kp value for reaction Caws CDF
t
coaly ) is 0.2 atm calculate its Kc ,

value .

"
Sort Kp = Kc ( Rt )
An = I

ke =
tip a 0-I_ =
4×10-3
RT 0.082 X 300

Eg : A vessel at sooo K contains Coa with a

-

atm Some Co2 is

pressure of 0.5
of
the
.

into addition
converted
of graphite what
co on .

is the value Kp if the total at

of pressure
is ?
equilibrium 0.8 atm

Sol ? .

Coacg ) t Ccs) → 20cg)

0.5 O

0.5 n-
2n
total
pressure = 0.5 tn = 0.8

.
'

.
N = 0.3

(2×0.3510-5-0.3)
atm
Kp =
=
18

#
Significance value Kc
of Equilibrium constant : -

4) A
very large of Kp signifies Oe

reaction to
that the
forward completion or
goes
very clearlysmall
so .

(2) A value Kc Kp
of signifies
or
very
forwardextent
that the Haction does not occur to

any significant
.

to
(3) A reaction is most
likely reach a state

of equilibrium in which both the reactants and

products are present if the numerical value af

Kc or
Kp is neither very large nor
small .
very
 Fe Ocs ) fees)
Ege Kp for the
equilibrium Coop
,
t
←
.

at soooo is 0.4
+
Cong) .

If cog) at a
pressure
of I atm and excess Feocs) are
placed in a

container at 1000°C what are the

,
pressures
and attained is ?
of Wcg ) way ) equilibrium
when

Sol ? Atsumi ideal behaviour

-

ng gas partial pressures ,

to
are
proportional the no .

of moles
present since .

moles of Co2
formed equals moles
of co consumed ,

the
drop in partial pressure of equal
co will the

let
partial pressure of wa produced . the
partial
' '
be Then
pressure of
Coa at
equilibrium X atm .
,

partial pressure of
co will be CI x ) -
atm .

Since
Kp =

ptcooz =

1¥ = 0.4 x - O 286-

Hence Pco = 2 -
X

= O 724
-

atm .

'
The Reaction Quotient '
d i -

consider the
Equilibrium : -

P Uscg) P Uscg ) t
Uscg)
←
At
equilibrium CUaJlPU# = Kc .
When the reaction

[ PUD
'
this ratio is called Oc
'
is not at
equilibrium i. e ,

Oc is the
general term used for the abou
given
instant And
ratio at
any af
time . at
equilibrium
Cfc becomes Kc .

Similarly ,
Paspalj is called Ip and at
equilibrium
Pp Is

it becomes Kp .

reaction is D= Kc
→
If the at
equilibrium ,

→ A net reaction
proceeds from left to
sight (forward
direction)
if Os Kc .

A
→ net reaction
proceeds from right to
left
(the direction)
reverse
if O Kc >

"
# Le ch atelier 's
Principle : -

to
when an
equilibrium is
subjected either a

change in concentration ,
temperature on , in external
that
pressure ,
the
equilibrium will
shift in

direction effects caused

where the by these
 "
seduced
changes Pets
are .

Past Us
we hate this reaction at
equilibrium and the
and
moles of Ua , Pcb pus at
equilibrium are
and
a ,
b and C
sespectirely ,
the total
pressure
be PT

i.
Isp =

-
( afbtx Pt) ( atbbtx PTI abPr
ccatbtc)
( a¥× F)
Since Pt =
( at btc)
-
RT

Kp abrt
'

=
n
.

CV

Now d of Pds is to
if moles added the
system ,

the value
of I would be , 9CbtdJRT
CV

we can see that this is more than Kp .

fo the

would to attain
system more reverse
equilibrium
 4) increase the volume the
of system
the
If we

ab RT
'
,

Q becomes i
where v >v .

If

O becomes less and the would

system
-

i .
,
more

forward to attain
equilibrium .

② add noble at constant

Ifamounts to
we a
gasthe pressure ,

volume
increasing system
it the
of
and
therefore the reaction mores
forward .

③ If add the noble at constant volume ,

we
gas
the D=
0
abaft and
remains
expression of
as

the to be
system
continues in
equilibrium .

i
nothing happens
.

4) le chattier 's
Therefor for using principle
-

expression of Kp and
convert the Kc into basic

terms and then see the effect of changes

various .

Effect of concentration : -

let us hate a
general reaction ,

AA t BB Cct DD
tf .
 constant,
at a
givenKc temperature ,
the
equilibrium
= %D3d b
CAJA ( BT
and S the mole
again if d. B. y of of
are no .

and
A. B. c D are at
equilibrium
then , ke =[Y5lS#
[ AT 9115dB
added to keep
If any of product will be ,
the

concentration reactants
Kc constant ,
of will increase

hare the reaction will more in reverse direction .

disturbance
Similarly if ,
any change
a in reactant
side will be done ,
change in
product 's concentration
take to the
will place minimise
effect .

# Effect of Pressure
change of
: -

The
of change of
effect chemical
pressure on

equilibrium be done
can
) by the
formula .

Kp =
Ipx plan
 Case A : when Dn -

-
O

Kp =
Op
And equilibria is independent of pressure

case B : when An = -

re
an
Kp P de
-

-
-

Op .
=

pan
Here external will
with increase
towards
in
pressure ,
shift
direction to
the
equilibrium forward maintain
decrease
Kp .
Similarly ,
in
pressure
will
shift the

direction
equilibrium in the reverse .

Case c : when An = tie

Op Pan and to that

Kp -
- .

'
effect will be
opposite
'
case
of B .

# Effect
of catalyst on
Equilibrium in

catalystdirectionassociated
is
since the with
forward as

reaction So at
well as reverse .
,
equilibrium ,

of forward
will
rate reaction be
equal to rate
of
 and hence
catalyst effect
reverse reaction will be

Hence
same on both
forward as well as reverse .

catalyst never
affect the
point of equilibrium
but it reduces the time to attain the
equilibrium .

Effect due to the addition inert

on
equilibrium of
gases
-

total volume
change
case Ai -

when bn=O and at

So ,
equilibrium remain constant . addition
of inert

will the the mixture

gases
increase no .

of moles in

but
partial pressure of each
component remains

Hence
constant .

,
equilibrium remains
unaffected .

Case B: -
when An = tre and but ¥0
total volume will addition
The
of
increase with

This will the

inert
gases
.

shift equilibrium in

forward direction .
Case c : when An = -
re and AVT f- 0
will
In this case ,
the addition of inert
gases
increase the total volume and the reaction will

direction
shift in reverse .

# Kc
Dependence of KpEaf IRT
or on
Temperature :
Kf
-

=
Ape -
q ,
where , Kf = rate constant
for forward reaction ,

Af = Arrhenius constant
of forward reaction ,

Eat =

Energy of activation of forward reaction

and backward reaction
for Earl RT
Are (2)
-

Kr = -

Ca ) Cs)
Dividing by get
we
,

YI =AfzeCEar-Ea RT

know ( )
k÷,=k equilibrium
we that constant

i .

k=An#eCEar-Ear RT
At temperature Ts
lets =

Aaf e
leafier ) - Cs )

At temperature Ta

ka -

AAT e
CE¥zEarI -
d)

Dividing d) by ③ we
get
kk¥=eE'EX÷ log 'f÷=eg;¥;If÷
-

definedDH in
The reaction is terms
enthalpy of a

activation Eat
of energies Ear
as -

s.is#fE-ED.ilogkEq--a.3otg,-(F-fa)-
i.
log k¥7 -
-

For exothermic (H would be

an reaction ,
negative .

If we increase the
temperature of the system
( Ta TD the
right hand side of the eggs (5)
>
,
 becomes
Kiss
negative
Kt that
.

constant at
.
:
, ,
is ,
the
equilibrium
less than that at
the higher temperature would be
the lower temperature .

Eg Kp for the reaction 2 Babes ) 82 Ba Oes ) t

02cg)
'
-
.

2.6×10-4 atm , at 400°C Heat reaction the

is .

of
-

2524 kcal . what will be the no .

of mole
af
Oa
gas produced at 500°C
temperature if ,
it is

carried in 2 life reaction vessel ?

Sofi .

we know that

log :# :# 1¥ II =

a
-

log
.fi#o..--a..o;:::.o-.f::3I:IJ--kriioeKim
.
'

. Kp = Pose = I 46 X
. 10-5 atm
,

since ,
PV = n RT

46×10-5×2
-2.96×10-5×20
I. = nX O -
0821 X 773 .
i n

-
0821 X 773

4. 602×10-7 moles
 Relation b/w vapour density and
degree of
dissociation
PV
ofRT gas a

=
n

M = WRT =eRt
PT P

-
i

.
V D= PRI
2P

Since P =
NRI

V.
PRIi V D=
X V
'

2n RT 2n

for a reaction at
eqb .

,
V is a constant and p te a

constant i
vapour density and
.

i.
Totalmolesateguilibn.am#=vapourdensityCinitial)-
Initial total moles
vapour density ( at equilibrium)
=

Dq =M_m
( : molecular
weight = 2x V D
-
)
 Here M= molecular
weight initial
molecular
m =

weight at equilibrium
let us take a reaction
P Us Pds t Ck
←
Initial moles C O 0

At Ccs L ) ca ca
eqb
-

i .

CHILL =

DI ; 2tL=dI=Mm