Prof Harishankar Mathroni

CHEMISTRY XI
CHAPTER NO. 7
CHEMICAL EQUILIBRIUM
Q.DEFINE CHEMICAL EQUILIBRIUM
Def
T h e state in chemical reaction which proceeds in both: directions and the
concentration of both sides remains same (equal) is.called chemical equilibrium.
Kinds of chemical reactions:-There are 2 kinds
(a) Ir- reversible (b) Reversible reaction.

71(a) IR- REVERSIBLE REACTION:- (Uni-Directional)

,
Def
Maerae.
Reactionwhich proceeds for completion in indefinite direction (ondirection) is
called ir-reversible" reaction
Example: NaCl +AgNO, AgCl+NaNO,
NaOH+HCI NaCI +H,C
L.HS)
(Reactants)
OCehCe
RHS
i.e Reactants Products
i.e shifting of rection oaneactant to product, therefore it is also called "one"
way reaction
Rep- . \arföwmark" (- )
SRettansBompletely converted into product i.e R P
Thus poHeentration of reactants is "zero" and concentration of product is 100%
Aef completion of reaction, reaction stops.
Such reactions are carried out in open vessel
b) REVERSIBLE REACTION:
Def:
Reaction which proceeds in both direction i.e from reactants to products and from
products to reactants is called reversible reaction.
>It is "both" (two) way.direction reaction.
Example:
Reactants Product
PCl PCl+Clh
Rep:- It is rep. by (two half headed arrows)
Concentration ofreactants and concentration of products is same i.e 50% each.

Concentration ofreactants Concentration of products

50% 50%6
When rate of forward reaction is equal to rate of reverse reaction or vice-versa
then such stáge of reaction is called equilibrium state and mixture in such
condition is called equilibrium mixture.
Reversible reaction never stops & thus it is dynamic.
Equilibrium condition does not depend upon time.
Eqtbrum condicion depcnds upon temperature.

Equulabriuni &8AdikiBN dagend UAoR, 0ORDentration temperature:

I t is carried in closed vessel
Composed By Azhar Ali 1
 Prof. Harishankar Mau
7.1.2 Q. LAW OF MASSSACTION:
LAW OF EQUILIBRIUM)
Introduction:-
It was introduced by Norwegian Scientist, C.M "Gold Berg and Peter Wage" in 1864
64.
Definitions:
(i) Rate of substance at which it under goes change is directly proportional to its
active mass.
(ii) Rate of chemical reaction is directly proportional to product of active masses of
reacting substances at constant temperature.
i.e Rate of chemical rcaction oc Product of active mass of reacting substances.
Active mass means Molar concentration o fsubstance = concentration in

moles/dm*.

Explanation:-To find out equilibrium constant.(i.e "Kc")

equilibrium constant is derived by using following reversible eagion.
aA +bB forward
Reverse
reac.
reac.
C e c enVeraloa
cC +dD

According to law of mass action:

Rate of forward reaction
[A]" [B]°,

Rate of backward
reastionfolCETP
Since chêmiçal PquilipftumiS dynamic representing equal rates in both directions.
1.eRate Onwardrëaction =Rate of backward reaction.
-KblCTD
By rearranging this we get
K = Kc constant
Kr 4} [B Kr -Concentration in
moles/dm
At given temperature both Kfand Kh are constant. Kc Equilibrium constant
Kc CFDr
AF BF
Example: PCls PCl3 + Ch

According to law of mass action:

Ke =PCI,|lci,]|
PC1,
Thus:
Equilibrium constant (Kc) is equal to multiplication of active masses of products
divided by multiplication of active masses of reactants.
Thus we can say that:
Product of active masses of "Products" will be in "numerator" and product of
active masses of "reactants" will be in "denominator".
i.e cquilibrium constant (Kc) is ratio of product of active masses of products to
product of active masses of reactants.
Equilibrium constant is independent of initial concentration.
I t is constant at constant temperature and changes with change in temperature.
InCase of Gases: In gases partial pressure is used instead of concentration.
Partial pressure of gas « concentration of gas (T is
constant).
Composed By Azhar Ali 2
 Prof. Harishankar Mathrani
Example
Ar)+B) Ce+D)
ACcording to law of mass action, equilibrium constant for gases (Kp) will be given
as
Kp-Pe
Kp PA [PD]
PB)
PA, PB, Pc, Pp are partial pressure of gasses
A, B, C, D, respectively
Kp= Equilibrium constant of gases

7.1.3 RELATIONSHIP OF "Kp" AND "K¢"

(a) If"Volume" increases from reactants to product then Kp > Kc.
Example:-
2NH() N2e+3H2(g)
(b)If"Volume" decreases then, Kp < Kc.
Example:
2S0+Oz 2SO(g)
ciencehMOerabad
(c) If"Volume" is same then, Kp= Kc.
Example

7.1.4 (b) APPLICATION QFLAKOAMASs/ACTION

AMOE EQUILIBRIUM)
This lawis applicable ekc is used to)
14 (1) Predieectton
oOIohGFe Preactión
acth (2) Extent to which reaction occur

7.1.4RRÈDICTDIRECTION OFREACTION:
yahe of equilibrium constant (Kc) helps in predicting direction of reaction in
which it will shift to achieve equilibrium.
Reactants Products (Initial concentration ofreactants is known)
Thus:
Products Initial
Reac tan tsInitial
Then there are "3*" possibilities.

(a) When:r ProductsInitial

Re ac tan tsInitial Kc[Qc> Ke]
>

Then reaction will shift in reverse direction i.e to left i.e in reverse direction to
form less quantity of products till ratio decreases to value of "Kc".

(b) When: [Products nitial<

ialKC
Kc [Qc <Kc]
Reac tan ts|Initial
Then reaction willshift towards "right" i.e in forward direction to form more
quantity of product till ratio increases to value of "Kc"

When ProductsInitial Kc
(c) Reac ac tan tsInitial
shifting of reactants if
Then equilibrium is already achieved and there is no

conditions are not changed.

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 Prof. Harishankar Math
7.1.4 USE OF KC TO FIND EXTENT TO WHICH REACTION OCCURS OR
TOPREDICT EXTENT OF REACTION:
From value of "Kc" we can predict the extent to which reaction will occur:

(a) When value of "Kc" is Very "high"

(i) Then forward reaction is almost complete.
(ii) Reactants are "Un-stable".
(i) Example: 203 10
302 "Kc" is very "high" i.e1.2x10s
CH+Clh CHCl3 + HCI Kc =

(b) When value of "Kc" is very "low

(i) Then forward reaction proceeds with negligible speed.
i) Reactants are 'stable".
H2+F2 *Kc" is very "low" i.e 101
Example: 2HF
N2 +O2 5 2NO Kc = 4.5 x 10-31 Kqis very
"low" (Reaction is low)
Moleraba
(c) When value of "Kc" is "moderate"
i) Then reaction occurs in "both" direction
(ii) Equilibrium is attained aftercertai
Example N2+3 NK"is moderate" i.e 10
2NO SR
K=43.44

1.20.LECHATELIER'SRRINCIPLE
This prigcipls Wasninkodastd by lechatelier in 1884. This principle study the
effect ofconceniraton,tempetaturc,pressure and catalyst.

sySem at equilibrium is disturbed in anyway, then the system will shift in a

direcfion so as minimize or undo the effect of change.
OR
"If a system in equilibrium is altered in any way then the system will shift in a
direction so as to minimize or undo the effect of change".

FactorsThere
which Effect Chemical Equilibriume
are "4" factors which effect chemical equilibrium.
(1) Concentration (2) Temperature (3) Pressure (4) Catalyst

(1) Effect ofconcentration (change):

A +B C+D

AB]
(a) If concentration of "A" or "B" is increased then, equilibrium will shifted
towards right i.e more "C" and "D" are formed (According to Lechatelier's
Principle).
(b) If concentration of "C" or "D" is increased then, cquilibrium will shift
towards left i.e more "A" and "B" are formed.
such away that
Thus according to "Lechatelier's Principle" equilibrium shifts in
Kc" remains constant i.e from higher concentration to lower concentration.
Example: CO+3H2 CH4+ HO If
If concentration C0 or H2 is increased then forward direction
reaction increases.
concentration of CH4 and H2 is increased then backward.

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 Pref. HarishankarMathrani
(2) Effect of Temperature (change)
(a) In
"endothermic" reaction if temperature is increased then reaction will
shift in forward direction as such more
product is formed.
Example:- Na+O2
* 2NO AH=+90.3 K.J/mole.
Thus due to increase in
temperature, more "NO" is formed and
temperature N2 and02 are formed by decreasing temperature more N2 + O2byare formed.
decrease in

(6)In "exothermic" reaction, if temperature is decreased then reaction will shift

in forward direction and more
products are formed.
Example:- N2 + 3H2 = 2NH AH = -92 KJ/mole.

Thus due to decrease in temperature, more "NH3" is formed and by increase in

temperature more N2 and H2 are formed.

(3) Effect ofPressure (change):-E

Change ofpressure is related to change of volume. Pressure only effects gaseous equilibrium.
(a) If pressure is increased then equilibrium will shift from more volunie \Jower
volume.
Example:
2NH 2e)+3Hpe
2-Volumes 4-Volumes
(6) If pressure is increased then equilibriut hIt from product towards reactant
side i.emore "NH" is formed,
Example:
2S02 te)
3-Volunes U blumes
Ifpresire Sincréased then equilibrium will shift from reactant side to product
sideliemot $Ois formed.
(4)Eect of Catalyst on equilibrium:
Catalyst has no effect on equilibrium due to catalyst more quickly equilibrium
state is reached by decreasing energy of activation.

7.10. DISTINGUISH BETWEEN IR-REVERSIBLE &REVERSIBLE REACTION:

IR-Reversible Reaction Reversible Reaction
Reaction which proceeds in definite Reaction which proceeds in both directions is
direction is called ir-reversible reaction. called reversible reaction.
I t is one way reaction. I t is two way reactions.
Reactant > Products. Reactant Product.
.NaCl+AgNO3 AgCl +NaNO; PCls PCl +Clp2
Zero% 100% 50% 50%
After completion After equilibrium
I t is rep: by
I t is rep: by
.Reactants are completely converted into Atequilibrium concentration ofreactants& product is same.
I t is dynamic means RFr= RBk
products.
I t stops after certain time. It does not depend upon time
I t depends upon time. I t depends upon conc: temperature pressure volume
When rate offorward reaction is equal to reverse reaction
& vice-versa then.
Such stage is called equilibrium stage.
Such condition is called equilibrium condition.

Such mixture is called equilibrium mixture.

I t is carried in closed vessel.

Composed By: Azhar Al

 Prof. Harishankar Math
7.4 Q. SOLUBILITY PRODUCT: [Kspl
When equilibrium is obtained between dissolved ions and ions of sparingly
Def
soluble salt in saturated solution. Then it is called solubility product.
eg AgCl, CaSO4 are sparingly soluble in water (Very slightly soluble)
Rep: It is rep. by Ksp.
Example:
AgCl Ag' +C (1)
Un-dissolved Dissolved

Explanation:- According to law of mass action.

Ex-1 Kc Ag lcr 2 ) | Ex-2 CaSO) >Ca2 +SO,2 or ki. Kc =[Ca*j [sO:j
AgCI
Ke= Ca|so. | orKsp=[Ca"sO
CasO
Ke Caso.
But at
saturation, concentration of solid AgCl is constant. Henee an be written as:
Ke= Agcr]
K'
OR
cxK= lAg] |Cr o
Ksp Ag|lc
Ksp is called solubilitproduct"
i.e solubility prodnet is equal to product of ionic
concentration
in molesdhmsIn saturated solution, Ksp remains constant:
(conc. of dissolved ions)
Temperature: Solubility product is effected by temperature and it .varies with
temperature.
Application of solubility product: Solubility product helps to predict that the
precipitation will occur or not under given concentration.

) If ionic product is equal to solubility product Qs SPthen solution is said

to be saturated.
Ksp Qsp]
(ii) If ionic product is less than solubility product then solution is not
Ksp »Qsp
saturated i.e more amount if solute can be dissolved into solution.

(iii) Ifionic product is larger than solubility product P then the solution
is said to be super- saturated and excess of solute will precipitate to re-store
equilibrium condition.

7.5 0. COMMON ION EFFECT:

Def: The behaviour of solution in which same ion is produced by 2-different compounds
is called common ion effect.

Explanation:- Addition of common ion to saturated solution which is in equilibrium

condition causes increase in solubility product and thus
precipitation is obtained.
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 Such effect of ion is called
Prof. Harishankar Mathrani
that already contain common ion effect i.e when salt is dissolved in solution
one of its
ions, its solubility is less than in pure water.
Example:- AgCI
AgCl is slightly soluble in water its equilibrium exists as
AgCl Ag +CI
(Un-dissolved) (Dissolved)
According to law of mass action
Ke Aa
In saturated
AgCl
solution concentration of solid AgCl is constant Hence.
AgC =Ksp=[Ag'1 [CT]
Ksp
Ksp [Ag][CI]
Ksp means "Solubility product" i.e solubility product (Ksp) is equal to product of
ionic concentration (i.e in
conc. moles/dm").
Precipitation of electrolytes is caused when the cone of ifsonxeeeds the
solubility product.
It is achieved by increasing
common ion solubility
concentration of any oneof the ions i.e by adding
product can be exçeeded n(o\
Explanation: Precipitation of Agcls dalsedb adding CI as common ion in the form of
Nacl or Ag' as a common ion
the ar oAgNO3
i.e. By adding Cl or Ag
ign\preoipitátes are formed. This is called common ion effect.
AgClo a CP«)
Appicatou
ApplicatA i useful in qualitative salt analysis
i ) It plays more important role in many areas of analytical chemistry.
Common ion effects:
i) Lowering in solubility of salt.
(ii) Formation of precipitates.

Industrial Application of Le-Chatelier's Principle (L.C.P)

Le-Chatelier's principle is applied to get maximum yield of products in shortest
possible time.
Industrialist uses knowledge of equilibrium constant and Le-Chatelier's principle
to sort out the most suitable and favourable conditions under which the reaction is to be
carried out to give (a) maximum yield of product (b) in shortest possible time (c) with
less expenditure.
According to Le-Chateliers principle there are three factors which effect maximum
yield in short time are:
) Concentration (i1) Temperature (ii) Pressure
Example-1
HABER'S PROCESS (Preparation of NH)
Na+3H2 2NH3 (AH= - 46.2 KJ/mole)
1-Vol. 3-Vol 2-Vol (Exothermic power)
(4-Vol)
This reaction is exothermic and volume decreases.

Composed By Azhar Ali

 Prof. Harishankar Math
Effeet of Concentration: According to Le-Chatelier's principle, by increasin
(i) forward direction as much more
concentration of N2 or H2 equilibrium will shift in
NH, will be formed till equilibrium is obtained. pressure equilibrium
(ii) Effect of Pressure: According to L.C principle by increasing
volume (2.Vol product side) as
will shift from volume (4 Vol reactant side) to less
more NH3 will be formed
till
such it will shift in forward direction hence
equilibrium is obtained.
to L.C
ii) Effect of Temperature: As reaction is exothermic hence according
as such
forward direction
principle by decreasing temperature reaction will shift in
more NH, will be formed till equilibrium is achieved. Decreasing (lowering) of
of reaction. Favourable optimum temperature is 400-
temperature decreases rate
500°C.

Example-2
CONTACT PROCESS (Preparation of HSO)
1 Step by Oxidation of SO to SO3 e i c eMderaoae
2802+O2 O 2sO,AH=-45KJ/mole
2-Vol 1-Vol 1-Vol (Exothermic power
3-Vol
This reaction is exothermic and yálme decteaaes.
Effect of ConcentrationAecdrdhng to L.C principle, by increasing concentration
of SO, and O2 Fuilitti shit in forward direction as much more SO will be
formed till equilibrinbained.
(i) EffcctofTempetautë: As reaction is exothermic hence according to L.C principle,
Hdreasing temperature equilibrium will shift in forward direction as such more
OyiY be formed till equilibrium is achieved.
(i)Efect of Pressure: According to L.Cprinciple, by increasing pressure, equilibrium
will shift from more volume (3-Vol reactant side) to less volume (2 Vol product
side) as such it will shift in forward direction hence more SO will be formed till
equilibrium is obtained.
Note: 1) Decreasing (lowering) temperature slow down the rate of reaction,
2) High pressure is dangerous for equipment.
3) Suitable optimum temperature is 450°C.
4) Suitable pressure is 1-2 atmospheres.
5) Suitable catalyst is V0s (vanadicim penaoxide).

7.1.1(a) CHEMICAL EQUILIBRIUM (Conceptand Explanation)

Int: It is a Latin word and derived from aqueous means equal + Libra means state of
balance.
Def: (i) The state of reversible reaction where net change in the concentration of
reactants and products take place with time is called chemical equilibrium.

(ii) The state at which rate of forward reaction and back word reaction is same
called chemical equilibrium.
Rate of forward reaction = Rate of back word reaction.

Explanation:
It takes place in reversible reaction.
Rate of both opposing reactions is same.
Composed By Azhar Ali
 Prof Harishankar Mathrani
Reactants and products continuously interconvert into each other with same rate.
Reactants Products
Example: H2+I2 2HI
(Purple colour) (Light purple colour) (Colourless)
(At equilibrium)

Forward reaction Reverse (Backward) reaction

Reactant product Reactant product
Left right Left right
Initial rate of reaction fast Initial rate of reaction is almost negligible
After same time reaction After sometime reaction speed up till
becomes slow equilibrium
I t is
represented by (two half headed arrow)
Concentration of reactants and products is same
I t does not depend upon timne.
I t may change with change in concentration, temperature pressurS9

7.1.1 b)cONDITIONS FORCHEMICAL EQUILIBRIuMOG

i) Reaction is carried out in closed ve@selA

ii)Concentration, temperaturepresture oldfemustbe constant.

ii) Rate of for wgrd andhackyadreaction must be same (dynamic)
iv) Concentfatipnrbhteactants
a n t s and products must be same i.e composition
and

omixtureremains
j cohstant.
aro
7.1.1REcoGNIZECHEMICAL EQUILIBRIUM
Z1
Méthods to find Chemical Equilibrium)
There are two methods to recognize chemical equilibrium:
i) Physical method
ii) Chemical method

) Physical method(Absorption of radiation)

. Concentration of chemical solution is directly proportional to absorption of light
(UV, IR or visible).,
.i.e Concentration of chemical solution oc absorption of light.
Reractants and and products absorb ultraviolet (UV) radiation.
Infrared or (IR) or visible radiations with respect to their equilibrium
concentration.
Absorption of radiation is determined by spectrometer.
of reaction mixture is determined by percentage (%) of
Equilibrium concentration
absorbance of radiation.

) Chemical method (Determination of Equilibrium Constant Kc)

Latus consider the Esterification of acetic acid and ethyl malcohol for determining

equilibrium constant.

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 Prof. Harishankar Mat

CHCOOC,Hs + H;O
Equation:
CH,COOH +C;H5OH

Cone. in moles/dm'[
Initial conc.
Change (used)
X X
Conc. At equilibrium a-X b-x,

Kc =
CH,cooC, H,][H,0]
[CH,COOH][C,H,OH]
X
Ke = X X [ x ] or Kc
[a-x]x [b-x] [a-x][b- x]
amount of reactants we wigketve that
B y repeating experiments (using different
value of Kc will be same at. Constant temperature.

7.1.3 RELATIONSHIP BETWEEN Kc, Kp, Kx and Kn

aA +bB cC+
According to law of mass action ygget

(1)Ke

[PA [P1
(3) Kn ncnpl n- No. of moles of A,B,C,D.

4) Kx xMole fraction of A, B, C, D

Kc (RT)An R Gas constant =0.082 atm. dm / mole K

(5) Kp
The relationship between Kp, Kx and
T#Absolute temperature
An = Sum of No. of moles of product
Kr is given berum Sum of No. of reactants balanced in given equation.
(6) Kp Kx (P)an

(7) Kp

7.1.4 IMPORTANCE OF Ke AND Xc(Reaction Quotient)

7.1.4 (a) Reaction quotient (Qc)
Def: Ratio of molar concentration of product to that of reactant in reversible reaction is
called reaction quotient.

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 Prof. HarishankarMathrani
Rep: It is represented by Qc.
Only at the equilibrium.
Qc = Kc
Other use (without equilibrium state) Qc may be less or more than Kc duo to
continuous increase in combination of reactants and product.
To find Q
Expression aA +bB cD +dD
Qc= C D
AJ [Al [B
Here
"1 represents concentration at any particular instant (time)
It is not necessary at equilibrium.
Qc (reaction quotient) depends upon the actual concentration of reactants and
products at any time during reaction and it changes with time.
Kc is constant at particular temperature. Maera0a

IGiice

of
Coere

enor

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