7

Chapter
EQUILIBRIUM

7.1 STATE OF EQUILIBRIUM

* A state of equilibrium is attained when two opposing process (forward and reverse) occur simultaneously at the same rate.
* The mixture of reactants and products in the equilibrium state is called an equilibrium mixture.
* Type of equilibrium involving ions in aqueous solution is called ionic equilibrium.

7.2 EQUILIBRIUM IN PHYSICAL PROCESSES

The physical equilibrium is a state of equilibrium between the same chemical species in different phases.
Types of Physical Equilibria : The various equilibria which can exist in any physical system are,
Solid  Liquid ; Liquid  Gas (vapour) ; Solid Gas (vapour)

7.2.1 Solid- Liquid Equilibrium :

* When a solid is heated it starts melting at a certain fixed temperature (melting point). At this stage even when the heating is
continued, the temperature does not change until the whole of solid is converted into liquid. The state when solid and liquid
phases of a substance coexist is called solid-liquid equilibrium.
* Rate of transfer of molecules from ice to water = Rate of transfer of molecules from water to ice.
Rate of melting of ice = Rate of freezing of water
At 273 K, and 1atm pressure, G = 0, Ice  Water
* For any pure substance at atmospheric pressure, the temperature at which the solid and liquid phases are at equilibrium is
called the normal melting point or normal freezing point of the substance.

7.2.2 Liquid-Vapour Equilibrium :

* The vaporization equilibrium of water is an example whose consequences appear in everyday life. The “fogging” of bathroom
mirrors, occurs when the water vapour in warm air comes into contact with the cooler surface of the mirror, causing vapour
to condense. H 2 O ()  H 2 O(g)
7.2.3 Solid - Vapour Equilibrium :
* Certain solid substances on heating get converted directly into vapour without passing through the liquid phase this
process is called sublimation. The vapour when cooled give back the solid is called disposition.
* The substances which undergo sublimation are camphor, iodine, ammonium chloride etc.
Camphor (solid)  Camphor (vapour) ; NH4Cl (solid)  NH4Cl (vapour)
* If we place solid iodine in a closed vessel, after sometime the vessel gets filled up with violet vapour and the intensity of
colour increases with time. After certain time the intensity of colour becomes constant and at this stage equilibrium is
attained. Hence solid iodine sublimes to give iodine vapour and the iodine vapour condenses to give solid iodine.
I2 (solid)  I2 (vapour)

7.2.4 Equilibrium Involving Dissolution of Solid in Liquids

* When a saturated solution is in contact with the solid solute, there exists a
dynamic equilibrium between the solid and the solution phases.
Solid substance  Solution of the substance. Example: sugar and sugar solution.
* In a saturated solution of sugar in contact with solid sugar, a dynamic equilibrium
Sugar (s)  Sugar (aq)
is established. At the equilibrium state the number of sugar molecules going into
the solution from the solid sugar is equal to the number of molecules precipitating
out from the solution, i.e., at equilibrium,
* Rate of dissolution of solid sugar = Rate of precipitation of sugar from the solution.
STUDYMATERIAL: XI CHEMISTRY 1 EQUILIBRIUM
7.2.5 Equilibrium Involving Dissolution of Gases in Liquids
* Henry’s law : Gases dissolve in liquids. The solubility of a gas in any liquid depends upon.
(i) Nature of the gas and that of the liquid.
(ii) Temperature of the liquid.
(iii) Pressure of the gas over the surface of the solution.
“At a certain temperature, the mass of a gas which dissolves in a definite volume of a liquid is proportional to the pressure
of the gas in equilibrium with the solution.”
Thus, at a constant temperature, the ratio of the molar concentration of the gas in the solution and into the phase is constant

* Limitations of Henry’s law : Henry’s law is applicable to ideal gases only. Henry’s law should be applied only at low
pressures because real gases behave like ideal gases at low pressures.
Henry’s law is not applicable to gases which react chemically with the solvent. Henry’s law will not apply to the solution of
gases like ammonia (NH3) and hydrogen chloride (HCl) in water because these gases react chemically with water.

* Why does a chilled soda water bottle fizz out when opened : Soda water is a solution of carbon dioxide gas (CO2 (g)) in water
at high pressure. As soon as the bottle is opened under normal atmospheric conditions. The dissolved gas escapes out to
reach a new equilibrium state required by the lower pressure (the atmospheric pressure). At lower pressure, the solubility of
the gas in water decreases.

7.2.6 Characteristics of Equilibria Involving Physical Processes

* Equilibrium is possible only in a closed system at a given temperature.
* Forward and backward processes occur at same rate.
* All measurable properties of the system remain constant.
* At equilibrium, the concentrations of substances become constant at constant temperature.
* Some Features of Physical Equilibria :

Process Conclusion
Liquid  Vapour PH2O constant at given temperature
H2O ()  H2O (g)
Solid  Liquid Melting point is fixed at constant pressure
H2O (s)  H2O ()
Solute(s)  Solute Concentration of solute in solution is constant
(solution) at a given temperature
Sugar (s) Sugar
(solution)
Gas(g)  Gas (aq) [Gas(aq)]/[Gas(g)] is constant at a given temperature
CO2(g)  CO2(aq) [CO2(aq)]/[CO2(g)] is constant at a given temperature.

7.3 EQUILIBRIUM IN CHEMICAL PROCESSES

* Chemical Equilibrium in a reversible reaction is a state at
which both backward and forward reaction occur at the
same speed.
* The stage of the reversible reaction at which the Ra
te o
concentrations of the reactants and products do not rea f for
ctio war
change with the time. n d
* It can be shown graphically. Equilibrium state

At Equilibrium state,
ar d
Rate of forward reaction = Rate of backward reaction
b a ckw
Rf = Rb f n Time at which system
eo
* Equilibrium is dynamic in nature. Rat reactio has reached equilibrium
Chemical Equilibrium can be attained from either of the side
Time
i.e. from side of reactants or products
2HI(g)  H2(g) + I2(g) or H2(g) + I2(g)  2 HI(g)

STUDYMATERIAL: XI CHEMISTRY 2 EQUILIBRIUM

* Homogeneous chemical equilibria : A reversible reaction in which all the reactants and products at equilibrium are in the same
phase is referred to as homogeneous equilibrium.
In the gas phase, H2 (g) + I2 (g) 2HI (g)
In the liquid phase : CH3COOH () + C2H5OH () CH3COOC2H5 () + H2O ()
In the solution phase : Fe3+ (aq) + SCN– (aq) Fe (SCN)2+ (aq)

* Heterogeneous chemical equilibria : A reversible reaction involving equilibrium between various chemical species present in
two or more phases is said to be a heterogeneous chemical equilibrium.
CaCO3 (s) CaO (s) + CO2(g)
3Fe (s) + 4H2O (g) Fe3O4 (s) + 4H2(g)

7.4 LAW OF CHEMICALEQUILIBRIUM

* At a given temperature, the rate of reaction at a particular instant is proportional to the product of the active masses of the
reactants at that instant raised to power which are numerically equal to their respective molecules in stoichiometric equation
describing the reaction.
* Equilibrium constant in terms of molar concentration
For the reaction : nA + mB  z C + wD
Rf  [A]n [B]m R  [C]z [D]w
b
Rf = K1 [A] [B]
n m Rb = K2 [C]z [D]w
At equilibrium : Rf = Rb
K1 [A]n [B]m = K2 [C]z [D]w

K1 [C]z [D]w [Product] K R K

  ; Kc = 1  f  f
K 2 [A] [B]
n m [Reactant] K2 R b Kb
* Equilibrium constant in terms of pressure

p zp w
Kp  c n d n
pa p b
* Relation between Kc and Kp :
Kp = Kc (RT)n ; where n = no. of moles of gaseous product – no. of moles of gaseous reactant
Case I : When n = 0
Kp = K c
N2 + O2  2NO (n = 0)
Case II : When n = + ve (n > 0)
Kp > Kc
PCl5  PCl3 + Cl2 (n = +1)
Case III : When n = – ve n < 0
Kp < K c
N2 + 3H2  2NH3 (n = –2)
* It must be remembered that for the existence of heterogeneous equilibrium pure solids or liquids must also be present (however
small the amount may be) at equilibrium, but their concentrations or partial pressures do not appear in the expression of the
equilibrium constant. In the reaction, Ag2O(s) + 2HNO3(aq)  2AgNO3(aq) + H2O()

[AgNO3 ]2
Kc 
[HNO3 ]2
* Magnitude of equilibrium constant depends upon the way in which a reaction is written.
Chemical equation Equilibrium constant
aA + bB cC + dD K
cC + dD aA + bB K1 = 1/K
naA + nbB ncC + ndD K2 = Kn
a b c d
A B  D K3 = K1/n
n n n n

STUDYMATERIAL: XI CHEMISTRY 3 EQUILIBRIUM

Example 1 :
The equilibrium constant of a reaction is 20.0. At equilibrium, the rate constant of forward reaction is 10.0. Find the rate constant
for backward reaction.
Sol. Kc = 20, Kf = 10, Kb = ?
Kf 10 10
Kc = ; 20 =  Kb = = 0.5
Kb Kb 20

Example 2 :
4 mole of A are mixed with 4 mole of B, when 2 mole of C are formed at equilibrium according to the reaction,
A + B  C + D . Find the equilibrium constant.
Sol. A + B C + D
Initially 4 4 0 0
At equilibrium 4 –  4 –   
Given at equilibrium mole of C = 2 (  = 2)
 [A] = 4 – 2 = 2 mole ; [B] = 4 – 2 = 2 mole ; [D] =  = 2 mole
[C][D] 2  2
Kc =  =1
[A][B] 2  2
Example 3 :
At 1000K, the value of Kp for the reaction PCl5 PCl3 + Cl2 is 20R, then find Kc.
Sol. Kp = 20R (given)
For the reaction n = (2 – 1) = 1
Kp = Kc (RT)n
20 R
20 R = Kc (RT)1 Kc = = 0.02
R  1000

Example 4 :
Phosphorus trichloride and chlorine react to form phosphorus pentachloride. At 544 K, Kc is 1.60 for
PCl3(g) + Cl2(g)  PCl5(g)
Calculate the concentration of chlorine when 1.00 L of 6.00 M PCl3 is added to 2.00 L of 1.50M Cl2 and allowed to reach
equilibrium at 544 K.
Chemical equation Expression for Concentration
Sol. and initial Prepare iCe table equilibrium Evaluate expression of
concentration constant species

Start with the iCe [initial concentration (i), change due to the reaction (C) and the equilibrium concentration (e)] table.
First write the initial concentration, the change, and the equilibrium concentration.
PCl3(g) + Cl2(g)  PCl5(g)
Initial, M 2.00 1.00 0.00
Change, M –y –y +y
Equilibrium, M 2.00 – y 1.00 – y y
[PCl5 ] y
Kc  ; 1.60 
[PCl3 ] [Cl 2 ] (2.00  y) (1.00  y)
Rearrange and combine terms
1.60y2 – 5.80y + 3.20 = 0 ;y = 0.68 or 2.95
Mathematically, a quadratic equation has two roots, but a chemical system has only one physically reasonable answer. The last
line of the iCe table indicates that [Cl2] = 1.00 – y. In this case, we reject y = 2.95, since it predicts a negative concentration for
chlorine.
We check the answer by calculating the concentrations of all the species, and substituting these back into the expression for the
equilibrium constant to be sure that the results are consistent.
[PCl5] = y = 0.68 M ; [Cl2] = 1.00 – y = 0.32 M ; [PCl3] = 2.00 – y = 1.32 M
[PCl5 ] 0.68
Kc    1.6
[PCl3 ] [Cl2 ] (1.32) (0.32)
This result is in agreement with the original value of 1.60, so we can be confident that the problem has been solved correctly.
STUDYMATERIAL: XI CHEMISTRY 4 EQUILIBRIUM
Example 5 :
You are given the following reaction and its equilibrium constant at a given temperature.
2HBr (g) + Cl2 (g)  2HCl (g) + Br2 (g) ; Kc = 4.0 × 104
Write the expression for, and calculate the numerical value of, the equilibrium constant for each of the following at the same
temperature.
(a) 4HBr (g) + 2Cl2 (g)  4HCl (g) + 2Br2 (g)
1 1
(b) HBr (g) + Cl2 (g)  HCl (g) + Br2 (g)
2 2
Sol. We recall the definition of the equilibrium constant. For the original equation,
[HCl]2 [Br2 ]
Kc = = 4.0 × 104
[HBr]2 [Cl2 ]
(a) The original equation has been multiplied by 2, so Kc must be squared.

[HCl]4 [Br2 ]2
K c  = (Kc)2 = (4.0 × 104)2 = 1.6 × 109
[HBr]4 [Cl2 ]2

1 1
(b) The original equation has been multiplied by (divided by 2), so Kc must be raised to the power. This is the same as
2 2
extracting the square root of Kc.

[HCl][Br2 ]1/2
K c  1/2
 K c  4.0  104  2.0  102
[HBr][Cl2 ]

7.5 APPLICATIONS OF EQUILIBRIUM CONSTANTS

7.5.1 Predicting the Extent of a Reaction
* If Kc > 103, products predominate over reactants, i.e., if Kc is very large, the reaction proceeds nearly to completion.
* If Kc < 10–3, reactants predominate over products, i.e., if Kc is very small, the reaction proceeds rarely.
* If Kc is in the range of 10–3 to 103, appreciable concentrations of both reactants and products are present.

7.5.2 Predicting the Direction of the Reaction

Consider the following reversible reaction
A+BC+D
The reaction quotient (Qc) is the ratio of the product of active masses of the products and product of active masses of the
reactants.
[C][D]
 Qc = [A][B]

The concentration are not necessarily equilibrium concentration. [At equilibrium Qc = Kc]
Case I : If Qc < Kc then : [Reactants] > [Products]
then the system is not at equilibrium
[Product]
The value of is small.
[Reactant]
 For establishment of equilibrium the reaction will go in forward direction. [Reactants  Products]
Case II : If Qc = Kc then : The system is at equilibrium and the concentration of the species C, D, B,A are at equilibrium.
Case III : If Qc > Kc then : [Products] > [Reactants]
The system is not at equilibrium.
[Product]
The value of is large.
[Reactant]
 For establishment of equilibrium the reaction will go in backward direction [Products  Reactants]

STUDYMATERIAL: XI CHEMISTRY 5 EQUILIBRIUM

Example 6 :
At a very high temperature, Kc = 1.0 × 10–13 for the following reaction :
2HF(g)  H2(g) + F2(g)
At a certain time the following concentrations were detected. Is the system at equilibrium ? If not, what must occur for equilibrium
to be established ?
[HF] = 0.500 M, [H2] = 1.00 × 10–3 M, and [F2] = 4.00 × 10–3 M
Sol. We substitute these concentrations into the expression for the reaction quotient to calculate Q. Then we compare Q with Kc to

[H 2 ][F2 ] (1.00  103 )(4.00  103 )

see whether the system is at equilibrium. Q 2
 2
 1.60  105
[HF] (0.500)
But Kc = 1.0 × 10–13, so Q > Kc. The system is not at equilibrium. For equilibrium to be established, the value of Q must decrease
until it equals Kc. This can occur only if the numerator decreases and the denominator increases. Thus, the right-to-left reaction
must occur to a greater extent than the forward reaction; i.e., H2 and F2 must react to form more HF to reach equilibrium.

7.5.3 Relationship between equilibrium constant, Reaction quotient (Q) and Gibbs energy (G) :
G = Gº + 2.303 RT log Q
where G = free energy change of the reaction at TK ; Gº = standard free energy change at 298 K ;
R = gas constant (= 8.314 J mol–1 K–1), and Q is the quotient of reaction.
[C]c [ D]d
For reaction : aA + bB  cC + dD, Q=
[A ]a [ B]b
At equilibrium, G = 0, so Q must be equal to equilibrium constant, K.
 0 =  Gº + 2.303 RT log K or Gº = – 2.303 RT log K or ln K = – Gº/RT
Taking antilog of both sides, we get, K  eG  /RT
The reaction spontaneity can be interpreted in terms of the value of Gº
G  /RT
* If Gº < 0, then –Gº/RT is positive, and e  1 , making K >1, which implies a spontaneous reaction or the reaction
which proceeds in the forward direction to such an extent that the products are present predominantly.
G  /RT
* If Gº > 0, then –Gº/RT is negative, and e  1 , that is , K < 1, which implies a non-spontaneous reaction or a
reaction which proceeds in the forward direction to such a small degree that only a very minute quantity of product is formed

Example 7 :
Hydrolysis of sucrose gives, Sucrose + H2O . Glucose + Fructose
Equilibrium constant Kc for the reaction is 2 × 1013 at 300 K. Calculate Gºat 300 K.
Sol. Gº = – RT ln Kc = – 8.314J mol–1K–1 × 300K × ln (2 × 1013) = – 7.64 × 104 J mol–1

7.6 LE CHATELIER'S PRINCIPLE

According to this principle, "If a system at equilibrium is subjected to a change of concentration, pressure or temperature, the
equilibrium shift in a direction that tends to undo the effect of the change".
(A) Effect of change in concentration : In a chemical equilibrium, increasing the concentration of the reactants result in shifting
the equilibrium in favour of products (i.e. equilibrium shift in forward direction). Increasing concentration of the products
results in shifting the equilibrium in favour of reactants (i.e in the backward direction).
Concentration Equilibrium shift
Concentration of reactant  Forward direction
Concentration of product  Backward direction
(B) Effect of change in pressure : According to lechatelier's principal if the pressure is increased reaction will take place in that
direction, which will bring lowering of pressure or lowering in number of mole.
(i) Increase of pressure shifts the equilibrium in that direction where number of moles decreases. (n < 0)
eg. N2 + 3H2  2NH3 ; n = 2 – 4 = – 2 <0
i.e. on pressure equilibrium shift in forward direction.
(ii) Decrease of pressure shifts the equilibrium in that direction where number of mole increase. (n > 0)
eg. PCl5PCl3 + Cl2 ; n = 2 – 1 = + ve
i.e. in pressure equilibrium shift in forward direction
(iii) Change of pressure has no effect if n = 0
eg. H2 + I2 2HI  n = 2 – 2 = 0

STUDYMATERIAL: XI CHEMISTRY 6 EQUILIBRIUM

 (C) Change in temperature :
(i) For endothermic reaction : If we increase the temperature equilibrium shift in forward direction which proceed with
absorption of heat.
(ii) For exothermic reaction : If we increased the temperature the equilibrium shifts in backward direction which proceed
with evolution of the heat.

(D) Role of Catalyst : Positive catalyst increase the rate of both the forward and backward reaction equally so the equilibrium will
be attained in less time. Negative catalyst decrease the rate of both forward and backward reaction so equilibrium will be
attained in more time.

7.6.1 Applications of Le-Chatelier's principle :

With the help of this principle, most favourable conditions for a particular reaction can be predicted :
* Formation of nitrogen peroxide :
2NO + O2 2NO2 + 27.8 kcal
(i) High pressure (ii) Low temperature, (iii) Excess of NO and O2.

* Formation of sulphur trioxide and hence sulphuric acid (Contact process).

2SO2 + O2 2SO3 + 45 kcal.
2vol 1 vol 2 vol
(i) High pressure (n < 0), (ii) Low temperature ; (iii) Excess of SO2 and O2.

* Synthesis of ammonia (Haber's process).

N2 + 3H2 2NH3 + 23 kcal (exothermic)
(i) High pressure (n < 0), (ii) Low temperature
(iii) Excess of N2 and H2, (iv) Removal of NH3 favours forward reaction.

* Dissociation of phosphorus pentachloride :

PCl5 PCl3 + Cl2 – X kcal
1 vol 1 vol 1 vol
(i) Low pressure or high volume of the container, n > 0, (ii) High temperature ; (iii) Excess of PCl5

* Oxidation of CO by steam (Bosch process).

CO + H2O (steam) CO2 + H2 + X kcal
(i) Low temperature ; (ii) Excess of steam.

* Boiling of water :
Water Water vapour – X kcal
(low volume) (high volume)
It is accompanied by absorption of heat and increase in volume.
(i) At high temperature more vapour is formed.
(ii) At higher pressures, vapour will be converted to liquid as it decreases volume.
(iii) At higher pressures, boiling point of water is increased (principle of pressure cooker).

* Solubility of salts : In most cases, when a solute passes into solution, heat is absorbed, i.e., cooling results. Therefore
according to Le Chatelier’s principle, when heat is applied to a saturated solution in contact with solute, the change will take
place in that direction which absorbed heat (i.e., which tends to produce cooling). Therefore, some more of the solute will
dissolve. In other words, the solubility of the substance increases with rise in temperature.
Dissociation of a few salts (e.g., calcium salts of organic acids) is accompanied by evolution of heat. In such cases, evidently,
the solubility decreases with rise in temperature.
If solubility of a salt is accompanied by absorption of heat, its solubility increases with rise in temperature ;
e.g. NH4Cl, K2SO4, KNO3, PbNO3 etc.
KNO3(s) + aq  KNO3 (aq) – Q kcal
On the other hand ; if it is accompanied by evolution of heat, solubility decreases with increase in temperature ; e.g.
CaCl2, Ca(OH)2, (CH3COO)2Ca, NaOH, KOH etc.
Ca(OH)2(s) + aq  Ca(OH)2 (aq) + Q kcal

STUDYMATERIAL: XI CHEMISTRY 7 EQUILIBRIUM

Example 8 :
For the exothermic formation of sulphur trioxide from sulphur dioxide and oxygen in the gas phase :
2SO2 (g) + O2 (g) 2SO3 (g)
Kp = 40.5 atm–1 at 900 K and rH = – 198 kJ mol–1
(i) Write the expression for the equilibrium constant for the reaction.
(ii) At room temperature (300 K) will Kp be greater than, less than or equal to Kp at 900 K.
(iii) How will the equilibrium be affected if the volume of the vessel containing the three gases is reduced, keeping the temperature
constant. What happens ?
(iv) What is the effect of adding 1 mole of He (g) to a flask containing SO2, O2 and SO3 at equilibrium at constant temperature.
Sol. (i) The equilibrium constant for this reaction is written in terms of the partial pressures of the reactants and products.

pSO
2
So, Kp  3 (g)
pSO
2
2 (g)
 pO2 (g)
(ii) This reaction is exothermic. So, its equilibrium constant should increase with the lowering of temperature. Therefore, the
value of Kp at 300 K will be greater than the value at 900 K.
(iii) When the volume of the vessel is reduced, the volume of the reaction mixture will decrease. As a result, pressure of the
gaseous mixture will increase. According to the Le Chatelier’s principle, the system will move in a direction to undo the effect
of the pressure increase. The system therefore will move in a direction so as to decrease the number of moles of the gaseous
substance in the system. The number of moles decrease in going from reactants to the product side. Therefore, a decrease
in the volume of the reacting system will shift the equilibrium to the right. That is, more SO3 (g) will be formed from the
reactants.
(iv) Addition of helium to the reaction mixture at equilibrium under constant volume has no effect on the equilibrium.

Example 9 :
Describe the effect of (a) Addition of H2 (b) Addition of CH3OH (c) Removal of CO (d) Removal of CH3OH on the equilibrium
of the reaction : 2H2(g) + CO(g) CH3OH(g)
[CH3OH]
Sol. The equilibrium constant for the given reaction is Kc =
[H 2 ]2 [CO]
(a) Addition of H2 will push the reaction in the forward direction.
(b) Addition of CH3OH will push the reaction in the backward direction.
(c) When CO is removed, the reaction will move in the backward direction.
(d) When CH3OH is removed, the reaction will move in the forward direction.

Example 10 :
Under what conditions will the following reactions go in the forward direction?
(a) 2SO2(g) + O2(g) 2SO3(g) + 45 k cal.
(b) 2NO(g) + O2(g) 2NO2(g) + 27.8 k cal.
(c) PCl5(g) PCl3(g) + Cl2(g)- X k cal.
Sol. (a) Low T, high P, excess of O2 and SO2
(b) Low T, high P, excess of NO and O2
(c) High T, low P, excess of PCl5

7.7 IONIC EQUILIBRIUM

7.7.1 Electrolytes :
* Solutes such as CuSO4 or NaCl, which yield electrically conducting aqueous solutions, are called electrolytes.
* Aqueous solutions of most molecular compounds do not conduct electricity, and such solutes are called nonelectrolytes.
Examples are sugar and ethylene glycol (the solute in antifreeze solutions).
* Strong electrolyte : Those ionic conductors which are completely ionized in aqueous solution are called as strong electrolyte.
Ex. Na+Cl–, K+Cl–, etc.
* Weak electrolytes : Those electrolytes which are partially ionized in aqueous solution are called as weak electrolytes.
Ex., HCN, CH3COOH, NH4OH, Cu(OH)2

STUDYMATERIAL: XI CHEMISTRY 8 EQUILIBRIUM

7.7.2 Acid-Base Arrhenius concept : According to Arrhenius concept
* Acid : The acid is defined as those compounds which given H+ in aqueous solution.
HCl + H2O  H+ + Cl–
(i) Strong acids : Almost completely ionized in water. Hence give more H+ ions.
e.g. : HCl, HNO3, H2SO4, etc.
(ii) Weak acids : Feebly ionized in water. Hence give less H+ ions.
e.g. : HCN, CH3COOH, H2CO3, H2S etc.
* Base : The base defined are those compounds which give OH– in aqueous solution.
NaOH + H2O  Na+ + OH–
(i) Strong bases : Almost completely ionized in water. Hence give more OH– ions.
e.g. : NaOH, KOH, RbOH etc.
(ii) Weak bases : Feebly ionized in water. Hence give less OH– ions.
e.g. : NH4OH, C2H5NH3+, OH–, Ba(OH)2, Al(OH)3, Ca(OH)2, etc.

Limitations of Arrhenius theory :

* Arrhenius explained the conductivity of ionic compound in aqueous solution or in presence of solvent only (i.e. presence of
solvent is must) while ionic compounds in fused state form conductive liquids.
* The increase of equivalent conductance for strong electrolytes is not due to increase in number of ions but due to the
increase in ionic mobility with dilution.
Ionic mobility = speed of ions/potential gradient
* Strong electrolytes do not obey Ostwald dilution law.

7.7.3 Bronsted-Lowry concept

* According to this concept, the acid is defined as a substance which give up proton & the base is defined as a substance
which accepts proton.
* Acids are proton donors and bases are proton acceptors.
* For example of dissolution of NH3 in H2O represented by the following equation:

adds proton

–
NH3 (aq) + H2O () NH4 + (aq) + OH (aq)
conjugate conjugate
acid base
base acid

loses proton

* The acid-base pair that differs only by one proton is called a conjugate acid-base pair. Therefore, OH– is called the conjugate
base of an acid H2O and NH4+ is called conjugate acid of the base NH3.
* If Brönsted acid is a strong acid then its conjugate base is a weak base and viceversa.
* It may be noted that conjugate acid has one extra proton and each conjugate base has one less proton.
* Consider the example of ionization of hydrochloric acid in water. HCl (aq) acts as an acid by donating a proton to H2O
molecule which acts as a base.

adds proton

–
HCl (aq) + H2O () H3O+ (aq) + Cl (aq)
acid base conjugate conjugate
acid base

loses proton
* Cl– is a conjugate base of HCl and HCl is the conjugate acid of base Cl–. Similarly, H2O is a conjugate base of an acid H3O+
and H3O+ is a conjugate acid of base H2O.
Note : In case of reaction with HCl water acts as a base while in case of ammonia it acts as an acid by donating a proton.

STUDYMATERIAL: XI CHEMISTRY 9 EQUILIBRIUM

Example 11 :
What are the conjugate bases of nitric acid, HNO3, and the hydrogen sulfate ion, HSO4– ?
Sol. A conjugate base is always found by removing one H+ from a given acid and adjusting the charge on the remainder.
Removing one H+ (both the atom and the charge) from HNO3 leaves NO3–. The nitrate ion, NO3–, is thus the conjugate base of
HNO3. Deleting an H+ from HSO4– leaves its conjugate base, SO42–. (Notice that the charge goes from 1- to 2- because we’ve
removed the positively charged H+.)

Example 12 :
Identify the conjugate acid-base pairs in the following chemical reactions :
(a) H2SO4(aq) + H2O () –– HSO4– (aq) + H3O+(aq) (b) H2O () + F– (aq)  OH– (aq) + HF (aq)
Sol. (a) The H2SO4 loses a proton to form HSO4– , so H2SO4 is the acid and HSO4– is the conjugate base. H2O accepts a proton,
forming H3O+. H2SO4/HSO4–, H3O+/H2O
(b) Water loses a proton to form OH–, so H2O is the acid and OH– is its conjugate base. The fluoride ion accepts the proton,
forming its conjugate acid, HF. H2O/OH–, HF/F–

7.7.4 Lewis concept

(i) Lewis acid : Compounds having nature of accepting electron pair are called acids.
e.g. : AlCl3, Co3+, Mg2+, ZnCl2, SnCl2 , SnCl4, BF3, Ag+, H+, Cu2+
(ii) Lewis base : Compounds having nature of donating electron pair are called bases.
e.g. : H2O, OH–, Cl–, CN–, NH2–, NH

3 , ROH
 , R – O
.. – R


Example 13 :
Classify the following species into Lewis acids and Lewis bases and show how these act as such:
(a) HO– (b) F– (c) H+ (d) BCl3
Sol. (a) Hydroxyl ion is a Lewis base as it can donate an electron lone pair (: OH– ).
(b) Flouride ion acts as a Lewis base as it can donate any one of its four electron lone pairs.
(c) A proton is a Lewis acid as it can accept a lone pair of electrons from bases like hydroxyl ion and fluoride ion.
(d) BCl3 acts as a Lewis acid as it can accept a lone pair of electrons from species like ammonia or amine molecules.

7.8 IONIZATION OFACIDS AND BASES

* Strong acids like perchloric acid (HClO4), hydrochloric acid (HCl), hydrobromic acid (HBr), hyrdoiodic acid (HI), nitric acid
(HNO3) and sulphuric acid (H2SO4) are termed strong because they are almost completely dissociated into their constituent ions
in an aqueous medium, thereby acting as proton (H+) donors.
* Strong bases like lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), caesium hydroxide (CsOH)
and barium hydroxide Ba(OH)2 are almost completely dissociated into ions in an aqueous medium giving hydroxyl ions, OH–.
* The equilibrium moves in the direction of formation of weaker acid and weaker base because the stronger acid donates a proton
to the stronger base.
* Strong acids have very weak conjugate bases.
* Very strong base would give a very weak conjugate acid.
* Certain water soluble organic compounds like phenolphthalein and bromothymol blue behave as weak acids and exhibit different
colours in their acid (HIn) and conjugate base (In–) forms.
HIn (aq) + H2O ()  H3O+ (aq) + In– (aq)
Acid Conjugate Conjugate
indicator acid base
colour A colour B
Such compounds are useful as indicators in acid-base titrations.

7.8.1 The Ionization Constant of Water and its Ionic Product

* Consider H2O () + H2O ()  H3O+ (aq) + OH–(aq)
acid base conjugate conjugate
acid base
[H3O  ] [OH  ]
* The dissociation constant is represented by, K 
[H 2 O]

STUDYMATERIAL: XI CHEMISTRY 10 EQUILIBRIUM

 * The concentration of water is omitted from the denominator as water is a pure liquid and its concentration remains constant.
[H2O] is incorporated within the equilibrium constant to give a new constant, Kw, which is called the ionic product of water.
Kw = [H+][OH–]
* At 298 K, [OH–] = [H+] = 1.0 × 10–7 M ; Kw = [H3O+][OH–] = (1× 10–7 )2 = 1 × 10–14 M2
* Value of Kw increases with increase in temperature and decreases with decrease in temperature.

7.8.2 The pH Scale

* The term pH was given by Sorenson. pH is defined as the negative logarithm to the base 10 of the hydrogen ion concentration
i.e. pH = –log[H+]
* pH lies from 0 to 14. For pure water pH = 7. For acidic solution pH is less than 7 and for basic solution pH is more than 7.
* Solution with pH = 0 is acidic.
* Value of pH of acid, base & salts having same concentration is different.
* Mid point of scale is pH = 7, represent neutrality.
At 298 K, Kw = [H3O+][OH–] = 10–14
Taking negative logarithm on both sides of equation,
–log Kw = – log {[H3O+] [OH–]} = – log [H3O+] – log [OH–] = – log 10–14
pKw = pH + pOH = 14
* Kw may change with temperature the variations in pH with temperature are so small that we often ignore it.
* pH meter is a device that measures the pH-dependent electrical potential of the test solution within 0.001 precision.

Example 14 :
At 25°C the [H+] of an acidic solution is 10–5 then find out its pH.
Sol. pH = – log [H+] = – log 10–5 = + 5 log 10 = 5

Example 15 :
At 25°C the [OH–] is 10–9 then find out the value of pH of the solution.
Sol. pH + pOH = 14
[H+] [OH–] = 10–14

1014
[H+] = 9
 105
10
pH = – log [H+] = – log [10–5] = + 5 log 10 = 5

7.8.3 Ionization Constants of Weak Acids

Consider a weak acid HX
HX (aq) + H2O () H3O+ (aq) + X– (aq)
Initial concentration C 0 0
Let  be the extent of ionization Change (M) –C +C +C
Equilibrium concentration (M) C – C C C
Here, C = Initial concentration of the undissociated acid.
HX at time, t = 0 ; = extent upto which HX is ionized into ions.

C 2 2 C 2
Ka   ; Ka is called the dissociation or ionization constant of acid HX. In terms of molar concentration
C (1   ) 1  

[H  ] [X  ]
Ka 
[HX]

7.8.4 Ionization of Weak Bases

Consider a weak base MOH : MOH (aq) M+ (aq) + OH– (aq)
 
The ionization constant of base can be denoted by K b  [M ] [OH ]
[MOH]

C 2
If C = initial concentration of base ; = degree of ionization of base ; Kb 
C (1   )
STUDYMATERIAL: XI CHEMISTRY 11 EQUILIBRIUM
Example 16 :
The pH of 0.004M hydrazine solution is 9.7. Calculate its ionization constant Kb and pKb.
Sol. NH2NH2 + H2O  NH2NH3+ + OH–
From the pH we can calculate the hydrogen ion concentration. Knowing hydrogen ion concentration and the ionic product of
water we can calculate the concentration of hydroxyl ions. Thus we have:
[H+] = antilog (–pH) = antilog (–9.7) = 1.67 × 10–10

Kw 1  1014
[OH  ]  
 10
 5.98  10 5
[H ] 1.67  10
The concentration of the corresponding hydrazinium ion is also the same as that of hydroxyl ion. The concentration of both
these ions is very small so the concentration of the undissociated base can be taken equal to 0.004 M.

[NH 2 NH3 ] [OH  ] (5.98  105 )2

Thus, K b    8.96  107
[NH 2 NH 2 ] 0.004
pKb = – log Kb = – log (8.96 × 10–7) = 6.04.

7.8.5 Relation between Ka and Kb :

Let us take an example of a weak acid which ionises in aqueous solution
HA + H2O H3O+ (aq) + A– (aq)
(acid) (conjugate base)

[H3O] [A  ]
Ka 
[HA]
Dissociation of a weak base (conjugate base) in water can be written as
B (aq) + H2O () BA (aq) + OH– (aq)
(base) (conjugate acid)

[BH  ] [OH  ]
Kb 
[B]
Ka × Kb = Kw
If we take negative logarithm on both sides of the equation
pKa + pKb = pKw = 14 (at 298 K)

Example 17 :
Calculate the pH of a solution that is 0.050 M in ammonium ion. (Kb for ammonia = 1.8 × 10–5)
Sol. First, write the chemical equation
NH4+(aq) + H2O () H3O+ (aq) + NH3(aq)
Calculate Ka from Kb for ammonia.
K w 1.0  1014
Ka   = 5.6 × 10–10
Kb 1.8  105
Now, write the iCe [initial concentration (i), change due to the reaction (C) and the equilibrium concentration (e)] table.
NH4+ + H2O  H3O+ + NH3
Initial, M 0.050 0 0
Change, M –y +y +y
equilibrium, M 0.050 – y y y
Substitute into the equilibrium constant expression and solve for y.

[H 3O  ] [NH 3 ] (y) (y)

Ka  ; 5.6  10 
10
[NH 4 ] 0.050  y

y2
If y << 0.050 then 5.6  1010  ; y2 = 0.050 × 5.6 × 10–10 = 2.8 × 10–11 ; y = 5.3 × 10–6
0.050
Is 5.3 × 10–6 << 0.050 ? Yes, it is. The assumption is good and we can accept the value.
[H3O+] = 5.3 × 10–6 ; pH = – log [5.6 × 10–6] = 5.28

STUDYMATERIAL: XI CHEMISTRY 12 EQUILIBRIUM

7.8.6 Di- and Polybasic Acids and Di- and Polyacidic Bases
The acids like oxalic acid, sulphuric acid and phosphoric acids have more than one ionizable proton per molecule of the acid.
Such acids are known as polybasic or polyprotic acids.
The ionization reactions for example for a dibasic acid H2X are represented by the equations:
H2X (aq)  H+ (aq) + HX– (aq)
HX– (aq) H+ (aq) + X2– (aq)
And the corresponding equilibrium constants are given below:

[H  ] [HX  ] [H  ] [X 2 ]
K a1  and K a 2 
[H 2 X] [HX  ]

Here, K a1 and K a 2 are called the first and second ionization constants.
K a1  K a 2

7.8.7 Factors Affecting Acid Strength :

* When the strength of H–A bond decreases. As the size of A increases down the group, H–A bond strength decreases and
so the acid strength increases.
Size increases

HF << HCl << HBr << HI

Acid strength increases

* In a period, as the electronegativity of A increases, the strength of the acid increases.
Electronegativity of A increases

CH4 < NH3 < H2O < HF

Acid strength increases

7.8.8 Common ion Effect :

* If we consider ionisation of a weak electrolyte say, CH3COOH, it ionises as :
CH3COOH CH3COO– + H+
 CH3COO   H  
  
 CH3COOH
Ka =

* Suppose some how CH3COO– ions are added to the solution to increase CH3COO– ions concentration since mathematical
calculation will tend to change itself to change that eq. constant, electrolyte (CH3COOH) will do same thing in order to keep
Ka constant because it has to be a constant it will reduce its ionisation thus [CH3COOH] will increase, [H+] will decrease and
Ka will remain constant.
* This is called Common ion Effect that if in a solution of weak electrolyte a solution of strong electrolyte with one of its
common ion is added ionisation of weak electrolyte is suppressed.

Applications of Common ion effect :

* H2S is used in presence of HCl as a group reagent for the analysis of second group. HNO3 cannot be used because it
oxidised H2S to sulphur.
* NH4OH and NH4Cl are used as group reagent for the analysis of third group.
* Purification of common salt by passing HCl gas in a saturated solution of NaCl.
* Soap is precipitated from its solution by adding some NaCl.

7.8.9 Hydrolysis of Salts and the pH of their Solutions

* Hydrolysis of salt of weak acid and strong base [CH3COONa, HCOONa]
Result : (a) Solution will be basic (b) Hydrolysis is anionic.
(c) pH of solution is > 7. (d) Red litmus change in to blue litmus.

STUDYMATERIAL: XI CHEMISTRY 13 EQUILIBRIUM

 * Hydrolysis of salt of a strong acid and a weak :
Result : (a) Hydrolysis is cataionic (b) Nature of solution is acidic.
(c) pH of solution is less than 7. (d) Blue litmus change into red litmus.
* Hydrolysis of salt of a weak acid and a weak base [CH3COONH4, AgCN]
1 1
pH = 7 + pKa – pKb
2 2
Conclusions :
Condition Behaviour pH Hydrolysis
of solution
Kb > Ka basic >7 anionic
Ka > Kb acidic <7 cataionic
Ka = Kb neutral =7 neutral

Example 18 :
The pKa of acetic acid and pKb of ammonium hydroxide are 4.76 and 4.75 respectively. Calculate the pH of ammonium acetate
solution.
1 1 1
Sol. pH = 7 + [pKa – pKb] = 7 + [4.76 – 4.75] = 7 + [0.01] = 7 + 0.005 = 7.005
2 2 2

7.9 BUFFER SOLUTION

A solution that resists change in pH upon addition of small amount of strong acid and strong base is called Buffer Solution.
Capacity of a solution to resist alteration in its pH value is known as buffer capacity.

7.9.1 Salient features of buffer solutions :

* Its pH does not change on standing for long.
* Its pH is slightly changed by the addition of small amount of acid & base.
* It has definite pH.
* It has reverse acidity or alkalinity.

7.9.2 Types of buffer solution

* Simple buffers :
(a) A salt of weak acid & weak base in water example CH3COONH4, NH4CN
(b) Proteins & Amino acids.
(c) A mixture of an acid salt & normal salt of a poly basic acid example Na2HPO4 + Na3PO4
* Mixed buffers : These are of two types
(a) Acidic buffer mixtures : Solution of a weak acid and its salt with strong base is acid buffer.
e.g. : NaHCO3 + H2CO3, CH3COOH + CH3COONa, Boric acid (H3BO3) + Borax (Na2B4O7)
Salt 
 
pH = pKa + log Acid . This equation is called Handerson equations.

(b) Basic buffer mixture : A weak base with it's salt with strong acid.
e.g. : NH4OH + NH4Cl, glycine + Glycine Hydrochloride
Salt 
 
pOH = pKb + log Base

7.9.3 Application of buffer solutions

* Qualitative analysis of mixture
* Quantitative analysis or estimations
* Industrial process such as manufacture of paper, dyes, inks, paint, drugs etc.
* Digestion of food
* Preservation of foods & Fruits
* Agriculture & Dairy products preservation.

STUDYMATERIAL: XI CHEMISTRY 14 EQUILIBRIUM

Example 19 :
50 mL of 0.1 M NaOH is added to 75 mL of 0.1 M NH4Cl to make a basic buffer. If pKa of NH4+ is 9.26, Calculate pH.
[salt]
Sol. Using Handerson equation for basic buffer pOH = pKb + log
[base]

 For NH4OH, (pK a )  + (pK b ) NH4OH = 14

NH 4

 (pK b ) NH4OH = 14– 9.26 = 4.74

NH4Cl + NaOH  NH4OH + NaCl
t=0 7.5 5
t=t 2.5 – 5 5
2.5
 pOH = 4.74 + log = 4.44  pH = 14 – 4.44 = 9.56
5

7.10 SOLUBILITY EQUILIBRIA OF SPARINGLY SOLUBLE SALTS

Solubility : At a constant temperature the mass of a solute present in 1 litre of solvent in its saturated solution is called its
Solubility.
Number of moles
Solubility =
Litres of thesolution
For a salt to be able to dissolve in a particular solvent its solvation enthalpy must be greater than its lattice enthalpy so that the
latter may be overcome by former. Each salt has its characteristic solubility which depends on temperature. We classify salts on
the basis of their solubility in the following three categories.

Category I Soluble Solubility > 0.1M

Category II Slightly soluble 0.01M < Solubility < 0.1M
Category III Sparingly soluble Solubility < 0.01M

7.10.1Solubility Product :
* Solubility product of a sparingly soluble electrolyte is equal to the product of ionic concentrations in a saturated solution at
a given temperature.
* Ionisation of compound AxBy may be shown as
AxBy xAy+ + yBx– ; Ksp = [Ay+]x[Bx–]y
* Let solubility of compound AxBy is S mol lit–1 equilibrium
AxBy xAy+ + yBx–
S xS yS
Ksp = (xS)x(yS)y
Ksp = xxyy Sx+y
* Ksp increases with increase in temperature.
* Consider AB  A+  B–
(a) In a saturated solution Ksp = [A+][B–]
(b) In an unsaturated solution of AB, Ksp > [A+][B–] i.e. more solute can be dissolved.
(c) In a super saturated solution Ksp < [A+] [B–] i.e precipitation will start to occur.

Example 20 :
If the solubility product of BaSO4 is 1.44 × 10–12 then find out the solubility of SO4–2.
Sol. BaSO4 Ba+2 + SO4–2

S  Ksp  1.44  1012 = 1.2 × 10–6

STUDYMATERIAL: XI CHEMISTRY 15 EQUILIBRIUM

Example 21 :
A 100.0 mL sample is removed from a water solution saturated with CaSO4 at 25°C. The water is completely evaporated from the
sample and a deposit of 0.24 g CaSO4 is obtained. What is Ksp for CaSO4 at 25°C ?
Sol. CaSO4(s)  Ca2+ (aq) + SO42– (aq), Ksp = ?,
Data shows that the solubility of CaSO4 is 0.24 g per 100 mL.
0.24 1000
 [CaSO4] =  mol L1  0.01765 M [Ca2+] = [SO42–] = 0.01765 M
100 136
 Ksp = [Ca2+] [SO42–] = (0.01765)2 = 3.115  10–4.

Example 22 :
The solubility product of lead iodide is 1.4 × 10–8. Calculate its molar solubility in 0.1 M KI solution.
Sol. Let the solubility of PbI2 be s. Then,
PbI2  Pb2+ + 2I–
s s 2s
Potassium iodide is a strong electrolyte and is completely ionised. It shall provide I– ion concentration = 0.1 M.
[Pb2+] = s
[I–] = (2s + 0.1) M
Ksp = [Pb2+][I–]2= s × (2s + 0.1)2 = s × (4s2 + 0.01 + 0.4s) = 4s3 + 0.01s + 0.4s2
1.4  108
Neglecting s3 and s2, 1.4 × 10–8 = 0.01s or s = = 1.4 × 10–6 mol L–1
0.01

7.10.2 Common Ion Effect on Solubility of Ionic Salts :

* Under equilibrium condition, Ksp = Qsp
* The solubility of salts of weak acids like phosphates increases at lower pH.
* If we take a saturated solution of sodium chloride and pass HCl gas through it, then sodium chloride is precipitated due to
increased concentration (activity) of chloride ion available from the dissociation of HCl. Sodium chloride thus obtained is of
very high purity and we can get rid of impurities like sodium and magnesium sulphates.

Example 23 :
Consider a saturated solution of CaCl2 at equilibrium with excess CaCl2(s). The solubility reaction follows :
CaCl2 (s) Ca2+ (aq) + 2Cl– (aq) ; H°rxn = + 585 kJ
How do the following changes affect the amount of dissolved CaCl2 :
(a) More CaCl2 (s) is added
(b) Some NaCl is dissolved in the solution
(c) Some NaNO3 is dissolved in the solution
(d) Some pure water is added
(e) The solution is heated.
Sol. According to Le Chaterlier’s principle, the system will respond in the direction that reduces the amount of change. It will only do
so, however, if an appropriate response exists. Changes in quantities of substances must be analyzed for their effect, if any, on
the value of Q. If Q becomes smaller, the reaction will proceed to the right, and more CaCl2 will dissolved. If Q becomes larger, the
reaction will proceed to the left, and CaCl2 will precipitate.
(a) More CaCl2 (s) is added. Because Q = [Ca2+] [Cl–]2, adding CaCl2 (s) does not change Q. The system remains at equilibrium.
There is no effect on the amount of dissolved CaCl2.
(b) Some NaCl is dissolved in the solution. This change increases [Cl–], making Q > Keq. The reaction proceeds to the left, and
some CaCl2 precipitates.
(c) Some NaNO3 is dissolved in the solution. There is no effect on Q, so there is no effect on the amount of dissolved CaCl2.
(d) Some pure water is added. Adding water dilutes the solution and lowers [Ca2+] and [Cl–]. Because Q is now less than Keq, the
reaction proceeds to the right. More CaCl2 dissolves.
(e) The solution is heated. Because the solubility reaction is endothermic (H° is positive), Keq increases as T increases. More
CaCl2 dissolves.

STUDYMATERIAL: XI CHEMISTRY 16 EQUILIBRIUM

 ADDITIONAL EXAMPLES
Example 1 :
Find out the value of KC for each of the following equilibria from the value of Kp
(a) 2NOCl(g) 
 2NO(g) + Cl (g) K = 1.8 × 10–2 at 500 K
2 p
(b) CaCO3(s) 
 CaO(s) + CO (g) K = 167 at 1073 K.
2 p
Sol. We know, Kc = Kp . (RT)–n ; where, n = ngaseous (product) – ngaseous (Reactant)
We know, R = 0.082 L atm mol–1 K–1.
(a) For this reaction, n = (2 + 1) – (2) = + 1
So Kc = Kp . (RT)–1 = 1.8 × 10–2 × (0.082 × 500)–1 =4.4 × 10–4
(b) For this reaction, n = (1 + 0) – 0 = 1
So Kc = Kp . (RT)–n = 167 × (0.082 × 1073)–1 = 1.90

Example 2 :
For the following equilibrium, Kc = 6.3 × 1014 at 1000 K
NO(g) + O3(g) 
 NO (g) + O (g)
2 2
Both the forward and reverse reactions in the equilibrium are elementary bimolecular reactions. What is Kc for the reverse
reaction?
Sol. The equilibrium constant for the reverse reaction is given by the expression,
1 1
K'c =  = 1.59 × 10–15
K c 6.3  1014

Example 3 :
A mixture of 1.57 mol of N2, 1.92 mol of H2 and 8.13 mol of NH3 is introduced into a 20 L reaction vessel at 500 K. At this
temperature, the equilibrium constant Kc for the reaction N2(g) + 3H2(g) 
 2NH (g) is 1.7 × 102. Is the reaction mixture at
3
equilibrium ? If not, what is the direction of the net reaction ?
Sol. The reactions N2(g) + 3H2(g) 
 2NH3(g)
Amount : 1.57 mol 1.92 mol 8.13 mol
1.57 mol 1.92 mol 8.13 mol
Concentration : 20 L 20 L ; Kc = 1.7 × 10
2
20L
The reaction quotient is

[NH3 ]2 (8.13 / 20 mol L1 )2 (0.406)2

Qc = = or Qc = L2 mol2 = 2.38 × 103 L2 mol–2
[N 2 ] [H 2 ]3 1.57 / 20 mol L 1
 (1.92 / 20 mol L )
1 3
(0.078)  (0.096)3
Since the value of Qc is much higher than the value of the equilibrium constant, the reaction mixture is not at equilibrium. The
direction of the net reaction is in the backward direction.

Example 4 :
Hydrogen gas is obtained from natural gas by partial oxidation with steam as per the following endothermic reaction.
CH4(g) + H2O(g)  CO(g) + 3H (g)
2
(a) Write an expression for Kp for the above reaction.
(b) How will the value of Kp and composition of the equilibrium mixture be affected by
(i) Increasing the pressure (ii) Increasing the temperature (iii) Using a catalyst

pCO  p3H 2
Sol. (a) Kp = p
CH 4  p H 2O(g)

(b) (i) This reaction proceeds with an increase in volume. So, an increase in pressure will shift the equilibrium in the backward
direction. Therefore, the reaction mixture will now contain lesser amounts of CO and H2 and larger amounts of CH4 and
H2O(g). As a result, Kp value for the reaction will decrease.

STUDYMATERIAL: XI CHEMISTRY 17 EQUILIBRIUM

 (ii) The reaction is an endothermic reaction. So, an increase in temperature will shift the equilibrium in the forward direction.
Therefore, the reaction mixture will now contain larger amounts of the products, (CO and H2), and lesser amounts of the
reactants (CH4 and H2O(g)). The value of KP will increase.
(iii) A catalyst has no effect on the position of the equilibrium. So, the composition of the reaction mixture and the value of
KP will remain unchanged.

Example 5 :
The ionisation constants of HF, HCOOH and HCN at 298 K are 6.8 × 10–4, 1.8 × 10–4 and 4.8 × 10–4 respectively. Calculate the
ionisation constants of the corresponding conjugate base.
Sol. For a conjugate acid base pair, Ka . Kb = Kw ; At 298 K, Kw = 1.0 × 10–14. So,

Acid Ka Conjugate base Kb = Kw / Ka

1  10 14
HF 6.8 × 10–4 F– = 1.47 × 10–11
6.8  104
1 1014
HCOOH 1.8 × 10–4 HCOO– = 5.55 × 10–11
1.8  104
1 10 14
HCN 4.8 × 10–4 CN– = 2.08 × 10–11
4.8  10 4

Example 6 :
Calculate [H+] or [OH–] as required for each of the following solutions at 25°C, and state wheter the solution is neutral, acidic, or
basic. (a) 1.0 × 10–5 M OH– (b) 10.0 M H+
Sol. (a) Kw = [H ] [OH ] = 1.0 × 10 .
+ – –14

1.0  1014 1.0  1014

Since [OH–] is 1.0 × 10–5 M, solving for [H+] gives [H ]    1.0  109 M


[OH ] 1.0  10 5

Since [OH–] > [H+], the solution is basic.

1.0  1014 1.0  1014
(b) Solving for [OH–] gives [OH  ]    1.0  1015 M . Since [H+] > [OH–], the solution is acidic.
[H  ] 10.0
Example 7 :
Ionic product of water at 310 K is 2.7 × 10–14. What is the neutral pH of water at this temperature ?
Sol. Water ionises as follows : H2O 
 H+ + OH–
As per definition, Kw = [H ] [OH–] = [H+]2
+ ; At 310 K, 2.7 × 10–14 = [H+]2
This gives, [H ] = (2.7 × 10 ) = 1.64 × 10 . So, pH = log [H+] = log (1.64 × 10–7) = 6.78
+ –14 1/2 –7

Example 8 :
The pH of 0.005 M codeine (C18H21NO3) solution is 9.95. Calculate its ionization constant and pKb.
Kw 1 1014
Sol. pH = 9.95 ; So [H+] = 1.12 × 10–10 or [OH–] = = = 8.93 × 10–5
[H  ] 1.12 1010

[OH  ]2 (8.93  105 ) 2

Then , Kb = = = 1.59 × 10–6. Then, pKb = – log Kb = – log (1.59 × 10–6) = 5.8
C 0.005

Example 9 :
Equal volumes of 0.002 M solutions of sodium iodate and copper chlorate are mixed together. Will it lead to precipitation of
copper iodate ? For copper iodate, Ksp = 7.4 × 10–8.
Sol. When equal volumes of the 0.002 M solutions of sodium iodate and copper sulphate are mixed, their effective concentration in
the mixture becomes 0.001 M.
Thus in the solution, [Iodate ion] = [IO3–] = 0.001 M ; [Copper ion] = [Cu2+] = 0.001 M
Then, the ionic product of Cu2+ and IO3– ions in the solution relative to Cu(IO3)2 is given by,
Ionic product in solution = [Cu2+] [IO3–]2 = (0.001) × (0.001)2 = 4 × 10–9. But Ksp (Cu(IO3)2) = 7.4 × 10–8.
Since the ionic product in the solution relative to Cu(IO3)2 is less than the Ksp for copper iodate, no precipitation will occur in the
solution.
STUDYMATERIAL: XI CHEMISTRY 18 EQUILIBRIUM