Chapter 7 Equilibrium in Brief

Chapter 7
Equilibrium
Chapter Contents
z Physical Equilibrium z Reversible processes : Reaction in which the products of the reaction
can react with one another under same conditions of the reaction to give
z Equilibrium in Chemical back the reactants e.g. formation of NH3, HI, SO3, etc. do not go to
Process completion.
z Homogeneous Equilibria z Irreversible processes : Those in which the products formed do not
react to give back the reactants e.g. 2KClO3  2KCl + 3O2. Such
z Heterogeneous Equilibria
processes go to completion e.g. precipitation, the reactions involving
z Applications of Equilibrium evolution of gases, etc.
Constant z Types of Equilibria
z Relationship between (1) Physical equilibrium e.g., H2O(l) H2O(g)
Equilibrium constant (K), (2) Chemical equilibrium e.g., PCl5(g) PCl3(g) + Cl2(g)
Reaction Quotient (Q) and
Gibbs Energy (G) (3) Ionic equilibrium e.g., CH3COOH(aq.) CH3COO–(aq.) + H+(aq.)
z Ionic Equilibria
PHYSICAL EQUILIBRIUM
z Ionization Constants of Weak
Acids and Weak Bases Process Property becoming
constant at equilibrium
z Common ion effect in the
ionisation of Acids and Bases Solid Liquid Melting point at constant
e.g., H2O(s) H2O(l) pressure
z Hydrolysis of Salts and the
pH of their Solution Liquid Vapour Vapour pressure (e.g., pH2O)
z Buffer Solution e.g., H2O() H2O(g) at constant temperature
z Solubility of Sparingly Soluble Solute (s) Solute (solution) Concentration of the solute
Salts e.g., Sugar(s) Sugar (solution) in the solution at the given
temperature
 Gas(aq) 
Gas(g) Gas(aq)  Gas(g)  at the given
 
e.g., CO2(g) CO2(aq) temperature, e.g.,
 CO2 (aq) 
 CO (g)  at the given
 2 
temperature
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2 Equilibrium NEET
General Characteristics of Equilibria involving Physical processes

(i) At equilibrium, some observable property of the system becomes constant.
(ii) Equilibria involving gases can be attained only in closed vessels.
(iii) Equilibrium is dynamic in nature i.e., there are two opposing processes taking place at equal rates.
(iv) At equilibrium, the concentrations of the different substances become constant at constant temperature.
(v) At equilibrium, the ratio of the species present in two different phases is constant at a constant
temperature.
For example,
For CO2(g) CO2(aq.)
[CO2 (aq)]
Ratio of = Constant
[CO2 (g)]
This constant is known as equilibrium constant.

(vi) The magnitude of the equilibrium constant represents the extent to which the process proceeds before
equilibrium is attained.
EQUILIBRIUM IN CHEMICAL PROCESS

Law of chemical equilibrium
“The rate at which a substance reacts is proportional to its active mass and the rate of a chemical reaction
is proportional to the product of the active masses of the reacting substances”. Active mass means molar
concentration i.e., the number of gram moles of the solute per unit volume. It is expressed by enclosing the
formula of the substance in square brackets. For example, [A] represents the active mass of the substance
A. The active mass of solids is taken as one.
Chemical Equilibrium
At same given set of condition, the rate at which products are produced from reactants equals the rate at which
reactants are produced from products is known as equilibrium of reaction.
e.g., aA + bB cC + dD
kf
(i) aA + bB  cC + dD …(1)
kb
(ii) cC + dD  aA + bB …(2)
Rate of forward reaction (1) 

rf  k f [A]a [B]b 
According to law of mass action
Rate of backward reaction (2)
c d
rb  k b [C] [D] 
At equilibrium rf = rb
kf [C]c [D]d
 
k b [A]a [B]b
kf [C]c [D]d
K 
kb [A]a [B]b
where K = equilibrium constant, kf and kb are rate constants for forward and backward reaction
NEET Equilibrium 3
[Pr oduct]
 K
[Reactant]
[HI]2
e.g., H2(g) + I2(g) 2HI(g); K 
[H2 ][I2 ]
Note : Solid and liquid (in excess) entities are not taken in this equation as their activity is taken as 1.
Characteristics of equilibrium constant

(i) The equilibrium constant does not depend upon initial concentration and has a definite value for every
chemical reaction at a given temperature.
Van't Hoff Equation
It gives variation of K with temperature.
K2 H  T2  T1 
log   
K1 2.303R  T1T2 
R is gas constant, H is enthalpy change, K1 and K 2 are equilibrium constants at temperatures

T1 and T2 respectively.
(ii) If the reaction is reversed, the value of equilibrium constant is reciprocated.
Example :
For reaction, H2(g) + I2(g) 2HI(g)
Kc = 50
If reaction is reversed
2HI(g) H2(g) + I2(g)
Now, the value of the equilibrium constant will be
1 [H ][I ] 1
Kc   2 22   0.02
Kc [HI] 50
(iii) If the reaction is multiplied by a factor (n) then the value of equilibrium constant becomes Kc = (Kc)n
Example :

A  B
2C ; Keq = Kc

2A  2B
4C ; Keq = Kc
Kc = (Kc)2
or

A  B
2C ; Keq = Kc
1 1
A  B
C ; Keq = Kc
2 2
Kc = (Kc)1/2
4 Equilibrium NEET
(iv) The pure solids and liquids are not considered for calculation of Kc because they have constant
concentration, if one of the reactant or product is gas.
(v) If any chemical reaction is completed in more than one step, then equilibrium constant for overall reaction
is equal to the product of equilibrium constant of all steps.
Example :
Step 1 : N2 + O2 2NO ; K1
Step 2 : 2NO + O2 2NO2 ; K2
N2 + 2O2 2NO2 Overall reaction; K

Here, K1 × K2 = K
[NO]2 [NO2 ]2 [NO2 ]2

  K
[N2 ][O2 ] [NO]2 [O2 ] [N2 ][O2 ]2
HOMOGENEOUS EQUILIBRIA
“When in an equilibrium reaction, all the reactants and the products are present in the same phase (i.e.,
gaseous or liquid) it is called a homogeneous equilibrium.”
For example, N2(g) + 3H2(g) 2NH3(g)
In the gaseous reaction, reactants and products are in the homogeneous phase. Similarly, for the reactions,
CH3COOC2H5(aq) + H2O (l) CH3COOH (aq) + C2H5OH (aq)
and, Fe3+(aq) + SCN–(aq) [Fe(SCN)]2+(aq)

all the reactants and products are in same phase. We shall now consider them in equilibrium constant for
some homogeneous reactions.
HETEROGENEOUS EQUILIBRIA
“When in an equilibrium reaction, the reactants and the products are present in two or more than two phases,
it is called a heterogeneous equilibrium.”
The equilibrium between water vapour and liquid water in a closed container is an example of heterogeneous
equilibrium.
H2O(l) H2O(g)
Let us take thermal dissociation of calcium carbonate which is an interesting and important example of
heterogeneous chemical equilibrium.


CaCO3(s)
CaO(s) + CO2(g)
On the basis of the stoichiometric equation, we can write,
[CaO(s)][CO2 (g)]
Kc 
[CaCO3 (s)]
Since [CaCO3(s)] and [CaO(s)] are both constant, therefore modified equilibrium constant for the thermal
decomposition of calcium carbonate will be
Kc = [CO2(g)] or Kp = pCO

2
NEET Equilibrium 5
Relation between Kp and Kc
Kp and Kc for same reaction are related as;
ng
K p  K c (RT)
ng = Number of moles of gaseous products – number of moles of gaseous reactants
Units of Equilibrium Constant

The units of equilibrium constant (Kc) can be determined by expressing the molar concentration in terms of
mol L–1. Similarly, the units of Kp can be expressed in terms of partial pressures as Pa, kPa, bar or
atmosphere.
Example 1 : Write the unit of equilibrium constant (Kc) for the given reaction.
BaCO3(s) BaO(s) + CO2(g)
Solution : Kc = [CO2] i.e. mol L–1
Example 2 : Write the relation between Kp and Kc for the following reactions.
(i) N2(g) + 3H2(g) 2NH3(g)
(ii) 2H2O(g) 2H2(g) + O2(g)
Solution : (i) Kp = Kc(RT)–2
(ii) Kp = Kc(RT)1
EXERCISE
1. In a closed system: A(s) 2B(g) + 3C(g) if the partial pressure of C is doubled then partial pressure of
B will be
(1) Twice the original pressure
(2) Half of its original pressure
1
(3) times the original pressure
2 2
(4) 2 2 times its original pressure
2. Sulphide ion reacts with solid sulphur
S2– (aq)  S(s) S2–

2 (aq) ; K1 = 10
S2– (aq)  2S(s) S32– (aq) ; K2 = 130
The equilibrium constant for the formation of S32–(aq) from S22–(aq) and sulphur is
(1) 10
(2) 13
(3) 130
(4) 1300
6 Equilibrium NEET
3. For the reaction, CaCO3(s) CaO(s) + CO2(g), Kp is equal to

(1) K c (2) KcRT
(3) Kc(RT)2 (4) Kc(RT)–1
4. For the system 3A + 2B C, the expression for equilibrium constant K is
3 A ]  [2B]  A ]3  [B]
(1) (2)
[C] [ C]
[ C] [C]
(3) 3 2 (4)
 A ]  [B] 3 A ]  [2B]
5. A state of equilibrium is reached when
(1) The rate of forward reaction is greater than the rate of the reverse reaction
(2) The concentration of the products and reactants are equal
(3) More product is present than reactant
(4) The concentration of the products and reactants have reached constant value
6. In which of the following cases, the reaction goes farthest to completion?
(1) A B (K = 103) (2) P Q (K = 10–2)
(3) A + B C + D (K = 10) (4) X + Y XY2 (K = 10–1)
7. For the reaction A + 3B 2C + D, initial mole of A is twice that of B. If at equilibrium moles of B and C
are equal, then percent of B reacted is
(1) 10% (2) 20%
(3) 40% (4) 60%
8. The equilibrium A(g) + 4B(g) AB4(g) is attained by mixing equal moles of A and B in a one litre vessel.
Then at equilibrium
(1) [A] = [B] (2) [A] > [B]
(3) [A] < [B] (4) [AB4] > [A]
APPLICATIONS OF EQUILIBRIUM CONSTANT

Predicting the Direction of Reaction
Qc or reaction quotient is defined in the same way as equilibrium constant Kc except that the concentration
in Qc are not necessarily equilibrium values.
[Product]
Qc =
[Reactant]
The direction of reaction is predicted as,
z If Qc < Kc, net reaction goes from left to right.
z If Qc > Kc, net reaction goes from right to left.
z If Qc = Kc, no net reaction occurs.
ent Qc
o vem ds
M ar
nt Qc Kc tow brium
Kc
o veme s ili Kc
M ard equ
tow brium
Qc ili
equ
Reactants  Products Reactants  Products
NEET Equilibrium 7
Predict the extent of a reaction

The magnitude of the equilibrium constant gives an idea of the relative amounts of the reactants and the
products.
(i) Large value of the equilibrium constant > 103 shows that forward reaction is favoured i.e., concentration
of products is much larger than that of the reactants at equilibrium e.g., for the reactions
300 K

H2(g) + Br2(g)
2HBr(g); Kc = 5.4 × 1018
1 500 K
H2(g) +
O (g)
H2O(g); Kc = 2.4 × 1047
2 2
This shows that at equilibrium, concentration of the products i.e., HBr and H2O, are very high and hence
the reactions has gone almost to completion.
(ii) Intermediate value of K(10–3 to 103) shows that the concentrations of the reactants and products are
comparable, e.g., for the reaction.
Fe+3(aq) + SCN–(aq) [Fe(SCN)]2+(aq); Kc = 138 at 298 K
H2(g) + I2(g) 2HI(g); Kc = 57.0 at 700 K
(iii) Low value of K(<10–3) shows that backward reaction is favoured i.e., concentration of reactants is much
larger than that of the products i.e., the reaction proceeds to a very small extent, e.g., for the reaction
N2(g) + O2(g) 2NO(g); Kc = 4.8 × 10–31 at 298 K
This shows that at equilibrium, the mixture contains mainly N2 and O2 and very little of NO.
These generalisations may be represented as follows
Negligible Kc Kc Extremely large Kc

–3 3
10 1 10
Reaction hardly Both reactants and Reaction proceeds
proceeds products are present almost to completion
at equilibrium
Fig. : Dependence of extent of reaction on Kc
Calculating equilibrium concentrations

We can calculate the value of equilibrium concentrations of all the reactants and products by knowing the initial
concentrations of reactants through the following steps :
Step-1 : Write the balanced equation for the reaction.
Step-2 : Assume ‘x’ as the amount of the reactant reacted or as the product formed.
Step-3 : Calculate the equilibrium concentration of each reactant and product from the stoichiometry of the
equation.
Step-4 : Write expression for Kc or Kp.
Step-5 : Substitute equilibrium concentrations and calculate ‘x’.
Step-6 : Calculate values of equilibrium concentrations by putting the value of x in the expression of Kc.
8 Equilibrium NEET
For example :
PCl5 PCl3 + Cl2
Initial 1 mol L–1 0 0
At equilibrium 1–x x x
[PCl3 ][Cl2 ]
Kc 
[PCl5 ]
xx x2
 
1 x 1 x
Example 3 : Two moles of PCl5 were heated to 327°C in a closed two litre vessel and when equilibrium was
achieved, PCl5 was found to be 40% dissociated into PCl3 and Cl2. Calculate the equilibrium
constant (Kc ) for the reaction.
n
Solution : PCl5 PCl3 + Cl2 Here concentration of PCl5 =
V
2
1 0 0 = 1
2
1–x x x
x = 40% = 0.4
1 – x = 1 – 0.4 = 0.6
[PCl3 ][Cl2 ]
Kc 
[PCl5 ]
0.4  0.4

0.6
1.6 0.8
 
6 3
 0.267 mole/L
Degree of dissociation and its relation with vapour density

Moles dissociated
z Degree of dissociation () 
Initial moles taken
z % dissociation =  × 100
Dd

(n  1)d
where D = Vapour density before dissociation

d = Vapour density after dissociation
n = Number of moles obtained from one mole of dissociating species
Le Chatelier’s Principle
“When the reaction is already their at equilibrium and if it is subjected to a change of concentration, pressure
or temperature, the equilibrium shifts in the direction that tends to undo the effect of the change”.
Factors influencing Equilibrium Reaction
1. Concentration; 2. Pressure; 3. Inert Gas; 4. Catalyst; 5. Temperature
NEET Equilibrium 9
1. Concentration
(i) If concentration of reactant increased reaction shifts in forward direction.
(ii) If concentration of reactant decreased reaction shifts in backward direction.
(iii) If concentration of product increased reaction shifts in backward direction.
(iv) If concentration of product decreased reaction shifts in forward direction.
2. Pressure : Effect of pressure depends on the ng of reaction
3. Inert Gas : Effect of inert gas is studied by adding it either at constant pressure or at constant volume
at equilibrium.
Inert gas ng  0 ng   ve ng   ve
At constant V No effect No effect No effect
Backward Forward
At constant P No effect    
4. Catalyst : A catalyst increases the speed of both the forward and backward reactions to the same extent
in a reversible reaction. Thus, a catalyst does not alter the concentration of the reactants and products
in a state of equilibrium.
5. Temperature : With increase or decrease in temperature reaction either shifts in forward or backward
direction and it also changes the equilibrium constant.
Endothermic Reaction Exothermic Reaction
(1) Increase in temperature, Increase in temperature,

shifts reaction in forward shifts reaction in backward
direction direction
(2) Decrease in temperature, Decrease in temperature,

shifts reaction in backward shifts reaction in forward
direction direction
(3) Increase in temperature, Increase in temperature,
increase the equilibrium decrease the equilibrium
constant constant
Note : Only temperature factor changes equilibrium constant value and rest only shifts the direction of reaction.
Example 4 : In the reaction A + B C + D, what will happen to the equilibrium if concentration of A is

increased?
Solution : It will shift to the right.
Example 5 : What will be the effect of increased pressure in the following equilibrium reaction?
(i) H2(g) + I2(g) 2HI(g)
(ii) N2(g) + 3H2(g) 2NH3(g)
(iii) N2O4(g) 2NO2(g)

Solution : (i) No effect.
(ii) Will shift to the right.
(iii) Will shift to the left.
10 Equilibrium NEET
RELATIONSHIP BETWEEN EQUILIBRIUM CONSTANT (K), REACTION QUOTIENT (Q) AND

GIBBS ENERGY (G)
 If G = 0; the reaction is in a state of equilibrium.
 If G is negative, the reaction is spontaneous in the forward direction.
The relation between free energy change and reaction quotient (Q) may be given as
G  G  RT lnQ
If the reaction has attained equilibrium under the reaction conditions, then G = 0
G  2.303 RT logK
K  e G /RT
 If G° < 0, then –G°/RT is positive and e–G°/RT > 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.
 If G° > 0, then –G°/RT is negative and e–G°/RT < 1, i.e., 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.
EXERCISE
9. The oxidation of SO2 and O2 to SO3 is an exothermic reaction. The yield of SO3 will be maximum if
(1) Temperature and pressure both are increased (2) Temperature decreased, pressure increased
(3) Temperature increased, pressure constant (4) Temperature and pressure both decreased
10. A + B C + D, Kc for this reaction is 10. If 1, 2, 3, 4 mole/litre of A, B, C and D respectively are present
in a container at 25ºC, the direction of reaction will be
(1) From left to right (2) From right to left
(3) Reaction is at equilibrium (4) Unpredictable
11. The equilibrium constant for the reaction, H2(g) + I2(g) 2HI(g)
is 32 at a given temperature. The equilibrium concentration of I 2 and HI are 0.5 × 10 –3 and
8 × 10–3 M respectively. The equilibrium concentration of H2 is
(1) 1 × 10–3 M (2) 0.5 × 10–3 M
(3) 2 × 10–3 M (4) 4 × 10–3 M
P
12. For the reaction equilibrium, 2NOBr(g) 2NO(g) + Br2(g). If PBr2  at equilibrium and P is total
9
Kp
pressure, the ratio of is equal to
P
1 1
(1) (2)
9 81
1 1
(3) (4)
27 3
NEET Equilibrium 11
13. At temperature T K, PCl5 is 50% dissociated at an equilibrium pressure of 4 atm. At what pressure it would
dissociate to the extent of 80% at the same temperature?
(1) 0.05 atm (2) 0.60 atm
(3) 0.75 atm (4) 2.50 atm
14. For the equilibrium, CH3CH2CH2CH3(g) CH3 –CH–CH 3 (g)
CH3
iso-butane
If the value of KC is 3.0, the percentage by mass of iso-butane in the equilibrium mixture would be
(1) 75% (2) 90%
(3) 30% (4) 60%
Fe2O3
15. In the manufacture of NH3 by Haber’s process involving the reaction. N 2 (g) + 3H 2 (g) 2NH 3 (g);
H = –22.08 kcal. The favourable conditions are
(1) High pressure and low temperature (2) Low pressure and low temperature
(3) High pressure and high temperature (4) Low pressure and high temperature
16. Ice and water are placed in a closed container at a pressure of 1 atm and 273.15 K temperature. If pressure
of the system is increased by 2 atm keeping temperature constant the correct observation would be
(1) The liquid phase disappears completely
(2) The amount of ice increases
(3) The solid phase (ice) disappears completely
(4) Volume of the system increases
17. A cylinder filled with a movable piston contains liquid water in equilibrium with water vapour at 25ºC. Which
one of the following operations results in a decrease in the equilibrium vapour pressure?
(1) Moving piston downward a short distance
(2) Removing a small amount of vapour
(3) Removing a small amount of the liquid water
(4) Dissolving salt in the water
18. Choose the correct statement
(1) Catalyst increases the rate of reaction
(2) Catalyst decreases the time of attainment of equilibrium
(3) Catalyst decreases the activation energy
(4) All are correct
19. If K1 is the equilibrium constant at temperature T1 and K2 is the equilibrium constant at temperature T2, and
if T2 > T1 and reaction is endothermic then
(1) K2 < K1 (2) K2 = K1
(3) K2 > K1 (4) All of these
IONIC EQUILIBRIA
Electrolytes are substances which in the dissolved state or in molten state conduct electricity. In fact they
dissociate into ions which cause conductance. Strong electrolytes are completely ionisable, e.g. HCl, H2SO4,
NaOH, KOH, NaCl, KNO3, HNO3, HI, HClO4, KCl, NaNO3, Na2SO4 etc.
Weak electrolytes : only slightly ionised CH3COOH, NH4OH, NH3,CH3NH2,(CH3)2NH,(CH3)3N etc.
12 Equilibrium NEET
Acid Base Concept :

z Arrhenius concept of Acids & Bases : Acids are substances which dissociate in water to produce H+ ions
while bases give OH– ions.
z Bronsted Lowry concept:
(i) An acid is a substance which can donate proton (H+) while a base is a subtance which can accept a
proton (H+). HCl + NH3 NH4+ + Cl–, CH3COOH + H2O CH3CO O O + H3O+.
(ii) Water is amphoteric. It can donate as well as accept protons.
(iii) Conjugate acid-base pairs are the pairs of substances which differ by one proton e.g. H3O+ and H2O, H2O
and OH○ , NH4+ and NH3, CH3COOH and CH3COO–, HCl and Cl– etc.
(iv) A strong acid has weak conjugate base and a strong base has weak conjugate acid and vice-versa.
+ –
HA ( aq) + H2O(l) H 3O (aq) + A (aq)
Acid Base Acid Base
Conjugate acid-base pairs
z Lewis concept: Acid is a substances which can accept a pair of electrons while a base can donate a pair
of electrons.
Acids: H+,Ag+, Cu2+, BF3, FeCl3, SnCl4, SiF4, CO2, SO2 etc.
.. .. ..
Bases: OH¯, Cl¯, SO42—, CH3COO—, H2 O,
..
NH3 , RNH2 , etc.
–
Acid, HA Base, A
Stronger
HClO4  Strong acids. ClO4–  Very weak bases.
acid
HCl  100% dissociated Cl–  Negligible tendency
H2SO4  in aqueous HSO4–  to be protonated in
 solution. –  aqueous solution.
HNO3  NO3 
H3O+ H2O
HSO4–  SO42– 
H3PO4  H2PO4– 
HNO2  NO2
–

HF  F
– 
 Weak acids.  Weak bases.
CH3CO2H  Exist in solution CH3CO2–  Moderate tendency
H2CO3  as a mixture of HCO3–  to be protonated in
 HA, A–, and H3O +. –  aqueous solution.
H2S  HS 
+
NH4  NH 3 
HCN  CN– 
 
HCO3–  CO32– 
–
H2O OH
–
NH3  Very weak acids. NH 2  Strong bases.
 Negligible tendency  100% protonated in
OH–  O 2–

Weaker H2  to dissociated H–  aqueous solution.
acid
Properties of water : Pure water is always neutral at all temperatures.

z Ionisation constant of water (Kw)
Kw = [H3O+] [OH–]
pKw = – log Kw
[HO] = Kw/[H3O+] or [H3O+] = Kw/[OH]–
Kw depends on the temperature. Kw increase with increase in temperature.
z Degree of ionization of water increase with increase of temperature.
NEET Equilibrium 13
pH Scale (Sorensen in 1909)
The pH is defined as negative logarithm 10 base of the activity (aH ) of hydrogen ion. At low concentration
the activity of hydrogen ion is numerically equal to its molarity which represented by [H+].
pH   log[H ] and pOH   log[OH ]
At 298K :
pH
0 acidic 7 basic 14
Neutral
e.g., pH for 10–3 M HCl is 3.

Note : pH + pOH = pKw i.e. pH + pOH = 14 (at 298K).
Kw changes with temperature and accordingly the pH scale also changes.
Example 6 : The concentration of H+ ion in a sample of soft drink is 3.8 × 10–3 M. What is its pH?
Solution : pH = –log[H+]
= –log [3.8 × 10–3]
= 3 – 0.58 = 2.42
Example 7 : If hydrogen ion concentration in a solution is 1 × 10–5 mole/litre, calculate the concentration of
OH– ion in this solution (Kw = 10–14 mole2 L–2).
Solution : Kw = [H+][OH–] = 10–14
10 14 10 14
[OH–] =   10 9 mol L1

[H ] 10 5
IONIZATION CONSTANTS OF WEAK ACIDS AND WEAK BASES

The dissociation of a weak acid in water can be represented by the equilibrium
HA + H2O H3O+ + A–
Initial concentration c 0 0
Concentration at equilibrium (c – c) c c (Here  is degree of ionisation)
c(1 – )
[H3 O  ][A  ] c  c  2c 2
Ka   
[HA] c(1   ) c(1   )
Hence for,  <<< 1
Ka = 2c
1/2
K 
   a
 c 
  (K a  V)1/2
1
Here, V is the volume of the solution in litres containing 1 mole of the electrolyte, c = .
V
14 Equilibrium NEET
In case of a weak electrolyte, at a given temperature, the degree of ionisation is inversely proportional to the
square root of the molar concentration or directly proportional to square root of the volume of the solution which
contains one mole electrolyte.
This is called Ostwald’s dilution law.
Similarly, the dissociation of a weak base in water can be represented by the equilibrium

 
B  OH
BOH
Concentration at equilibrium c(1 – ) c c
[B  ][OH ]  c   c  2c
Now, K b   
[BOH] c(1   ) 1  
For a weak electrolyte, if  is very small, it can be neglected.
 K b   2c
1/2
Ka Ka
Degree of ionisation for acid () = or and c = [H3O+]
c c
1/2
Kb Kb
Degree of ionisation for base () = or and c = [OH–]
c c
1
For weak acid pH = (pKa  logc)
2
1
For weak base pOH = (pKb  logc)
2
Example 8 : If Ka of a weak acid is 4 × 10–6 and its concentration is 0.1 M. Find pH of solution.
1
Solution : pH = [pKa – logc]
2
1
= [–log4 × 10–6 – log10–1]
2
1
= [–0.6020 + 6 + 1]
2
1
= [7 – 0.602] = 3.199
2
Relation between Ka and Kb of acid-base conjugates pair

Consider the weak acid, HF. Its conjugate base is F–. They dissociate as follows :

 
H F
HF
[H ][F  ]
Ka  ...(i)
[HF]

and F– + H2O
OH– + HF
[OH ][HF]
Kb  ...(ii)
[F ]
Now, K w  K a  K b
pK a  pK b  pK w  14 at 298 K
NEET Equilibrium 15
Example 9 : The dissociation constant of a base MOH is 4 × 10–6, then calculate the dissociation constant
of its conjugate acid.
Solution : Kw = Ka × Kb
10 14
Ka   2.5  10 9
4  10 6
Example 10 : The dissociation constant of 0.01 M CH3COOH is 1.8 × 10–5, then calculate the dissociation
constant of its conjugate base (CH3COO–).
Solution : Kw = Ka × Kb
Kw 10 14
Kb    5.6  10 10
K a 1.8  10 5
Di and Polybasic Acids and Di and Polyacidic Bases

Some acids like sulphuric acid (H2SO4), carbonic acid (H2CO3), oxalic acid (COOH)2, phosphoric acid H3PO4
and some bases like Ca(OH)2, Al(OH)3 etc. contain more than one ionisable proton and hydroxide ion. Such
type of acids and bases are called polybasic or polyprotoic acids and polyacidic bases respectively. They ionise
in steps.
For example, the dibasic acid (H2X) may ionise in two steps as follows :
H2X(aq) H+(aq) + HX–(aq)
HX–(aq) H+(aq) + X–2(aq)
Their ionisation constant, K a1 and K a2 called the 1st and the 2nd ionisation constant respectively, will be given
by the equations.
[H ][HX ] [H ][X2 ]

K a1  and K a2 
[H2 X] [HX ]
The overall equilibrium may be obtained by adding the stepwise dissociation equilibria. Thus, for the above
process, the overall equilibrium will be
H2X(aq) 2H+(aq) + X–2(aq)
[H ]2 [X 2 ]
Ka 
[H2 X]
Therefore, K a  K a  K a
1 2
Similarly, a tribasic acid like H3PO4 has three ionisation constants. The overall ionisation constant (Ka) will
be the product of the ionization constants of the three steps. i.e.,
K a  K a1  K a2  K a3
Similarly, for polybasic acids

K a  K a1  K a2 .....
Similarly, for polyacidic bases
K b  Kb1  K b2  K b3  .....
16 Equilibrium NEET
COMMON ION EFFECT IN THE IONISATION OF ACIDS AND BASES

“The suppression in the dissociation of a weak electrolyte by the addition of a strong electrolyte having a
common ion is called common ion effect”.
For example : Ionisation of acetic acid (CH3COOH) and effect of addition of a small amount of acetate ion
CH3COOH(aq) CH3COO–(aq) + H+(aq)
CH3COONa(aq) CH3COO–(aq) + Na+(aq)

Common ion
Due to the presence of common CH3COO–(aq) ions, the equilibrium will be shifted to the left according to Le
Chatelier’s principle.
Example 11 : The dissociation constant of 0.01 M CH 3COOH is 1.8 × 10 –5 , then calculate CH 3COO –
concentration in 0.1 M HCl solution.
Solution : CH3COOH CH3COO– + H+
HCl Cl– + H+
Common ion
CH3COOH CH3COO– + H+
0.01 0 0
0.01 – x x x
Here x is very small value.
[CH3 COO ][H ]

ka 
[CH3 COOH]
1.8  10 5  0.01
[CH3 COO ]  ([H+] is taken from 0.1 M HCl)
0.1
[CH3COO ] = 1.8 × 10–6 mol/L
–
EXERCISE
20. With increase in temperature, pH of pure water
(1) Increases
(2) Decreases
(3) Remains constant
(4) May increase or decrease
21. The pH of a solution is increased from 3 to 6, its H+ concentration will be
(1) Reduced to half
(2) Doubled
(3) Reduced by 1000 times
(4) Increased by 1000 times
NEET Equilibrium 17
22. Which pair will show common ion effect?
(1) BaCl2 + Ba(NO3)2 (2) NaCl + HCl
(3) NH4OH + NH4Cl (4) NaCN + KCN
23. The compound that is not a Lewis acid
(1) AlCl3 (2) BF3
(3) NF3 (4) SnCl4
24. Fear and excitement generally cause one to breathe rapidly and it results in the decrease of CO2 concentration
in the blood. In what way will it change the pH of the blood?
(1) pH will decreases
(2) pH will increases
(3) pH will adjust to 7
(4) pH will remain unchanged
HYDROLYSIS OF SALTS AND THE pH OF THEIR SOLUTION

Hydrolysis is a process in which a salt reacts with water to form acid and base.

Salt + Water
Acid + Base
Thus, the salt hydrolysis is the reverse of neutralisation reaction. The nature of the solution after hydrolysis
depends upon the relative strengths of the acid and base formed. On this basis, the salts are divided into four
categories.
1. Salts of strong acid and strong bases :
The examples of these salts are NaCl, KNO3, Na2SO4, K2SO4, NaNO3 etc.
In general salts of strong acid and strong base do not undergo hydrolysis. They simply form ions in
solution.
2. Salts of strong acid and weak base :
The salts belonging to this type are NH4NO3, NH4Cl, (NH4)2SO4, CuSO4, AlCl3 etc.
It is known as cationic hydrolysis and proceeds as follows

B+ + H2O
BOH + H+
[BOH][H ]
Now, Kh 
[B ]
For the dissociation of weak base,

B+ + OH–
BOH
[B  ][OH ]
Kb 
[BOH]
Ionic product (Kw) for water is

Kw = [H+][OH–]
K h  K b [BOH][H ] [B ][OH ] 1 Kw

Now,     1 Kh 
Kw 
[B ] [BOH] [H ][OH ] Kb
18 Equilibrium NEET
K

h
B+ + H2O
BOH + H+
Concentration at equilibrium c(1 – h) ch ch
H ][BOH] ch  ch ch2

Now, Kh  
 
[B ] c(1  h) 1  h
Kh = ch2 (1 – h 1 for weak electrolyte)
Kh
h
c
Kw
h
Kb  c
1/2
Kw Kw  c
[H ] = ch = c  
Kb  c Kb
1/2
Kw  c
pH = –log[H+] = –log
Kb
1
pH =  [logKw – logKb + logc]
2
1
pH  7  [pK b  logc] at 298 K
2
The resulting solution after hydrolysis is acidic and its pH will be less than 7.
3. Salt of strong bases and weak acids :
The salts belonging to this type are CH3COONa, Na2CO3, Na3PO4, K2CO3 etc.
It is called anionic hydrolysis and proceeds as follows

A– + H2O
HA + OH–

H+ + A–
HA
[H ][A  ]
Ka 
[HA]
Kh  Ka [HA][OH ] [H ][A  ] 1

Now,     1
Kw [A  ] [HA] [H ][OH ]
Kw
Kh 
Ka
Kh Kw
and h 
c Ka  c
[OH–] = ch
Kw Kw
 [H ]  

[OH ] ch
NEET Equilibrium 19
Kw Ka  c K w  Ka
[H ]   
c Kw c
pH = –log[H+]
K w  Ka
  log
c
1
pH =  [logKw + logKa – logc]
2
1
pH  7  [pK a  logc]
2
It involves anionic hydrolysis. The resulting solution after hydrolysis is basic (pH > 7).
4. Salts of weak acid and weak base :
The salts belonging to this type are CH3COONH4, (NH4)2CO3, Ca3(PO4)2 etc.
It is called cationic as well as anionic hydrolysis and proceeds as follows

B+ + A– + H2O
BOH + HA
Initial concentration c c 0 0
Concentration at equilibrium c(1 – h) c(1 – h) ch ch
Kw
Kh 
K a  Kb
Kw
h  Kh 
Ka  Kb
Dissociation of weak acid
HA H+ + A–
[H ] [A ] K [HA]

 Ka =  [H ] = a 
[HA] [A ]
K a  ch
[H ] 
c(1  h)
[H+] = Ka × h [As (1 – h) = 1]
[H+] = Ka × Kh
1/2
Kw K w  Ka
[H ] = K a  
K a  Kb Kb
1/2
K w  Ka
pH = – log[H+] = – log
Kb
1
pH =  [logKa + logKw – logKb]
2
1
pH  7  [pK a  pK b ]
2
It involves cationic as well as anionic hydrolysis. The nature of the solution or its pH depends upon the
relative strengths of the acid and base that are formed on hydrolysis.
20 Equilibrium NEET
Example 12 : Calculate the degree of hydrolysis of 0.1 M solution of acetate at 298 K.

Given : Ka = 1.8 × 10–5
Kw 1  10 14
Solution : Hydrolysis constant (Kh) =   5.5  10 10
K a 1.8  10 5
Kh 5.5  10 10
Degree of hydrolysis (h) =  = (55 × 10–10)1/2 = 7.42 × 10–5
c 0.1
Example 13 : Calculate the pH of 0.10 M solution of NH4Cl. The dissociation constant (Kb) of NH3 is 1.8 × 10–5.
Solution : NH4Cl is a salt of strong acid and weak base.
1
pH = 7 – [pkb + logc]
2
1
=7– [–log(1.8 × 10–5) + log 0.10]
2
1
=7– (5 – 0.26 – 1) = 5.12
2
Example 14 : The pKa of acetic acid and pKb of ammonium hydroxide are 4.76 and 4.75 respectively. Calculate
the pH of ammonium acetate solution.
Solution : As CH3COONH4 is a salt of weak acid and weak base,
1
pH = 7 + [pKa – pKb]
2
1
=7+ (4.76 – 4.75)
2
= 7 + 0.005 = 7.005
Example 15 : Calculate the percentage hydrolysis of decinormal solution of ammonium acetate given that
Ka = 1.75 × 10–5, Kb = 1.8 × 10–5, Kw = 1 × 10–14.
Solution : Ammonium acetate is a salt of weak acid and weak base
Kw 1 1014
Kh    3.175  105
K a  K b 1.75  105  1.8  105
h  k h  (3.175  10 5 )1/2
h = 5.63 × 10–3
BUFFER SOLUTION
Solutions which resist the change in pH value by the addition of a small amount of an acid or base or the
solvent. Buffers may be acidic or basic. Acidic buffer is made by mixing a weak acid and its salt with a strong
base (CH3COOH + CH3COONa) while a basic buffer is the solution of a weak base and its salts with a strong
acid (NH4OH + NH4Cl). pH of buffers can be determined by using Henderson’s equation e.g. for the acidic
buffer,
NEET Equilibrium 21
Example : CH 3COOH + CH 3COONa, COOH COOK etc.
+
COOH COOK
pH = pK a + log [Salt]/[Acid]
For basic buffer (e.g. : NH4OH + NH4Cl, etc.)
pH = 14 – pKb + log [Base]/[Salt]
[Salt]
or pOH = pKb + log
[Base]
Note : z For preparing the buffer solution of the required pH we select that acid whose pKa is close to the
required pH.
z pH of the buffer solution is not affected by dilution.
z Buffer capacity. It is defined as number of equivalents of acid or base to be added to 1 litre of buffer solution
so as to change its pH by 1.
No. of moles of acid or base added L–1

Buffer capacity = .
change in pH.
z Application of buffer solutions
(i) pH of blood is maintained with the help of buffer (HCO3– and H2CO3). pH of blood is 7.42.
(ii) It is used to precipitate group III radicals as hydroxides.
(iii) It is maintained for manufacture of dyes and drugs.
Example 16 : Calculate the pH of buffer solution formed by mixing 60 g CH3COOH and 82 g CH3COONa (pKa
of CH3COOH is 4.75)
60
Solution : z mol of CH3COOH = 1
60
82
mol of CH3COONa = 1
82
z pH of acid buffer of CH3COOH and CH3COONa is
 CH COONa 
pH  pKa  log  3 
 CH3 COOH 
 1
= 4.75 + log    4.75
 1
SOLUBILITY OF SPARINGLY SOLUBLE SALTS

Solubility Product : Ksp
Different salts dissolve to different extent in a solvent. Some salts are highly soluble while the others dissolve
to smaller extent. The relative solubilities of the salts is compare with the help of a constant known as solubility
product (Ksp).
Solubility product is calculated for sparingly soluble salt.
Solubility product constant is equal to the product of the ionic concentration in the saturated salt solution at
a given temperature.
The solution in which any solid is in equilibrium with it's ions is called as saturated solution.
AB(Solid) AB A   B
unionised
dissolved ions
22 Equilibrium NEET
Since the solution is saturated, the concentration of unionised molecules of the electrolyte is constant at a
particular temperature i.e. [AB] is constant.
 Ksp = [A+] [B–]
where Ksp = solubility product.
For general electrolyte AxBy which is dissociated as
A xB y xA+y + yB–x
 Ksp = [A+y]x [Bx–]y
z Relation between solubility (s) and solubility product (Ksp)
(i) AgBr (s) Ag+ + Br– ; Ksp = [Ag+][Br–]
Ksp = s × s = s2 therefore s = K sp
Where 's' is solubility in mol L–1.
(ii) Ag2CrO4 2Ag+ + CrO42- Ksp = [Ag+]2[CrO42–]
K sp
Ksp = (2s)2 (s) = 4s3 therefore s = 3
4
(iii) Al(OH)3 Al3+ + 3OH–
Ksp = [Al3+][OH¯]3
K sp
Ksp = s (3s)3 = 27 s4 therefore s = 4
27
(iv) Ca3 (PO4)2 3Ca2+ + 2PO43–
K sp
Ksp = [Ca2+]3 [PO43-]2 = (3s)3 (2s)2 = 108s5 therefore s = 5
108
Example 17 : The solubility of AgCl in water at 298 K is 1.06 × 10–5 mole per litre. Calculate its solubility product
at this temperature.
Solution : AgCl(s) Ag+ + Cl–

s s
Ksp = [Ag+][Cl–]
= s × s = s2
= (1.06 × 10–5)2
= 1.12 × 10–10 mol2 L–2
Example 18 : Calculate the solubility product of PbCl2 at a certain temperature if the solubility of PbCl2 is
4.4 g/L at the same temperature. (Pb = 207, Cl = 35.5)
Solution : Molar concentration of PbCl2 = 1.6 × 10–2 M
4.4
[Concentration of PbCl2 = 4.4 g/L = = 1.6 × 10–2 mol/L]
278
PbCl2 Pb+2 + 2Cl–
s 2s
Ksp = [Pb+2][Cl–]2
= s × (2s)2 = 4s3
= (1.6 × 10–2)3 × 4 = 1.63 × 10–5
NEET Equilibrium 23
Example 19 : Calculate the solubility of A2X3 in pure water, assuming that neither kind of ion reacts with water.
The solubility product of A2X3, ksp = 1.1 × 10–23.
Solution :

2A+3 + 3X–2
A2X3
2s 3s
Ksp = [A+3]2 [X–2]3
(2s)2 × (3s)3
= 4s2 × 27s3
= 108s5 = 1.1 × 10–23
1/5 1/5
K sp  1.1 1023 
s    105 mol L1
108  108 
Example 20 : Give reason why BaSO4 will precipitate out when equal volumes of 2 × 10–3 M BaCl2 solution and
2 × 10–4 M Na2SO4 solution are mixed. Given that the solubility product of BaSO4 is 1 × 10–10.
Solution : BaCl2 and Na2SO4 are ionises completely in the solution
BaCl2  Ba+2 + 2Cl–
[Ba+2] = [BaCl2] = 2 × 10–3 M
Na2SO4  2Na+ + SO4–2
[Na2SO4] = [SO4–2] = 2 × 10–4 M
Equal volumes of the two solutions are mixed together, therefore, the concentration of Ba+2 ions
and SO4–2 ions after mixing will be
2  10 3
[Ba+2] =  10 3 M
2
2  10 4
and [SO4–2] =  10 4 M
2
 Ionic product of BaSO4 = [Ba+2][SO4–2] = 10–7 M
Here, ionic product of BaSO4 is greater than solubility product value. Hence, a precipitate of BaSO4
will be formed.
Example 21 : Two sparingly soluble salts AB and xy2 have the same solubility product. Which salt will be more
soluble?
Solution : Let the solubility of AB = s1 mol L–1
The solubility of xy2 = s2 mol L–1
AB A+ + B–
s1 s1
Ksp = [A+] [B–]
Ksp = s12
s1  (K sp )1/2
xy2 x+2 + 2y–1

s2 2s2
Ksp = [x+2] [2y–]2
= 4s23
1/3
 K sp 
s2   
 4 
Obviously s2 > s1 (as Ksp have values with negative power of 10). Hence, salt xy2 is more soluble.
24 Equilibrium NEET
Example 22 : Calculate solubility of AgCl in 0.1 M NaCl at 25°C if its solubility product at same temperature
is 2.0 × 10–10.
Solution : In presence of common ion
K sp 2.0  1010
s   2.0  109 mol L1
Concentration of common ion 0.1
Example 23 : What is the minimum concentration of Ba+2 ions required in order to initiate the precipitation of
BaSO4 from a solution containing 0.002 mol L–1 of SO4–2 ions? (Given Ksp for BaSO4 = 1.4 ×
10–10)
Solution : If ionic product of [Ba+2] [SO 4–2 ] is greater than Ksp for BaSO4, then the precipitation occur.
[Ba 2 ]  (2  10 3 )  1.4  10 10
[Ba 2 ]  0.7  10 7 mol L1
Thus, minimum concentration of Ba+2 ions required for the precipitation of BaSO4 is 0.7 × 10–7 M.
z Criteria of Precipitation of an Electrolyte

(1) When IP < Ksp then solution is unsaturated in which more solute can be dissolved.
(2) When IP = Ksp then solution is saturated in which no more solute can be dissolved.
(3) When IP > Ksp then solution is supersaturated and precipitation takes place.
[IP = Ionic product; Ksp = Solubility product]
Common Ion Effect on Solubility of Ionic Salts

The common ion effect helps in purification of an impure sample of NaCl (common salt) containing the impurities
of soluble salts. A saturated solution of the impure sample is first prepared and is then transferred to another
container. HCl(g) is now passed through the solution with the help of a pipe, Cl– ions will act as common
ion.
NaCl(s) Na+(aq) + Cl–(aq)

(Saturated
solution)
HCl(aq) H+(aq) + Cl–(aq)

Common ion
As a result, pure sodium chloride will get precipitated from the solution leaving behind the impurities in the solution.
K sp  [Na  ][Cl ]
If HCl gas is passed through the saturated solution of NaCl, Cl– ion concentration will increase so that
I.P. > Ksp. In order that I.P. may become equal to Ksp, equilibrium will shift in the backward direction and
the concepts of solubility product and common ion effect combined together play an important role in the
inorganic quantitative analysis. For example,
Precipitation of Hydroxides of group-III

NEET Equilibrium 25
The radicals of group-III (Fe+3, Cr+3, Al+3) are precipitated as their hydroxides by the addition of NH4OH in
excess. But before this, solid NH4Cl is added. This is necessary as otherwise the radicals of group-IV may
precipitate as hydroxides.
NH4OH NH4+ + OH–
NH4Cl NH4+ + Cl–

Common
ion
By the addition of NH4Cl, the dissociation of NH4OH is further suppressed and [OH–] concentration becomes
low. But this low concentration of [OH–] ions is sufficient to precipitate the radical of 3rd group (Ksp of their
hydroxide being low) and not the radicals of group IV. So, NH4Cl is added to prevent the precipitation of
radicals of group IV as their hydroxides.
z Phenolphthalein is suitable indicator for titration of strong base and weak acid because phenolphthalein is
a weak organic acid. e.g. NaOH and oxalic acid titration, it is suitable.
z Methyl orange is a weak organic base therefore, it is used for titration of strong acid and weak base
e.g. HCl and NH4OH titration.
EXERCISE
25. For a MX2 type salt if Ksp is solubility product, then solubility will be
K sp K sp
(1) s  (2) s  3
2 4
K sp K sp
(3) s  3 (4) s  3
6 8
26. The compound whose 0.1 M solution is basic is

(1) Ammonium acetate (2) Ammonium chloride
(3) Ammonium sulphate (4) Sodium acetate
27. The correct order of increasing solubility of AgCl in
(A) Water (B) 0.1 M NaCl
(C) 0.1 M BaCl2 (D) 0.1 M NH3
is
(1) A < B < C < D (2) B < C < A < D
(3) C < B < D < A (4) C < B < A < D
28. Which of the following increasing order of pH of 0.1 M solution of the compound A HCOONH 4 ,
B CH3COONH4, C CH3COONa, D NH4Cl is correct?
(1) A < D < B < C (2) D < A < C < B
(3) A < D < C < B (4) D < A < B < C
26 Equilibrium NEET
29. Ksp of Mg(OH)2 is 4.0 × 10–12. The number of moles of Mg2+ ions in one litre of its saturated solution in 0.1
M NaOH is
(1) 4.0 × 10–10 (2) 1.0 × 10–4
(3) 2.0 × 10–6 (4) 8.0 × 10–6
30. Which of the following is correct for the solution of the salt of weak acid & weak base?
1 1
(1) pH =
2
pK w  pKa – pKb  (2) pH =
2
pK w – pK a – pKb 
1 1
(3) pH =
2
pK w  pK a  pKb  (4) pH =
2
pK w  pK a  pKb 

nt
me nment
sigAnssig
Assignment
As
Assignment
4. Ammonium carbamate decomposes as
SECTION - A
NCERT Based MCQs

NH2COONH4(s) 2NH3(g) + CO2(g)
For this reaction, KP = 108 × 10–6 atm3. If we start
1.

For a chemical reaction of the type A
B, with 1 mole of the compound, the total pressure at

equilibrium would be [NCERT Pg. 203, 204]
K 1 = 3.0 and B
C, K 2 = 0.03, then
(1) 0.058 atm (2) 0.048 atm

equilibrium constant for the reaction 2C
2A
(3) 0.09 atm (4) 0.03 atm
is (K1 and K2 are equilibrium constant)
5. In a reversible reaction, two substances are in
[NCERT Pg. 201]
equilibrium. If the concentration of one of them is
reduced to half, then the equilibrium constant will
1
(1)
81 104 [NCERT Pg. 205]
(1) Reduce to half of its initial value
(2) 81 × 104
(2) Become twice of its initial value
1
(3) (3) Remain same
9  104
(4) Reduce to one-fourth of its initial value
(4) 9 × 104
6. Inert gas has been added to the following
2. Which of the following values of equilibrium
equilibrium system at constant volume
constant predict almost completion of the reaction?
[NCERT Pg. 205]

SO2(g) + 1/2 O2(g)
SO3(g)
(1) K = 10–2 To which direction will the equilibrium shift?

(2) K = 100 [NCERT Pg. 211]
(3) K = 10 (1) Forward
(4) K = 104 (2) Backward
3. What will be the total pressure of the gaseous (3) No effect
mixture at equilibrium if AB2 is 20% dissociated
according to the following reaction, (4) Unpredictable

7. Which of the following reactions has minimum
AB2 (g) A(g)  2B(g) ? (K P represents the
KP
equilibrium constant of the reaction) value of K ? [NCERT Pg. 202]
C
[NCERT Pg. 207]
(1) 4 KP

(1) 2NO2 (g) N2O4 (g)
(2) 7KP1/2

(2) SO2Cl2 (g) SO2 (g)  Cl2 (g)
(3) 2KP1/2

(3) N2 (g)  3H2 (g) 2NH3 (g)
(4) 3KP1/2

(4) 2HBr(g) H2 (g)  Br2 (g)
28 Equilibrium NEET
8. Consider the following graph for the chemical reaction 11. The dissociation constant of a weak monoacidic
base is 10–5. The pH of its 0.1 M solution will be

H2(g) + I2(g) 2HI(g) approximately equal to [NCERT Pg. 221]
(1) 11 (2) 8
(3) 7.5 (4) 10
Concentration
HI
H2, I2
12. K1
HF  H2O  H3 O  F
F  H2O 
K2
HF  OH
Time Equilibrium Time For the above two reactions which of the given
relation is correct? [NCERT Pg. 223]
The inference that can be obtained from this graph
(2) K 2  1
about chemical equilibrium is that
(1) K2 = Kw
[NCERT Pg. 198] Kw
(1) Equilibrium can be attained only when it starts K1

(3) Kw = K1K2 (4) K w 
from pure product K2
(2) Equilibrium can be attained only when it starts
13. pH of solution formed by mixing 40 ml of 0.1 M
from pure reactants
HCl with 10 ml of 0.45 M of NaOH is
(3) Equilibrium can be attained from both sides,
[NCERT Pg. 218]
either it starts from pure product or from pure
reactants (1) 10 (2) 12
(4) Equilibrium can’t be attained in reverse (3) 8 (4) 6
direction if it starts from pure reactants
14. What is the pH of 10–6 M HCl at 25°C?
9. Out of the following, choose an incorrect statement.
[NCERT Pg. 218]
[NCERT Pg. 195]
(1) 6 (2) 7

(1) For solid liquid equilibrium, there is (3) < 6 (4) > 7
only one temperature that is melting point at
which the two phases can coexist at a given 15. The solubility of sparingly soluble salt Bi2S5 is
pressure S mol dm3. Its solubility product is
[NCERT Pg. 229]

(2) For liquid
vapour equilibrium, the vapour
pressure is constant at a given temperature (1) 6250 S5 (2) 3125 S6
(3) When radioactive sugar is dissolved into (3) 108 S7 (4) 12500 S7
saturated solution of non-radioactive sugar,
then after some time radioactivity is observed SECTION - B
both in the solution and in the solid sugar
Objective Type Questions

(4) For Ice(s)
water (), on increasing the
1. The equilibrium constant K C for the following
pressure melting of ice decreases
reaction will be
10. The pK a and pK b value of acetic acid and
K2CO3(aq) + BaSO4(s) BaCO3(s) + K2SO4(aq)
ammonium hydroxide are 4.78 and 4.7 respectively,
then the pH of ammonium acetate solution is [CO23 – ] [K 2CO3 ]
(1) (2)
[NCERT Pg. 226] [SO24– ] [K 2SO4 ]
(1) 8.04 (2) 6.02 [BaSO 4 ] [SO24– ]
(3) (4)
(3) 7.04 (4) 5.04 [CO23 – ] [CO23 – ]
NEET Equilibrium 29
2. When 3.00 mole of A and 1.00 mole of B are mixed 8. For the equilibrium AB(g) A(g) + B(g), Kp is
in a 1.00 litre vessel, the following reaction takes equal to four times the total pressure. The number
place of moles of 'A' formed is
A(g) + B(g) 2C(g)
5
(1) (2) 2
The equilibrium mixture contains 0.5 mole of C. 2
What is the value of equilibrium constant for the
reaction? 2
(3) 5 (4)
(1) 0.12 (2) 6 5
(3) 1.5 (4) None of these 9. Kp is how many times equal to Kc for the given
reaction?
3. In which of the following does the reaction go
almost to completion? N2(g) + 3H2(g) 2NH3(g)
(1) Kc = 103 (2) Kc = 102
1
(3) Kc = 10–2 (4) Kc = 10–3 (1) (2) R2T2
R2T 2
4. 4.0 moles of PCl5 dissociate at 760 K in a 2 litre
flask PCl5 (g) PCl3(g) + Cl2(g) at equilibrium. R
(3) (4) RT
0.8 mole of Cl 2 was present in the flask.The T
equilibrium constant would be
10. 4 gm H2, 32 gm O2, 14 gm N2 and 11gm CO2 are
(1) 1.0 × 10–1 (2) 1.0 × 10–4 taken in a bulb of 500 ml. Which one of these has
maximum active mass?
(3) 1.0 × 10–2 (4) 1.0 × 10–3
(1) H2 (2) O2
5. Two moles of NH 3 gas are introduced into a
previously evacuated one litre vessel in which it (3) N2 (4) CO2
partially dissociates at high temperature as 11. At temperature T, a compound AB2(g) dissociates
2NH3 (g) . N2 (g) + 3H2 (g). At equilibrium, one according to the reaction
mole of NH3(g) remain. The value of Kc is
2AB2(g) 2AB(g) + B2(g) with a degree of
(1) 3
dissociation 'x' which is small as compared to
(2) 27/16 unity. The expression for Kp in terms of 'x' and total
(3) 3/2 pressure P is
(4) 27/64 Px3

(1)
6. 1 mole of NO2 and 2 moles of CO are enclosed in 2
a one litre vessel to attain the following equilibrium
NO2 + CO NO + CO2. It was estimated that Px2
(2)
at the equilibrium, 25% of initial amount of CO is 3
consumed. The equilibrium constant Kp is
Px3
(1) 1 (3)
3
(2) 1/2
(3) 1/4 Px2
(4)
2
(4) 1/3
12. When ethyl alcohol and acetic acid mixed together
7. In a chemical equilibrium the rate constant of the in equimolecular proportions, equilibrium is attained
backward reaction is 7.5 × 10–4 and the equilibrium when two–third of the acid and alcohol are
constant is 1.5. So the rate constant of the forward consumed. The equilibrium constant of the reaction
reaction is will be
(1) 2 × 10–3 (2) 15 × 10–4 (1) 0.4 (2) 4
(3) 1.125 × 10–3 (4) 9.0 × 10–4 (3) 40 (4) 0.04
30 Equilibrium NEET
13. XY2 dissociates as, 19. By the addition of an inert gas to the system
2HI H2 + I2, the degree of dissociation of HI
XY2(g) XY(g) + Y(g)
will be
Initial pressure of XY2 is 600 mm of Hg. The total
(1) Suppressed (2) Not altered
pressure at equilibrium is 800 mm of Hg. Assuming
volume of system to remain constant, the value of (3) Increased (4) Doubled
Kp is
20. Kc for A(g) + B(g) 3C(g) is 30 at 298 K. If a two
(1) 50 (2) 100
litre vessel contains 1, 2 and 5 moles of A, B and C
(3) 20 (4) 400 respectively, the reaction at 298 K shall
14. Ammonium carbamate dissociates as (1) Proceed from left to right
NH2COONH4(s) 2NH3(g) + CO2(g) (2) Proceed from right to left
In a closed vessel containing ammonium carbamate (3) Be at equilibrium
in equilibrium, ammonia is added such that the
partial pressure of NH3 now equals to the original (4) Can’t be predicted
total pressure. The ratio of total pressure now to
21. In the equilibrium, Ice Water, on increasing
the original pressure is
pressure, melting point of ice
27 31
(1) (2) 27 (1) Decreases
31
(2) Increases
4 5P
(3) (4)
9 9 (3) Remains same
15. By the addition of an inert gas to the system (4) May increase or decrease
PCl5 PCl3 + Cl2 at constant volume the degree 22. Select the species which can act both as an acid
of dissociation of PCl5 will and as a base
(1) Increase (2) Decrease (1) H2SO4 (2) HSO4–
(3) Double (4) Not change (3) H3O+ (4) CO32–
16. Which one of the following equilibrium moves
23. BF3 is
backward when pressure is applied?
(1) Lewis acid (2) Lewis base
(1) N2 (g) + 3H2 (g) 2NH3 (g)
(3) Bronsted acid (4) Arrhenius acid
(2) N2 (g) + O2 (g) 2NO (g)
24. The decreasing order of strength of following bases
(3) Water Ice
(4) I2 (g) I2 (s) NH3, CH3COO– and Cl– is
17. When 1 mole of N2 and 1 mole of H2 is enclosed (1) Cl–, CH3COO–, NH3 (2) CH3COO—, NH3, Cl–
in 3L vessel and the reaction is allowed to attain (3) CH3COO–, Cl– , NH3 (4) NH3 , CH3COO–, Cl–
equilibrium, it is found that at equilibrium there is
'x' mole of H2. The number of moles of NH3 formed 25. An example of a salt dissolved in water to give
would be acidic solution is
(1) Ammonium chloride
2x 2(1  x)
(1) (2)
3 3 (2) Sodium acetate
2(1  x) (1  x) (3) Potassium nitrate

(3) (4)
3 2 (4) Barium bromide
18. What is the unit of K for the following equilibria?
26. If 100 ml of 1N H2SO4 were mixed with 100 ml of
2NO(g) + Cl2 (g) 2NOCl (g) 1M NaOH, the solution will be
(1) Mol–1 (2) L mole–1 (1) Acidic (2) Basic
(3) L cm–1 (4) Mol–1 lit–1 (3) Neutral (4) Slightly acidic
NEET Equilibrium 31
27. At 100°C, K w = 10 –12 . pH of pure water at 35. The solubility product of AgCl is Ksp. Then the
100° C will be solubility of AgCl in x M KCl is
(1) 7.0 (2) 6.0 x
(1) Ksp × x2 (2) K
(3) 8.0 (4) 12.0 sp
28. Calculate the percentage ionization of 0.01 M acetic K sp K sp

acid in 0.1 M HCl K a of acetic acid is (3) 2 (4)
x x
1.8 × 10–5
36. Degree of hydrolysis (h) of a salt of weak acid and
(1) 0.18% (2) 0.018%
a strong base is given by
(3) 1.8% (4) 18%
29. A solution of NaOH contain 0.04 gm of NaOH per (1) h  K h (2) h  K h
litre. Its pH is c
(1) 10 (2) 9 c Kw
(3) h  (4) h 
(3) 11 (4) 12 Kh Kb
30. The number of hydrogen ions in 10 ml of a solution 37. The K SP for a sparingly soluble Ag 2 CrO 4 is
with pH = 13 is 4 × 10–12. The molar solubility of the salt is
(1) 1013 (2) 6.023 × 108 (1) 2.0 × 10–6 mol L–1 (2) 1.0 × 10–4 mol L–1
(3) 6.023 × 1010 (4) 6.023 × 1013 (3) 2.0 × 10–12 mol L–1 (4) 1.0 × 10–15 mol L–1
31. 1 c.c of 0.1 N HCl is added to 1 litre solution of 38. A solution of pH = 2 is more acidic than of
sodium chloride. The pH of the resulting solution pH = 6 by a factor of
will be
(1) 4 (2) 12
(1) 7 (2) 0
(3) 400 (4) 10,000
(3) 10 (4) 4
39. An acidic solution of pH 6 is diluted thousand
32. The following reactions are known to occur in the times. The pH of solution becomes approx
body
(1) 9 (2) 6
CO2 + H2O H2CO3 H+ + HCO3
(3) 3 (4) 6.96
If CO2 escapes from the system
40. Solubility product of
(1) pH will decrease
(a) MnS is 1.4 × 10–10 (b) ZnS is 1.2 × 10–28
(2) Hydrogen ion concentration will diminish
(c) CdS is 3.6 × 10–28 (d) CuS is 8.5 × 10–36
(3) H2CO3 concentration will be promoted
(4) The forward reaction will be promoted Which of these has maximum solubility?
33. The precipitate of CaF 2 (K sp = 1.7 × 10 –10) is (1) (a) (2) (b)
obtained when equal volumes of the following are (3) (c) (4) (d)
mixed
41. For preparing a buffer of pH = 6 by mixing sodium
(1) 10–4 M Ca2+ + 10–4 M F– acetate and acetic acid the ratio of the
(2) 10–2 M Ca2+ + 10–3 M F– concentration of salt and acid should be (Ka = 10–5)
(3) 10–4 M Ca2+ + 10–3 M F– (1) 1 : 100 (2) 10 : 1

(4) 10–3 M Ca2+ + 10–5 M F– (3) 100 : 1 (4) 1 : 100
34. A monoprotic acid in a 0.1 M solution ionises to 42. The salt whose aqueous solution has highest pH
0.001%. Its ionisation constant is is
(1) 1.0 × 10–3 (2) 1.0 × 10–6 (1) KCl (2) NH4Cl
(3) 1.0 × 10–8 (4) 1.0 × 10–11 (3) (NH4)2CO3 (4) Na2CO3
32 Equilibrium NEET
43. In which solution, AgCl has minimum solubility? 7. Which one of the following conditions will favour
(1) 0.01 M NaCl (2) 0.01 M CaCl2 maximum formation of the product in the reaction,
(3) 0.05 M AgNO3 (4) Pure water X2 (g) r H = –X kJ?

A 2 (g) + B2 (g)
[NEET-2018]
SECTION - C (1) Low temperature and high pressure
Previous Years Questions (2) Low temperature and low pressure
1. THe pH of 0.01 M NaOH (aq) solution will be (3) High temperature and low pressure
[NEET-2019 (Odisha)] (4) High temperature and high pressure

8. The solubility of BaSO4 in water is 2.42 × 10–3 gL–1 at
(1) 9 (2) 7.01
298 K. The value of its solubility product (Ksp) will
(3) 2 (4) 12 be
2. Which of the following cannot act both as (Given molar mass of BaSO4 = 233 g mol–1)
Bronsted acid and as Bronsted base? [NEET-2018]
[NEET-2019 (Odisha)] (1) 1.08 × 10–10 mol2L–2
(2) 1.08 × 10–12 mol2L–2
(1) HSO4 (2) HCO3
(3) 1.08 × 10–8 mol2L–2
(3) NH3 (4) HCl (4) 1.08 × 10–14 mol2L–2
3. The molar solubility of CaF2(Ksp = 5.3 × 10–11) in 9. Following solutions were prepared by mixing
0.1 M solution of NaF will be different volumes of NaOH and HCl of different
[NEET-2019 (Odisha)] concentrations :
(1) 5.3 × 10–10 mol L–1 (2) 5.3 × 10–11 mol L–1 M M
a. 60 mL HCl + 40 mL NaOH
10 10
(3) 5.3 × 10–8 mol L–1 (4) 5.3 × 10–9 mol L–1
M M
4. pH of a saturated solution of Ca(OH)2 is 9. The b. 55 mL HCl + 45 mL NaOH
solubility product (Ksp) of Ca(OH)2 is: [NEET-2019] 10 10
(1) 0.5 × 10–15 (2) 0.25 × 10–10 M M

c. 75 mL HCl + 25 mL NaOH
5 5
(3) 0.125 × 10–15 (4) 0.5 × 10–10
M M
d. 100 mL HCl + 100 mL NaOH
5.
ii
Conjugate base for Br onsted acids H2O and HF 10 10
are : [NEET-2019] pH of which one of them will be equal to 1?
(1) OH– and H2F+, respectively [NEET-2018]

(1) b (2) a
(2) H3O+ and F–, respectively
(3) c (4) d
(3) OH– and F–, respectively
10. A 20 litre container at 400 K contains CO2(g) at
(4) H3O+ and H2F+, respectively pressure 0.4 atm and an excess of SrO (neglect
6. Which will make basic buffer? [NEET-2019] the volume of solid SrO). The volume of the
containers is now decreased by moving the
(1) 50 mL of 0.1 M NaOH + 25 mL of 0.1 M
movable piston fitted in the container. The
CH3COOH
maximum volume of the container, when pressure
(2) 100 mL of 0.1 M CH3COOH + 100 mL of 0.1 M of CO2 attains its maximum value, will be
NaOH

(Given that : SrCO3(s) SrO(s) + CO2(g).
(3) 100 mL of 0.1 M HCl + 200 mL of 0.1 M Kp = 1.6 atm) [NEET-2017]
NH4OH (1) 5 litre (2) 10 litre
(4) 100 mL of 0.1 M HCl + 100 mL of 0.1 M NaOH (3) 4 litre (4) 2 litre
NEET Equilibrium 33
11. The equilibrium constants of the following are. 17. MY and NY3, two nearly insoluble salts, have the

same K SP values of 6.2 × 10 –13 at room
N2 + 3H2
2NH3 K1
temperature. Which statement would be true in

N2 + O2
2NO K2 regard to MY and NY3? [NEET-2016]
(1) The addition of the salt of KY to solution of MY
1
H2  O2  H2O K3 and NY3 will have no effect on their solubilities
2
The equilibrium constant (K) of the reaction: (2) The molar solubilities of MY and NY3 in water
are identical
5 K

2NH3  O2 2NO  3H2O, will be (3) The molar solubility of MY in water is less than
2 that of NY3
[NEET-2017] (4) The salts MY and NY3 are more soluble in
0.5 M KY than in pure water
(1) K1K33 / K2 (2) K2K33 / K1
18. Consider the following liquid-vapour equilibrium.
(3) K2K3 / K1 (4) K32K3 / K1

Liquid
Vapour
12. Concentration of the Ag + ions in a saturated
solution of Ag 2 C 2 O 4 is 2.2 × 10 –4 mol L –1 . Which of the following relations is correct?
Solubility product of Ag2C2O4 is [NEET-2017]
[NEET-2016]
(1) 2.42 × 10–8 (2) 2.66 × 10–12
(3) 4.5 × 10–11 (4) 5.3 × 10–12 dlnP Hv dlnG Hv
(1)  (2) 
13. The percentage of pyridine (C5H5N) that forms
dT RT 2 dT 2 RT 2
pyridinium ion (C5H5N+H) in a 0.10 M aqueous
pyridine solution (Kb for C5H5N = 1.7 × 10–9) is dlnP – Hv dlnP – Hv
(3)  (4) 2

dT RT dT T2
[NEET (Phase-2) 2016]
19. If the equilibrium constant for
(1) 0.0060% (2) 0.013%

N2 (g)  O2 (g) 2NO(g) is K, the equilibrium
(3) 0.77% (4) 1.6%
1 1
14. The solubility of AgCl(s) with solubility product constant for N2 (g)  O2 (g) NO(g) will
2 2
1.6 × 10–10 in 0.1 M NaCl solution would be be [Re-AIPMT-2015]
[NEET (Phase-2) 2016] (1) K (2) K2
(1) 1.26 × 10–5 M (2) 1.6 × 10–9 M 1
(3) K1/2 (4) K
(3) 1.6 × 10–11 M (4) Zero 2
15. Boric acid is an acid because its molecule 20. Which one of the following pairs of solution is not
an acidic buffer? [Re-AIPMT-2015]
[NEET (Phase-2) 2016]
(1) Contains replaceable H+ ion (1) H2CO3 and Na2CO3
(2) Gives up a proton (2) H3PO4 and Na3PO4
(3) Accepts OH– from water releasing proton (3) HClO4 and NaClO4
(4) Combines with proton from water molecule (4) CH3COOH and CH3COONa
16. Which of the following fluoro-compounds is most 21. What is the pH of the resulting solution when
likely to behave as a Lewis base? equal volumes of 0.1 M NaOH and 0.01 M HCl are
[NEET (Phase-2) 2016] mixed? [Re-AIPMT-2015]
(1) BF3 (2) PF3 (1) 7.0 (2) 1.04
(3) CF4 (4) SiF4 (3) 12.65 (4) 2.0
34 Equilibrium NEET
22. Which of the following statements is correct for a 28. For the reversible reaction
reversible process in a state of equilibrium?

N2(g)+3H2(g)
2NH3(g) + heat
[AIPMT-2015]
The equilibrium shifts in forward direction
(1) G° = 2.30 RT log K
[AIPMT-2014]
(2) G = –2.30 RT log K
(1) By increasing the concentration of NH3(g)
(3) G = 2.30 RT log K
(2) By decreasing the pressure
(4) G° = –2.30 RT log K
(3) By decreasing the concentrations of N2(g) and
23. The K sp of Ag 2CrO 4, AgCl, AgBr and AgI are
H2(g)
respectively, 1.1 × 10–12, 1.8 × 10–10, 5.0 × 10–13,
8.3 × 10–17. Which one of the following salts will (4) By increasing pressure and decreasing
precipitate last if AgNO3 solution is added to the temperature
solution containing equal moles of NaCl, NaBr, NaI
29. Identify the correct order of solubility in aqueous
and Na2CrO4? [AIPMT-2015]
medium [NEET-2013]
(1) Ag2CrO4 (2) AgI
(1) ZnS > Na2S > CuS
(3) AgCl (4) AgBr
(2) Na2S > CuS > ZnS
24. If the value of an equilibrium constant for a
particular reaction is 1.6 × 1012, then at equilibrium (3) Na2S > ZnS > CuS
the system will contain [AIPMT-2015]
(4) CuS > ZnS > Na2S
(1) Similar amounts of reactants and products
30. KMnO4 can be prepared from K2MnO4 as per the
(2) All reactants reaction,
(3) Mostly reactants

3MnO24 + 2H2O 
2MnO4 +MnO2 + 4OH–
(4) Mostly products
The reaction can go to completion by removing
25. Which of the folowing salts will give highest pH in OH – ions by adding [NEET-2013]
water? [AIPMT-2014]
(1) KOH (2) CO2
(1) KCl (2) NaCl
(3) SO2 (4) HCl
(3) Na2CO3 (4) CuSO4
31. Buffer solutions have constant acidity and alkalinity
26. For a given exothermic reaction, Kp and Kp are because [AIPMT (Prelims)-2012]
the equilibrium constants at temperatures T1 and
T2, respectively. Assuming that heat of reaction is (1) They have large excess of H+ or OH– ions
constant in temperature range between T1 and T2,
(2) They have fixed value of pH
it is readily observed that [AIPMT-2014]
(3) These give unionised acid or base on reaction
(1) Kp > Kp (2) Kp < Kp
with added acid or alkali
1
(3) Kp = Kp (4) Kp = (4) Acids and alkalies in these solutions are
K p shielded from attack by other ions
27. Using the Gibbs energy change, G = +63.3 kJ, 32. pH of a saturated solution of Ba(OH)2 is 12. The
for the following reaction, value of solubility product (Ksp) of Ba(OH)2 is

2
2Ag+ (aq) + CO3 (aq)
Ag2CO3(s) [AIPMT (Prelims)-2012]
the Ksp of Ag2CO3(s) in water at 25C is (1) 4.0 × 10–6
(R = 8.314 J K–1 mol–1) [AIPMT-2014] (2) 5.0 × 10–6
(1) 3.2 × 10–26 (2) 8.0 × 10–12 (3) 3.3 × 10–7
(3) 2.9 × 10–3 (4) 7.9 × 10–2 (4) 5.0 × 10–7
NEET Equilibrium 35
33. Given that the equilibrium constant for the reaction 37. In qualitative analysis, the metals of group  can be
separated from other ions by precipitating them as
2SO2(g) + O2(g) 2SO3(g), has a value of
chloride salts. A solution initially contains Ag+ and
278 at a particular temperature. What is the value
Pb2+ at a concentration is 0.10 M. Aqueous HCl is
of the equilibirum constant for the following reaction
added to this solution until the Cl– concentration is
at the same temperature ?
0.10 M. What will the concentration of Ag+ and
1 Pb2+ be at equilibrium ?

SO3(g)
SO2(g) + 2 O2(g)
(Ksp for AgCl = 1.8×10–10, Ksp for PbCl2 = 1.7×10–5)
[AIPMT (Mains)-2012]
[AIPMT (Mains)-2011]
(1) 1.8 × 10–3 (2) 3.6 × 10–3
(3) 6.0 × 10–2 (4) 1.3 × 10–5 (1) [Ag+] = 1.8 × 10–9 M [Pb2+] = 1.7 × 10–3 M
34. Given the reaction between 2 gases represented by (2) [Ag+] = 1.8 × 10–11 M [Pb2+] = 1.7 × 10–4 M
A2 and B2 to give the compound AB(g). (3) [Ag+] = 1.8 × 10–6 M [Pb2+] = 1.7 × 10–11 M

A2(g) + B2(g)
2AB(g) (4) [Ag+] = 1.8 × 10–11 M [Pb2+] = 8.5 × 10–5 M
At equilibrium, the concentration
38. The value of H for the reaction
of A2 = 3.0 × 10–3 M
X2(g) + 4Y2(g) 2XY4 (g)
of B2 = 4.2 × 10–3 M
is less than zero. Formation of XY 4(g) will be
of AB = 2.8 × 10–3 M
favoured at: [AIPMT (Prelims)-2011]
If the reaction takes place in a sealed vessel at
(1) High pressure and low temperature
527C, then the value of Kc will be
[AIPMT (Mains)-2012] (2) High temperature and high pressure
(1) 2.0 (2) 1.9 (3) Low pressure and low temperature
(3) 0.62 (4) 4.5 (4) High temperature and low pressure
35. A buffer solution is prepared in which the 39. In which of the following equilibrium Kc and Kp are
concentration of NH 3 is 0.30 M and the not equal? [AIPMT (Prelims)-2010]
concentration of NH4+ is 0.20 M. If the equilibrium

(1) 2NO(g)
N2 (g) + O2 (g)
constant, Kb for NH3 equals 1.8 × 10–5, what is
the pH of this solution? (log 2.7 = 0.43)

(2) SO2 (g) + NO2 (g)
SO3 (g) + NO(g)
[AIPMT (Prelims)-2011]
(1) 8.73 (2) 9.08

(3) H2 (g) + I2 (g)
2HI(g)
(3) 9.43 (4) 11.72

(4) 2C(s) + O2 (g)
2CO2(g)

36. For the reaction, N2 (g)  O2 (g) 2NO(g) ,
the equilibrium constant is K1. The equilibrium 40. What is [H+] in mol/L of a solution that is 0.20 M
constant is K 2 for the reaction
CH3COONa and 0.10 M in CH3COOH ? (Ka for

2NO(g)  O2 (g)
2NO2 (g) . What is K for the CH3COOH = 1.8×10–5) [AIPMT (Prelims)-2010]

1
N2 (g)  O2 (g) ?
reaction NO2 (g) (1) 3.5 × 10–4 (2) 1.1 × 10 –5
2
[AIPMT (Prelims)-2011] (3) 1.8 × 10–5 (4) 9.0 × 10–6
1 1 41. In a buffer solution containing equal concentration

(1) (K K ) (2) (2K K ) of B– and HB, the Kb for B– is 10–10. The pH of
1 2 1 2
buffer solution is [AIPMT (Prelims)-2010]
1/2
1  1  (1) 10 (2) 7
(3) (4)  K K 
(4K1K 2 )  1 2 (3) 6 (4) 4
36 Equilibrium NEET

42. The reaction, 2A(g) + B(g)
3C(g) + D(g) 48. The values of KP and KP for the reactions
1 2
is begun with the concentrations of A and B both

X
Y+Z ...(i)
at an initial value of 1.00 M. When equilibrium is
reached, the concentration of D is measured and

A
2B ...(ii)
found to be 0.25 M. The value for the equilibrium are in ratio of 9:1. If degree of dissociation X and
constant for this reaction is given by the A be equal, then total pressure at equilibrium (i)
expression [AIPMT (Mains)-2010] and (ii) are in the ratio [AIPMT (Prelims)-2008]
(1) [(0.75)3(0.25)]  [(1.00)2(1.00)] (1) 1 : 1 (2) 3 : 1
(2) [(0.75)3(0.25)]  [(0.50)2(0.75)] (3) 1 : 9 (4) 36 : 1
(3) [(0.75)3(0.25)]  [(0.50)2(0.25)] 49. If the concentration of OH– ions in the reaction
(4) [(0.75)3(0.25)]  [(0.75)2(0.25)]

Fe(OH) 3 (s)
Fe 3+ (aq) + 3OH – (aq) is
43. The dissociation constants for acetic acid and 1
HCN at 25C are 1.5×10 –5 and 4.5×10 –10 decreased by times, then equilibrium
4
respectively. The equilibrium constant for the
concentration of Fe3+ will increase by

equilibrium, CN–+ CH COOH
HCN + CH COO–
3 3 [AIPMT (Prelims)-2008]
would be [AIPMT (Prelims)-2009] (1) 4 times (2) 8 times
(1) 3.0 × 10–5 (2) 3.0 × 10–4 (3) 16 times (4) 64 times
(3) 3.0 × 104 (4) 3.0 × 105 50. The dissociation equilibrium of a gas AB2 can be
44. The ionization constant of ammonium hydroxide is represented as, 2AB2(g)
2AB (g) + B2(g).
1.77 × 10 –5 at 298 K. Hydrolysis constant of The degree of dissociation is 'x' and is small
ammonium chloride is [AIPMT (Prelims)-2009] compared to 1. The expression relating the degree
(1) 6.50 × 10–12 (2) 5.65 × 10–13 of dissociation (x) with equilibrium constant KP and
total pressure P is [AIPMT (Prelims)-2008]
(3) 5.65 × 10–12 (4) 5.65 × 10–10
45. What is the [OH–] in the final solution prepared by  KP   2K P 
(1)   (2)  
mixing 20.0 mL of 0.050 M HCl with 30.0 mL of  P   P 
0.10 M Ba(OH)2? [AIPMT (Prelims)-2009] 1/3 1/2
 2K P   2K P 
(1) 0.40 M (2) 0.0050 M (3)   (4)  
 P   P 
(3) 0.12 M (4) 0.10 M
51. Equimolar solutions of the following were prepared
46. The value of equilibrium constant of the reaction in water separately. Which one of the solutions will
record the highest pH? [AIPMT (Prelims)-2008]
1 1

Hl(g)
H2 (g)  l2 is 8.0. The equilibrium (1) CaCl2 (2) SrCl2
2 2

constant of the reaction, H2(g) + l2(g) (3) BaCl2 (4) MgCl2
2Hl(g)
will be [AIPMT (Prelims)-2008] 52. The following equilibrium constants are given
1 1 N2 + 3H2  2NH3 ; K1
(1) (2)
8 16 N2+ O2  2NO ; K2
1 1
(3) (4) 16 H2 + O  H2O ; K3
64 2 2
47. Equal volumes of three acid solutions of pH–3, 4 The equilibrium constant for the oxidation of NH3 by
and 5 are mixed in a vessel. What will be the H+ oxygen to give NO is [AIPMT (Prelims)-2007]
ion concentration in the mixture?
K1 K 2 K 2 K 33
[AIPMT (Prelims)-2008] (1) K3 (2)
K1
(1) 1.11 × 10–3 M (2) 1.11 × 10–4 M
K 2 K 32 K 22 K 3
(3) 3.7 × 10–4 M (4) 3.7 × 10–3 M (3) (4)
K1 K1
NEET Equilibrium 37
53. Calculate the pOH of a solution at 25C that 59. At 25C, the dissociation constant of a base, BOH,
contains 1 × 10–10 M of hydronium ions, i.e. H3O+ is 1.0 × 10–12. The concentration of hydroxyl ions
in 0.01M aqueous solution of the base would be
(1) 1.000 (2) 7.000
(1) 2.0 × 10–6 mol L–1 (2) 1.0 × 10–5 mol L–1
(3) 4.000 (4) 9.000
(3) 1.0 × 10–6 mol L–1 (4) 1.0 × 10–7 mol L–1
54. A weak acid, HA has a Ka of 1.00 × 10–5. If 0.100
60. Equilibrium constants K1 and K2 for the following
mol of this acid is dissolved in one litre of water,
equilibria:
the percentage of acid dissociated at equilibrium is
closest to [AIPMT (Prelims)-2007] 1 K1
NO(g) + O NO2(g) and
(1) 0.100% (2) 99.0% 2 2
K2
(3) 1.00% (4) 99.9%
2NO2(g) 2NO(g) + O2(g)
55. Which one of the following ionic species has the are related as [AIPMT (Prelims)-2005]
greatest proton affinity to form stable compound ?
1
[AIPMT (Prelims)-2007] (1) K2 = (2) K2 = K12
K1
(1) – (2) HS–
K1 1
(3) K2 = (4) K2 =
(3) NH2– (4) F– 2 K12
56. For the reaction, 61. H 2 S gas when passed through a solution of
cations containing HCl precipitates the cations of

CH4(g) + 2O2(g)
CO2(g) + 2H2O(l), second group of qualitative analysis but not those
rH = –170.8 kJ mol–1 belonging to the fourth group. It is because
Which of the following statements is not true ? [AIPMT (Prelims)-2005]
[AIPMT (Prelims)-2006] (1) Presence of HCl decreases the sulphide ion

concentration
(1) At equilibrium, the concentrations of CO2(g)
(2) Presence of HCl increases the sulphide ion
and H2O(l) are not equal
concentration
(2) The equilibrium constant for the reaction is (3) Solubility product of group II sulphides is more
given by Kp =
CO2  than that of group IV sulphides
CH4 O2  (4) Sulphides of group IV cations are unstable in
(3) Addition of CH4(g) or O2(g) at equilibrium will HCl
cause a shift to the right
Questions asked Prior to Medical Ent. Exams. 2005
(4) The reaction is exothermic 62. The dissociation constant of a weak acid is 1 × 10–4.
57. Which of the following pairs constitutes a buffer ? In order of prepare a buffer solution with a pH = 5 the
[Salt]/[Acid] ratio should be
(1) 1 : 10 (2) 4 : 5
(1) HNO2 and NaNO2 (2) NaOH and NaCl
(3) 10 : 1 (4) 5 : 4
(3) HNO3 and NH4NO3 (4) HCl and KCl
63. Which one of the following is not acid-base
58. The hydrogen ion concentration of a 10–8 M HCl conjugate pair?
aqueous solution at 298 K (Kw = 10–14) is (1) HONO, NO2–
[AIPMT (Prelims)-2006] (2) CH3NH3+, CH3NH2
(1) 1.0 × 10–6 M (2) 1.0525 × 10–7 M (3) C6H5 – COOH, C6H5COO–
(3) 9.525 × 10–8 M (4) 1.0 × 10–8 M (4) H3O+, OH–
38 Equilibrium NEET
64. For the reactions 69. Which one of the following species acts only as a
base?

I2(aq)
I2(oil) Equilibrium constant is K1
(1) H2S (2) HS–

I2(oil)
I2(ether) Equilibrium constant is K2
(3) S2– (4) H2O
for the reaction
70. At 100°C the Kw of water is 55 times its value at

I2(aq)
I2(ether) Equilibrium constant is K3 25°C. What will be the pH of neutral solution?
(log 55 = 1.74)
The relation between K1, K2, K3 is
(1) 6.13 (2) 7.00
(1) K3 = K1 + K2
(3) 7.87 (4) 5.13
(2) K3 = K1K2
71. Which one of the following is most soluble?
(3) K3 = K1/K2
(1) Bi2S3 (Ksp = 1 × 10–70)
(4) K3 = K2/K1
(2) Ag2S (Ksp = 6 × 10–51)
65. Given exothermic reaction
(3) CuS (Ksp = 8 × 10–37)

CoCl24 (aq)  6H2 O(l) 2
[Co(H2 O)6 ]  4Cl

(4) MnS (Ksp = 7 × 10–16)

Which one of the following will decrease the
equilibrium concentration of CoCl24 ? 72. At 80°C, distilled water has [H3O+] concentration
equal to 1 × 10–6 mole/litre. The value of Kw at this
(1) Addition of HCl temperature will be
(2) Addition of Co(NO3)2 (1) 1 × 10–12 (2) 1 × 10–15
(3) The solution is diluted with water (3) 1 × 10–6 (4) 1 × 10–9
(4) The temperature is increased 73. The pH value of blood does not appreciably change
by a small addition of an acid or a base, because
66. For preparing a buffer solution of pH = 7.0, which
the blood
buffer system you will choose?
(1) Can be easily coagulated
(1) H3PO 4 , H2PO 4– (2) H2PO 4– , HPO2–
4
(2) Contains iron as a part of the molecule
(3) HPO 2– 3–
4 , PO 4
(4) H3PO 4 , PO3–
4 (3) Is a body fluid
67. For a chemical reaction of the type (4) Contains serum protein which acts as buffer
A B, K = 2.0 and B C, K = 0.01 74. The pH value of 10–7 M solution HCl is
Equilibrium constant for the reaction 2C 2A (1) Equal to 1

is (2) Equal to 2
(1) 25 (2) 50 (3) Less than 7
(3) 2500 (4) 4 × 10–4 (4) Equal to 0
68. A solution is 0.1 M with respect to Ag+, Ca2+, Mg2+ 75. Standard state Gibb’s free energy change for
and Al 3+ which will precipitate at lowest isomerization reaction cis-2-pentene trans-2-
concentration of [PO3–4 ]
when solution of Na3PO4 pentene is –3.67 kJ/mol at 400 K. If more
is added? trans-2-pentene is added to the reaction vessel, then
(1) Ag3PO4(Ksp = 1 × 10–6) (1) Equilibrium remains unaffected
(2) Ca3(PO4)2(Ksp = 1 × 10–33) (2) Equilibrium is shifted in the forward direction
(3) Mg3(PO4)2(Ksp = 1 × 10–24) (3) More cis-2-pentene is formed
(4) AlPO4(Ksp = 1 × 10–20) (4) Additional trans-2-pentene is formed
NEET Equilibrium 39
76. The equilibrium constant for the reaction 82. The concentration of [H+] and concentration of [OH– ]
N2 + 3H 2 2NH 3 is K, then the equilibrium of a 0.1 M aqueous solution of 2% ionised weak acid
constant for the equilibrium 2NH3 N2 + 3H2 is is [ionic product of water = 1 × 10–14]
(1) 2 × 10–3 M and 5 × 10–12 M
1
(1) K (2) (2) 1 × 10–3 M and 3 × 10–11 M
K
(3) 0.02 × 10–3 M and 5 × 10–11 M
1 1
(3) (4) (4) 3 × 10–2 M and 4 × 10–13 M
K K2
83. The values of K sp of CaCO 3 and CaC 2O4 are
77. The ionic product of water at 25°C is 10–14. Its
4.7 × 10–9 and 1.3 × 10–9 respectively at 25°C. If
ionic product at 90°C will be
the mixture of these two is washed with water,
(1) 1 × 10–14 (2) 1 × 10–16 what is the concentration of Ca2+ ions in water?
(3) 1 × 10–20 (4) 1 × 10–12 (1) 7.746 × 10–5 M (2) 5.831 × 10–5 M
78. If  is degree of dissocliation, then the total number (3) 6.856 × 10–5 M (4) 3.606 × 10–5 M
of moles for the reaction starting with 1 mole of HI
2HI = H2 + I2 will be 84. The solubility of a saturated solution of calcium
fluoride is 2 × 10–4 moles per litre. Its solubility
(1) 1 (2) 1 –  product is
(3) 2 (4) 2 –  (1) 22 × 10–11 (2) 14 × 10–4
79. Which of the following is not a Lewis acid? (3) 2 × 10–2 (4) 32 × 10–12
(1) SiF4 (2) C2H4 85. Equilibrium constant Kp for following reaction
(3) BF3 (4) FeCl3
MgCO3(s) MgO(s) + CO2(g)
80. The solubility product of CuS, Ag2S and HgS are
10–31, 10–44, 10–54 respectively. The solubilities of (1) K p  PCO
2
these sulphides are in the order
(1) HgS > Ag2S > CuS PCO2  PMgO
(2) K p  PCO2 
(2) CuS > Ag2S > HgS PMgCO3
(3) Ag2S > CuS > HgS

PCO2  PMgO
(4) AgS > HgS > CuS (3) K p 
PMgCO3
81. If K 1 and K 2 are the respective equilibrium
constants for the two reactions,
PMgCO3
XeF6(g) + H2O(g) XeOF4(g) + 2HF(g) (4) K p 
PCO2  PMgO
XeO4(g) + XeF6(g) XeOF4(g) + XeO3F2(g).
The equilibrium constant of the reaction, 86. Correct relation between dissociation constants of
a di-basic acid
XeO4(g) + 2HF(g) XeO3F2(g) + H2O(g), will be
(1) K a1  K a2 (2) K a1  K a2
K1
(1) K 1
2 (3) K a1  K a2 (4) K a1 
K a2
(2) K1 · K2
87. Conjugate acid of NH2–
K1
(3) (1) NH4OH
(K 2 )2
(2) NH4+
K2 (3) NH2–
(4)
K1 (4) NH3
40 Equilibrium NEET
88. Which statement is wrong about pH? 94. The solubility product of AgI at 25°C is
(1) pH of pure water is not zero 1.0 × 10–16 mol2 L–2. The solubility of AgI in 10–4 M
solution of KI at 25ºC is approximately (in mol L–1)
(2) Adding 1 N, solution of CH3COOH and 1 N
NaOH pH will be seven (1) 1.0 × 10–16
(3) pH of dilute and hot H2SO4 is less than 7 (2) 1.0 × 10–12
(4) Mixing solution of CH3COOH and HCl, pH will (3) 1.0 × 10–10
be less than 7 (4) 1.0 × 10–8
89. In HS–, I–, R – NH2, NH3 order of proton accepting 95. The solubility product of a sparingly soluble salt
tendency will be AX2 is 3.2 × 10–11. Its solubility (in moles/litre) is
(1) I– > NH3 > R – NH2 > HS– (1) 5.6 × 10–6
(2) NH3 > R – NH2 > HS– > I– (2) 3.1 ×10–4
(3) R – NH2 > NH3 > HS– > I– (3) 2 × 10–4
(4) HS– > R – NH2 > NH3 > I– (4) 4 × 10–4
90. Ionisation constant of CH3COOH is 1.7 × 10–5 and 96. The rapid change of pH near the stoichiometric point
concentration of H+ ions is 3.4 × 10–4. Then find of an acid-base titration is the basis of indicator
out initial concentration of CH3COOH molecules detection. pH of the solution is related to ratio of the
concentration of the conjugate acid (HIn) and base
(1) 3.4 × 10–4
(In–) forms of the indicator by the expression
(2) 3.4 × 10–3
(3) 6.8 × 10–4 [ln – ]
(1) log  pK ln  pH
(4) 6.8 × 10–3 [HIn]
91. Solution of 0.1 N NH4OH and 0.1 N NH4Cl has

[Hln]
pH 9.25. Then find out pKb of NH4OH (2) log  pK ln  pH
[In – ]
(1) 9.25
(2) 4.75 [Hln]
(3) log  pH  pK ln
(3) 3.75 [In – ]
(4) 8.25
92. Which one of the following compounds is not a [ln – ]
(4) log  pH  pK ln
protonic acid? [HIn]
(1) B(OH)3 97. What is the correct relationship between the pHs
(2) PO(OH)3 of isomolar solutions of sodium oxide (pH 1),
sodium sulphide (pH2), sodium selenide (pH3) and
(3) SO(OH)2
sodium telluride (pH4)?
(4) SO2(OH)2
(1) pH1 > pH2 > pH3 > pH4
93. The reaction quotient (Q) for the reaction
(2) pH1 > pH2  pH3 > pH4
N 2 (g) + 3H 2 (g) 2NH 3 (g) is given by
(3) pH1 < pH2 < pH3 < pH4
[NH3 ] 2
Q . The reaction will proceed from (4) pH1 < pH2 < pH3  pH4
[N 2 ][H 2 ] 3
98. Which of the following molecules acts as a Lewis
right to left if acid?
(1) Q = Kc (1) (CH3)3 N
(2) Q < Kc (2) (CH3)3 B
(3) Q > Kc (3) (CH3)2 O
(4) Q = 0 (4) (CH3)3 P
NEET Equilibrium 41
4. If pressure applied on the following reaction
SECTION - D
becomes four times H2 (g) + I2 (g) 2HI(g) then
NEET Booster Questions
1. Which of the following graph may be correct for (1) Reaction moves forward
A B? (2) Reaction moves backward
(3) No change
A
(4) Can’t be predicted
(1) Conc.
5. pH of an acidic buffer solution is 5.74 and
Time pK a (CH 3 COOH) = 4.74 then the ratio of
B
[Salt]/[Acid] will be
(1) 10
A
(2) 20
(2) Conc.
(3) 30
B Time (4) 40
6. pH of which salt is same for 1 M and 5 M solution
A both?
(1) HCOONa
Conc.
(3)
(2) C6H5NH3+Cl
B Time
(3) NH4CN
(4) All of these
(4) NaCN
2. For the following reaction,
7. NH4OH is highly soluble in
Ag2SO4 (s) 2Ag+ (aq) + SO24 (aq) (1) CuSO4 (aq)
more SO24 can be produced by (2) AgNO3(aq)

(3) NH4Cl
(1) Adding Na2SO4
(4) Both (1) & (2)
(2) Adding NH3
8. If the value of Ka of 1 M HCN is 10–5 then its degree
(3) Adding AgNO3
of dissociation in 0.1 M HCl will be ( < < < 1)
(4) Adding K2SO4
(1) 10–5
3. For two reactions in equilibrium in same container
(2) 10–4
(i) A(s) 2B(g) + C(g); (K p )1 = 27 atm3 (3) 10–3
(4) 10–2
3
(ii) D(s) 2B(g) + E(g); (K p )2 = 81 atm
9. Which of the following salt will have pH less than
Pressure of B(g) at equilibrium will be 7 when dissolved in water?
(1) 6 atm (1) CuSO4
(2) 3 atm (2) K2CO3
(3) 5 atm (3) Na3PO4
(4) 9 atm (4) KCN
42 Equilibrium NEET
10. For 15. Vapour density of PCl5 at 400 K is found to be 90.

Degree of dissociation of PCl5 will be
(i) A + B C; K C = K1
(1) 15.8% (2) 13.6%
(ii) 2C D; K C = K 2 . (3) 14.25% (4) 90%
Then the value of KC for 2D + A + B 5C will 16. Correct basic strength order will be
be (1) HSO4– < ClO4– < NO3– < NH3
(2) ClO4– < HSO4– < NO3– < NH3
K 22 K1
(1) (2)
K1 K22 (3) ClO4  HSO4  NO3  NH3
K1 1
(3) (4) (4) NO3  ClO4  NH3  HSO4
K2 K1K 22
17. In 10 ml of pH = 4 HCl solution 990 ml of 0.2 M
11. Kp for the equation A(s) B(g) + C(g) + D(s) is NaCl solution is added the pH of resulting solution
9 atm2. Then the total pressure at equilibrium will will be
be (1) pH = 5 (2) pH = 5.5
(1) 3 atm (2) 9 atm (3) pH = 6 (4) pH = 4
(3) 6 atm (4) 12 atm 18. For the gaseous reaction
12. In the equilibirum mixture A(g) + 2B(g) 2C(g) + D(g),
CaCO3(s)
CaO(s) + CO2(g). Pressure of Initial concentration of B was 1.5 times of A. At
CO2(g) at 27°C is 2 atm. What will be the pressure equilibrium concentration of A and C is equal. The
of CO2(g) when 2 moles of CO2 are added into value of Kp will be
equilibirum mixture? (1) 0.32 (2) 0.64
(1) 4 atm (2) 2 atm (3) 6 (4) 8
(3) 6 atm (4) 5 atm 19. Buffer capacity of buffer containing acid with
pKa = 4.75 will be highest when its pH is equal to
13. 1 mol of HI converts into H2 and I2 at 400 K. Value
(1) 6 (2) 4.75
2
of K p will be, if rd of HI left at gaseous (3) 5 (4) 8
3
20. On adding 0.1 M solution each of Ag, Ba2+, Ca2+
equilibrium 2HI H2  I2 ions in a Na 2 SO 4 solution, species first
precipitated will be (Given Ksp of BaSO4 = 10–11,
1 1 Ksp of CaSO4 = 10–6, Ksp of Ag2SO4 = 10–5)
(1) (2)
4 2
(1) Ag2SO4
1 (2) BaSO4
(3) (4) 1
16
(3) CaSO4
14. Consider the following statements
(4) All will precipitate simultaneously
(i) Melting point of ice decreases on increasing
21. Correct statement(s) among the following is/are
pressure
(a) Solubility of CaF2 increases in acidic medium
(ii) Melting point of Fe increases on increasing
pressure (b) pH of CH 3COONH 4 is independent of salt
concentration
(iii) Increasing pressure will increase the boiling
point of liquid (c) Buffer action of blood is due to H2CO3 and
Correct statement(s) among the following is/are HCO3 ion
(1) (i) only (2) (i), (ii) & (iii) (1) (a) & (b) (2) (a) & (c)
(3) (ii) only (4) (iii) only (3) (a), (b) & (c) (4) (a) only
NEET Equilibrium 43
22. If new equilibrium concentration of OH– in the 28. Ammonium carbamate dissociates as
following reaction NH2COONH4(s) 2NH3(g) + CO2(g)
Fe(OH)3(s) Fe3+(aq) + 3OH– (aq) is increased In a closed vessel containing ammonium carbamate
by 4 times, then equilibrium concentration of Fe3+ in equilibrium, ammonia is added such that the
ion will decrease by partial pressure of NH3 now equals to the original
(1) 8 times total pressure. The ratio of total pressure now to the
original pressure is
(2) 16 times
(3) 64 times 27 31
(1) (2) 27
(4) 4 times 31
23. Which of the following will act as buffer? 4 5

(3) (4)
(1) H2CO3 + Na2CO3 (2) Borax + Boric acid 9 9
(3) NH4Cl + NH4OH (4) All of these 29. When 1 mole of N2 and 1 mole of H2 is enclosed
24. The pH at which Ni(OH)2 begins to precipitate from in 3 L vessel and the reaction is allowed to attain
a solution containing 10–3M Ni2+ ions. equilibrium, it is found that at equilibrium there is
'x' mole of H2. The number of moles of NH3 formed
[Ksp of Ni(OH)2 = 10–11]
would be
(1) pH = 3 (2) pH = 10
2x
(3) pH = 13 (4) pH = 11 (1)
3
25. In what volume ratio NH4Cl and NH4OH having 1 M
concentration should be mixed to get a buffer 2(1  x)
(2)
solution of pH = 9.26? (pKb of NH4OH = 4.74) 3
(1) 1 : 2.5 (2) 2.5 : 1
2(1  x)
(3) 1 : 1 (4) 3.5 : 1 (3)
3
26. The equilibrium constant K C for the following
reaction will be (1  x)
(4)
2
K2CO3(aq) + BaSO4(s) BaCO3(s)+ K2SO4(aq)
30. 1 mole of 'A', 1.5 mole of 'B' and 2 mole of 'C' are
taken in a vessel of volume one litre. At equilibrium
[CO32– ] [K 2CO3 ]2 concentration of C is 0.5 mole/L. Equilibrium
(1) (2)
[SO2–
4 ] [K 2SO4 ] constant for the reaction, A(g) + B(g) C(g) is
(1) 0.66
[BaSO4 ] [SO 24– ]
(3) (4) (2) 0.066
[CO32– ]2 [CO 32 – ]
(3) 66
27. At temperature T, a compound AB2(g) dissociates (4) 6.6
according to the reaction,

31. N2  3H2
2NH3 ; K c  1.2
2AB2(g) 2AB(g) + B2(g) with a degree of
dissociation 'x' which is small as compared to At the start of a reaction, there are 0.249 mol N2,
unity. The expression for Kp in terms of 'x' and total 3.21 × 10–2 mol H2 and 6.42 × 10–4 mol NH3 in a
pressure P is 3.50 L reaction vessel at 375°C. Hence reaction
will proceed in
Px 3 Px 2 (1) Forward direction
(1) (2)
2 3 (2) Backward direction
3 2 (3) At equilibrium
Px Px
(3) (4)
3 2 (4) Stops
44 Equilibrium NEET
32. Solid ammonium carbamate dissociated according 37. Following three gaseous equilibrium reactions are
to the given reaction occurring at 27°C

A; 2CO + O2 2CO2
2NH3 (g)  CO2 (g)
NH2COONH4 (s)
Total pressure of the gases in equilibrium is 5 atm. B; PCl5 PCl3 + Cl2

Hence Kp is
C; 2HI H2 + I2
(1) 18.5
(2) 25 KP
The correct order of K for the following
(3) 1/ 5 C
(4) 12.5 reactions is
33. 1.1 mole of A is mixed with 1.2 mol of B and the (1) A < C < B (2) A < B < C
mixture is kept in a 1 L flask till the equilibrium (3) C < B < A (4) B < C < A

A  2B
2C  D is reached. At equilibrium

38. C(s)  H2 O(g)
CO(g)  H2 (g); H  0 .
0.1 mol of D is formed. The Kc of the reaction is
The above equilibrium will proceed in forward
(1) 0.002 (2) 0.004
direction when
(3) 0.001 (4) 0.003
(1) It is subjected to high pressure

SO2 (g)  Cl2 (g)
34. In the equilibrium SO2 Cl2 (g) (2) It is subjected to high temperature
at 2000 K and 10 atm pressure, % Cl2 = % SO2 (3) Inert gas (Argon) is added at constant pressure
= 40 (by volume). Then correct option is
(4) Carbon (solid) is added
(1) Kc = 0.1 mol L–1
39. Le-Chatelier's principle is not applicable to
n(SO2Cl2 ) 1
(2)  at equilibrium (1)

Fe(s)  S(s)
FeS(s)
n(SO2 ) 4
(3) n(SO2Cl2) = n(SO2) = n(Cl2) (2)

H2 (g)  I2 (g)
2HI(g)
(4) Kp = 8 atm
(3)

N2 (g)  3H2 (g)
2NH3 (g)

35. For the reaction, N2 (g)  O2 (g)
2NO(g)
(4)

N2 (g)  O2 (g)
2NO(g)
Equilibrium constant Kc = 2.
Degree of association is 40. Which causes the change in the value of
equilibrium constant of any equilibria?
1 1 (1) Adding of inert gas at constant pressure
(1) (2)
1 2 1 2
(2) Increasing the pressure
2 2 (3) Adding of inert gas at constant volume

(3) (4)
1 2 1 2 (4) Decreasing the temperature
36. The value of Kp for the reaction, 41. The equilibrium constants for A2 (g) 2A (g)
at 400 K and 600 K are 1 × 10–8 and 1 × 10–2
2SO2(g) + O2(g) 2SO3(g) is 5.
respectively. The reaction is
What will be the partial pressure of O 2 at
(1) Exothermic
equilibrium when equal moles of SO2 and SO3 are
present at equilibrium? (2) Endothermic
(1) 0.5 (2) 0.3 (3) May be exothermic or endothermic
(3) 0.2 (4) 0.1 (4) No heat is evolved or abosorbed
NEET Equilibrium 45
42. The number of hydrogen ions in 10 ml of a solution 49. The pH of a mixture of 100 ml 1M H2SO4 and 200
with pH = 13 is ml 1N NaOH at 25°C is
(1) 1013 (1) More than 7 (2) Less than 7
(2) 6.023 × 108 (3) Equal to 7 (4) Can’t predict
(3) 6.023 × 1010 50. The pH of a mixture of 0.01M HCl and 0.1M
(4) 6.023 × 1013 CH3COOH is approximately
43. In the following reaction (1) 1 (2) 2
(3) 4 (4) 7
HC2 O 4  PO34

2 2
HPO 4  C2O 4
51. Two samples of CH3COOH each of 10 g were
which pair can act as Bronsted bases only? taken separately in two vessels containing water of
(1) HC2O4– and PO43– (2) HPO42– and C2O42– 6 litre and 12 litre respectively at 27°C. The degree
of dissociation of CH3COOH will be
(3) HC2O4– and HPO42– (4) PO43– and C2O42–
(1) More in 12 litre vessel
44. Which of the following solutions will have pH close
to 1? (2) More in 6 litre vessel
M M (3) Equal in both vessels

(1) 100 ml, HCl  100 ml, NaOH
5 5 (4) Half in 6 litre vessel than in 12 litre vessel
M M 52. Which is incorrect?

(2) 55 ml, HCl  45 ml, NaOH
10 10 (1) Conjugate acid of H2O is H3O+
(2) Conjugate base of HCO3– is CO32–
M M
(3) 10 ml, HCl  90 ml, NaOH
10 10 (3) Conjugate base of NH3 is NH2
(4) Conjugate base of HOCl is Cl–
M M
(4) 75 ml, HCl  25 ml, NaOH
5 5 53. When a small amount of HCl is added to a buffer
solution of acetic acid and sodium acetate
45. If ionic product of water is Kw = 10–16 at 4°C, then
a solution with pH = 7.5 at 4°C will (1) pH Increases
(1) Turn blue litmus red (2) Turn red litmus blue (2) [H+] decreases
(3) Be neutral to litmus (4) Be alkaline (3) Dissociation of acetic acid decreases
46. The pH of 10–11 M HCl at 25°C is (4) [CH3COO–] increases

(1) 11 54. A buffer solution can be obtained from
(2) 3 (1) HCN and KCN (2) CH3COONH4
(3) Slightly greater than 7 (3) NH4Cl and NH4OH (4) All of these
(4) Slightly less than 7 55. At 30°C, the solubility of Ag2CO3 (Ksp = 8 × 10–12)
47. When equal volumes of pH = 4 and pH = 6 are would be maximum in 1 litre of
mixed together then the pH of the resulting solution (1) 0.05 M Na2CO3 (2) 0.05 M AgNO3
will be [log 5 = 0.7]
(3) Pure water (4) 0.05 M NH3
(1) 4.3 (2) 4.7
56. Silver nitrate is gradually added to an aqueous
(3) 5 (4) 5.3 solution containing 0.01 M each of chloride,
bromide and iodide ions. The correct sequence
M (decreasing order) in which the halides will be
48. The pH of Ca(OH)2 is
100 precipitated is
(1) 1.699 (2) 12 (1) Br–, Cl–, I– (2) I–, Cl–, Br–
(3) 12.301 (4) 12.699 (3) I–, Br–, Cl– (4) Cl–, Br–, I–
46 Equilibrium NEET
57. The solubility product of AgBr is 4.9 × 10–9. The 59. The solubility product of BaSO4 is 4 × 10–10. The
solubility of AgBr will be solubility of BaSO4 in presence of 0.02 N H2SO4
(1) 7 × 10–4 mole/litre will be
(2) 7 × 10–5 g/litre (1) 4 × 10–8 M (2) 2 × 10–8 M
(3) 1.316 × 10–2 g/litre (3) 2 × 10–5 M (4) 2 × 10–4 M

(4) 1 × 10–3 mole/litre 60. Solubility product of the salt, A x B y will be
represented most suitably, if the solubility is
58. In which of the following solution, AgCl has
represented by s
minimum solubility?
(1) 0.05 M AgNO3 (1) Ksp = xyyx(s)x×y
(2) 0.01 M CaCl2 (2) Ksp = xy + yx + sx+y
(3) 0.01 M NaCl (3) Ksp = xxyy(s)x+y

(4) 0.01 M NH4OH (4) Ksp = x·sx+y·y


Chapter 7 Equilibrium in Brief

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Chapter 7 Equilibrium in Brief

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Chapter 7

General Characteristics of Equilibria involving Physical processes

This constant is known as equilibrium constant.

EQUILIBRIUM IN CHEMICAL PROCESS

Rate of forward reaction (1) 

Characteristics of equilibrium constant

R is gas constant, H is enthalpy change, K1 and K 2 are equilibrium constants at temperatures

N2 + 2O2 2NO2 Overall reaction; K

[NO]2 [NO2 ]2 [NO2 ]2

and, Fe3+(aq) + SCN–(aq) [Fe(SCN)]2+(aq)

On the basis of the stoichiometric equation, we can write,

Kc = [CO2(g)] or Kp = pCO

ng = Number of moles of gaseous products – number of moles of gaseous reactants

Units of Equilibrium Constant

(4) 2 2 times its original pressure

2. Sulphide ion reacts with solid sulphur

S2– (aq)  S(s) S2–

S2– (aq)  2S(s) S32– (aq) ; K2 = 130

3. For the reaction, CaCO3(s) CaO(s) + CO2(g), Kp is equal to

APPLICATIONS OF EQUILIBRIUM CONSTANT

Reactants  Products Reactants  Products

Predict the extent of a reaction

Fe+3(aq) + SCN–(aq) [Fe(SCN)]2+(aq); Kc = 138 at 298 K

H2(g) + I2(g) 2HI(g); Kc = 57.0 at 700 K

N2(g) + O2(g) 2NO(g); Kc = 4.8 × 10–31 at 298 K

These generalisations may be represented as follows

Negligible Kc Kc Extremely large Kc

Calculating equilibrium concentrations

Step-1 : Write the balanced equation for the reaction.

Step-4 : Write expression for Kc or Kp.

Step-5 : Substitute equilibrium concentrations and calculate ‘x’.

Degree of dissociation and its relation with vapour density

where D = Vapour density before dissociation

Endothermic Reaction Exothermic Reaction

(1) Increase in temperature, Increase in temperature,

(2) Decrease in temperature, Decrease in temperature,

Example 4 : In the reaction A + B C + D, what will happen to the equilibrium if concentration of A is

(i) H2(g) + I2(g) 2HI(g)

(ii) N2(g) + 3H2(g) 2NH3(g)

(iii) N2O4(g) 2NO2(g)

RELATIONSHIP BETWEEN EQUILIBRIUM CONSTANT (K), REACTION QUOTIENT (Q) AND

 If G is negative, the reaction is spontaneous in the forward direction.

G  2.303 RT logK

Acid Base Concept :

Conjugate acid-base pairs

Properties of water : Pure water is always neutral at all temperatures.

pH   log[H ] and pOH   log[OH ]

e.g., pH for 10–3 M HCl is 3.

Solution : Kw = [H+][OH–] = 10–14

IONIZATION CONSTANTS OF WEAK ACIDS AND WEAK BASES

Relation between Ka and Kb of acid-base conjugates pair

Di and Polybasic Acids and Di and Polyacidic Bases

H2X(aq) H+(aq) + HX–(aq)

HX–(aq) H+(aq) + X–2(aq)

[H ][HX ] [H ][X2 ]

Similarly, for polybasic acids

COMMON ION EFFECT IN THE IONISATION OF ACIDS AND BASES

CH3COOH(aq) CH3COO–(aq) + H+(aq)

CH3COONa(aq) CH3COO–(aq) + Na+(aq)

Solution : CH3COOH CH3COO– + H+

[CH3 COO ][H ]

HYDROLYSIS OF SALTS AND THE pH OF THEIR SOLUTION

For the dissociation of weak base,