7

EQUILIBRIUM

FACT / DEFINITION TYPE QUESTIONS (b) The rate of condensation from vapour to liquid state is
equal to the rate of evaporation.
1. Which of the following is not a general characteristic of (c) The rate of condensation from vapour to liquid state is
equilibria involving physical processes ? much less than the rate of evaporation.
(a) Equilibrium is possible only in a closed system at a (d) The rate of condensation from vapour to liquid state is
given temperature. equal or less than the rate of evaporation.
(b) All measurable properties of the system remain 6. When pressure is applied to the equilibrium system
constant. Ice Water
(c) All the physical processes stop at equilibrium. Which of the following phenomenon will happen?
(d) The opposing processes occur at the same rate and (a) More ice will be formed
there is dynamic but stable condition. (b) Water will evaporate
2. The liquid which has a ………..vapour pressure is more (c) More water will be formed
volatile and has a ………….boiling point. (d) Equilibrium will not be formed
(a) Higher , higher (b) Lower, lower 7. A reaction is said to be in equilibrium when
(c) Higher, lower (d) Lower, higher (a) the rate of transformation of reactant to products is
3. Boiling point of the liquid depends on the atmospheric equal to the rate of transformation of products to the
pressure. It depends on the altitude of the place; at high reactants.
altitude the boiling point………….. (b) 50% of the reactants are converted to products.
(a) increases (c) the reaction is near completion and all the reactants
(b) decreases are converted to products.
(c) either decreases or increases (d) the volume of reactants is just equal to the volume of
(d) remains same the products.
4. In an experiment three watch glasses containing separately 8. Which of the following is not true about a reversible
1mL each of acetone, ethyl alcohol, and water are exposed reaction?
to atmosphere and the experiment with different volumes of (a) The reaction does not proceed to completion
the liquids in a warmer room is repeated, it is observed that (b) It cannot be influenced by a catalyst
in all such cases the liquid eventually disappears and the (c) Number of moles of reactants and products is always
time taken for complete evaporation in each case was equal
different. The possible reason is/are (d) It can be attained only in a closed container
(a) the nature of the liquids is different 9. If the synthesis of ammonia from Haber's process is carried
(b) the amount of the liquids is different out with exactly the same starting conditions (of partial
(c) the temperature is different pressure and temperature) but using D2 (deuterium) in place
(d) All of the above of H2. Then
5. A small amount of acetone is taken in a watch glass and it is (a) the equilibrium will be disturbed
kept open in atmosphere. Which statement is correct for (b) the composition of reaction mixture will remain same at
the given experiment? equilibrium.
(a) The rate of condensation from vapour to liquid state is (c) Use of isotope in reaction will not produce ammonia.
higher than the rate of evaporation. (d) At equilibrium rate of forward reaction will be greater
than the rate of reverse reaction
112 EQUILIBRIUM
10. Consider the following graph and mark the correct statement. 1
(a) (b) 6
6
HI
1
(c) (d) 36
HI 36
Conc.
H2+I2 H 2 + I2 16. Given the reaction between 2 gases represented by A2 and
B2 to give the compound AB(g).
A2(g) + B2(g) 2 AB(g).
Time Equal Time
At equilibrium, the concentration
of A2 = 3.0 × 10–3 M
(a) Chemical equilibrium in the reaction, H 2 I2 2HI of B2= 4.2 × 10–3 M
of AB = 2.8 × 10–3 M
can be attained from other directions.
lf the reaction takes place in a sealed vessel at 527°C, then
(b) Equilibrium can be detained when H2 and I2 are mixed
the value of KC will be :
in an open vessel.
(a) 2.0 (b) 1.9
(c) The concentrations of H2 and I2 keep decreasing while
(c) 0.62 (d) 4.5
concentration of HI keeps increasing with time.
(d) We can find out equilibrium concentration of H2 and 17. A reaction is A + B C + D. Initially we start with
I2 from the given graph. equal concentrations of A and B. At equilibrium we find
11. What are the product formed when Deuterium is added that the moles of C is two times of A. What is the equilibrium
equilibrium reaction of H2 and I2 ? constant of the reaction?
(i) HD (ii) DI 1 1
(a) (b)
(iii) D2 (iv) HI 4 2
(a) (i), (ii) and (iv) (b) (i) and (ii) (c) 4 (d) 2
(c) (ii) and (iv) (d) All of these
12. If a system is at equilibrium, the rate of forward to the reverse 18. In A B C . The unit of equilibrium constant is :
(a) Litre mole –1 (b) Mole litre
reaction is :
(a) less (b) equal (c) Mole litre–1 (d) No unit
(c) high (d) at equilibrium 19. For the reaction C(s) CO 2 (g) 2CO(g) , the partial
13. K1 and K2 are equilibrium constant for reactions (1) and (2) pressures of CO2 and CO are 2.0 and 4.0 atm respectively at
N2(g) + O2 (g) 2 NO (g) .............(1) equilibrium. The Kp for the reaction is.
1 1 (a) 0.5 (b) 4.0
NO(g) N 2 (g ) O 2 (g ) ......(2) (c) 8.0 (d) 32.0
2 2
20. In which of the following equilibrium Kc and Kp are not
Then,
equal?
2
(a) K1 = 1 (b) K1 = K22 (a) 2 NO( g ) N 2 (g)+O 2 ( g )
K2
(b) SO 2 (g)+NO2 ( g ) SO3 (g)+NO( g )
1 (c) H 2 (g)+I 2 ( g ) 2HI(g)
(c) K1 = (d) K1 = (K2)0
K2
(d) 2C(s)+O 2 ( g ) 2CO2(g)
14. The equilibrium constant for the reversible reaction
21. For the following reaction in gaseous phase
N2 + 3H2 2NH3 is K and for reaction
1
1 3 CO( g ) O 2 ( g ) CO 2 ( g ), K p / K c is
N2 H2 NH3, the equilibrium constant is K ' 2
2 2 (a) (RT)1/2 (b) (RT)–1/2
The K and K ' will be related as: (c) (RT) (d) (RT)–1
(a) K × K ' = 1 (b) K= K' 22. The KP/KC ratio will be highest in case of
(c) K ' K (d) K K' 1
(a) CO (g) O (g) CO2 (g)
15. In the following equilibrium reaction 2 2
2A B + C, (b) H2 (g) + I2 (g) 2HI (g)
the equilibrium concentrations of A, B and C are 1 × 10–3 M,
2 × 10–3 M and 3 × 10–3 M respectively at 300 K. The value (c) PCl5 (g) PCl3(g) + Cl2 (g)
of Kc for this equilibrium at the same temperature is
(d) 7H2 (g) + 2NO2 (g) 2NH3 (g) + 4H2O(g)
EQUILIBRIUM 113
23. For a chemical reaction ; 30. The thermal dissociation of calcium carbonate showing
A (g) + B ( ) D (g) + E (g) heterogeneous equilibrium is
Hypothetically at what temperature, Kp = Kc CaCO 3 (s) CaO(s) CO 2 (g)
(when, R = 0.08 -atm/mole-K)
(a) T = 0 K (b) T = 1K For this reactions which of the following is/are true
(c) T = 12.5 K (d) T = 273 K (i) Kć = [CO2(g)]
24. Steam reacts with iron at high temperature to give hydrogen (ii) Kp = pCO2
gas and Fe3O4 (s). The correct expression for the equilibrium (iii) [CaCO 3 (s)] and [CaO(s)] are both con stant
constant is (iv) [ CO2(g)] is constant
(a) (i), (ii) and (iv) (b) (i), (ii) and (iii)
PH2 (PH 2 ) 4 (c) (ii) and (iv) (d) (i), (iii) and (iv)
2
(a) (b)
PH2 O (PH 2O ) 4 31. In a reversible chemical reaction having two reactants in
2
equilibrium, if the concentration of the reactants are doubled
then the equilibrium constant will
(PH 2 ) 4 [Fe 3O 4 ] [Fe 3O 4 ]
(c) (d) (a) Also be doubled (b) Be halved
(PH 2O ) 4 [Fe] [Fe] (c) Become one-fourth (d) Remain the same
25. For the reaction C(s) + CO2(g) 2CO(g), Kp = 63 atm at 1000 32. On doubling P and V with constant temperature the
K. If at equilibrium : Pco = 10 Pco2, then the total pressure equilibrium constant will
of the gases at equilibrium is (a) remain constant (b) become double
(a) 6.3 atm (b) 6.93 atm (c) become one-fourth (d) None of these
(c) 0.63 atm (d) 0.693 atm 33. If for the reaction
26. The rate constant for forward and backward reaction of N2 + 3H2 2NH3, H = –92.38KJ/mole than what
hydrolysis of ester are 1.1 10 2 and 1 .5 10 3 per minute happens if the temperature is increased?
respectively. Equilibrium constant for the reaction
(a) Reaction proceed forward
CH3COOC2 H 5 H CH 3COOH C 2 H 5OH is
(b) Reaction proceed backward
(a) 4.33 (b) 5.33 (c) No effect on the formation of product
(c) 6.33 (d) 7.33
(d) None of these
27. Value of KP in the reaction
34. If Kc is in the range of ………………… appreciable
MgCO3(s) MgO(s) CO 2(g ) is concentrations of both reactants and products are present.
(a) KP = PCO (a) 10–4 to 104 (b) 10 – 3 to 103
2
PCO 2 PMgO (c) 10+3 to 10 – 3 (d) 10 – 5 to 103
(b) KP PCO 2 35. The reaction quotient (Q) for the reaction
PMgCO 3
N 2 ( g ) 3H 2 ( g ) 2NH 3 ( g )
PCO 2 PMgO
(c) KP
PMgCO 3 [ NH 3 ]2
is given by Q . The reaction will proceed from
PMgCO 3 [ N 2 ][ H 2 ] 3
(d) KP
PCO 2 PMgO right to left if
28. Which of the following is an example of homogeneous (a) Q = 0 (b) Q = Kc
equilibrium ? (c) Q < Kc (d) Q > Kc
where Kc is the equilibrium constant
(a) 2SO2 (g) O2 (g) 2SO3 (g)
36. The reaction quotient Q is used to
(b) (a) predict the extent of a reaction on the basis of its
C(s) H 2 O(g) CO(g) H 2 (g)
magnitude
(c) CaCO3 (s) CaO(s) CO 2 (g) (b) predict the direction of the reaction
(c) calculate equilibrium concentrations
(d) NH 4 HS(s) NH3 (g) H 2S(g) (d) calculate equilibrium constant
29. Unit of equilibrium constant for the given reaction is 37. The correct relationship between free energy change in a
Ni(s) + 4CO(g) Ni (CO)4(g) reaction and the corresponding equilibrium constant, Kc is
(a) (mol/l)–3 (b) (mol/l)3 (a) G = RT ln Kc (b) – G = RT ln Kc
(c) (mol/l) –4 (d) (mol/l)4 (c) G° = RT ln Kc (d) – G° = RT ln Kc
114 EQUILIBRIUM
43. Which of the following reaction will be favoured at low
38. Usin g the equation ( K e G /RT ), the reaction
pressure ?
spontaneity can be interpreted in terms of the value of G°
is/are (a) H 2 I 2 2HI

(a) If G > 0, then – G /RT is positive, and e G /RT> 1 (b) N 2 3H 2 2NH3

making K > 1, which implies a spontaneous reaction or
(c) PCl5 PCl3 Cl 2
the reaction which proceeds in the forward direction
to such an extent that the products are present (d) N2 O2 2NO
predominantly. 44. The equilibrium which remains unaffected by pressure
(b) If G > 0, then – G /RT is negative, and e G /RT change is
< 1 making K < 1, which implies a non-spontaneous (a) N 2 (g) O2 (g) 2NO(g)
reaction or a reaction which proceeds in the forward
(b) 2SO2 (g) O2 (g) 2SO3 (g)
direction to such a small degree that only a very minute
quantity of product is formed. (c) 2O3 (g) 3O2 (g)
(c) Both (a) and (b)
(d) 2NO 2 (g) N2 O4 (g)
(d) None of the above
39. Which of the following relation represents correct relation 45. Suitable conditions for melting of ice :
between standard electrode potential and equilibrium (a) high temperature and high pressure
constant? (b) high temperature and low pressure
nFE (c) low temperature and low pressure
I. log K (d) low temperature and high pressure
2.303 RT
46. In which of the following reactions, the equilibrium remains
nFE
unaffected on addition of small amount of argon at constant
II. K e RT volume?
nFE (a) H2 (g) + I2 (g) 2HI (g)
III. log K
2.303 RT (b) PCl5 (g) PCl3 (g) + Cl2 (g)
nFE
IV. log K 0.4342 (c) N2 (g) + 3H2 (g) 2NH3 (g)
RT (d) The equilibrium will remain unaffected in all
Choose the correct statement(s). the three cases.
(a) I, II and III are correct
47. Le-Chatelier principle is not applicable to
(b) II and III are correct
(a) H 2 ( g ) I 2 ( g ) 2HI( g )
(c) I, II and IV are correct
(d) I and IV are correct (b) Fe(s) S(s) FeS(s)
40. According to Le-chatelier’s principle, adding heat to a solid (c) N 2 ( g ) 3H 2 ( g ) 2NH 3 ( g )
liquid equilibrium will cause the
(a) temperature to increase (d) N 2 ( g ) O2 ( g ) 2NO( g )
(b) temperature to decrease 48. In an equilibrium reaction if temperature increases
(c) amount of liquid to decrease (a) equilibrium constant increases
(d) amount of solid to decrease (b) equilibrium constant decreases
41. Which one of the following information can be obtained on (c) any of the above
the basis of Le Chatelier principle? (d) no effect
(a) Dissociation constant of a weak acid 49. In a two-step exothermic reaction
(b) Entropy change in a reaction A2(g) + B2(g) 3C(g) D(g)
(c) Equilibrium constant of a chemical reaction Step 1 Step 2
(d) Shift in equilibrium position on changing value of a Steps 1 and 2 are favoured respectively by
constraint (a) high pressure, high temperature and low pressure, low
42. For the manufacture of ammonia by the reaction temperature
N2 3H2 2NH3 2 kcal (b) high pressure, low temperature and low pressure, high
the favourable conditions are temperature
(a) Low temperature, low pressure and catalyst (c) low pressure, high temperature and high pressure, high
(b) Low temperature, high pressure and catalyst temperature
(c) High temperature, low pressure and catalyst (d) low pressure, low temperature and high pressure, low
(d) High temperature, high pressure and catalyst temperature
EQUILIBRIUM 115
50. What happens when an inert gas is added to an equilibrium 59. Which of the following can act as both Bronsted acid and
keeping volume unchanged? Bronsted base?
(a) More product will form (a) Na2CO3 (b) OH–
(b) Less product will form (c) HCO3 – (d) NH3
(c) More reactant will form
(d) Equilibrium will remain unchanged 60. Conjugate acid of NH 2 is :
51. In a vessel N2, H2 and NH3 are at equilibrium. Some helium (a) NH4+ (b) NH3
gas is introduced into the vessel so that total pressure (c) NH2 (d) NH
increases while temperature and volume remain constant. 61. Among boron trifluoride, stannic chloride and stannous
According to Le Chatelier’s principle, the dissociation of chloride, Lewis acid is represented by
NH3 (a) only stannic chloride
(a) increases (b) decreases (b) boron trifluoride and stannic chloride
(c) remains unchanged (d) equilibrium is disturbed (c) boron trifluoride and stannous chloride
52. Effect of a catalyst on a equilibrium reaction. (d) only boron trifluoride
(i) A catalyst increases the rate of the chemical reaction 62. Which of the following molecules acts as a Lewis acid ?
by making available a new low energy pathway for the (a) (CH3)2 O (b) (CH3)3 P
conversion of reactants to products.
(c) (CH3)3 N (d) (CH3)3 B
(ii) It increases the rate of forward and reverse reactions
63. Which one of the following molecular hydrides acts as a
that pass through the same transition state and does
Lewis acid?
not affect equilibrium.
(iii) It lowers the activation energy for the forward and (a) NH3 (b) H2O
reverse reactions by exactly the same amount. (c) B2H6 (d) CH4
Which of the above statement(s) is/are correct ? 64. Which of these is least likely to act as Lewis base?
(a) Only (i) (b) (i) and (ii) (a) F– (b) BF3
(c) (i), (ii) and (iii) (d) (ii) and (iii) (c) PF3 (d) CO
53. Which of the following is/are electrolytes? 65. Which one of the following is the correct statement ?
(i) Sugar solution (ii) Sodium chloride (a) HCO3– is the conjugate base of CO32–.
(iii) Acetic acid (iv) Starch solution (b) NH2– is the conjugate acid of NH3.
(a) (i) and (iv) (b) (ii) and (iv) (c) H2SO4 is the conjugate acid of HSO4–.
(c) (ii) and (iii) (d) (i) and (iii) (d) NH3 is the conjugate base of NH2–.
54. The geometry of hydronium ion is 66. Water is well known amphoprotic solvent. In which chemical
(a) tetrahedral (b) linear reaction water is behaving as a base?
(c) trigonal pyramidal (d) trigonal planer (a) H 2SO 4 H 2 O H 3 O + HSO 4 –
55. Which of the following statements are correct regarding
Arrhenius theory of acid and base? (b) H 2O H2O H3O + OH –
(a) This theory was applicable to only aqueous solutions (c) H2O NH2 – NH3 OH –
(b) This theory was applicable to all solutions (d) H 2 O NH 3 NH 4 OH –
(c) This theory could not explain the basicity of
substances like ammonia which do not possess a 67. An acid/ base dissociation equilibrium is dynamic involving
hydroxyl group a transfer of proton in forward and reverse directions. Now, with
(d) Both (a) and (c) passage of time in which direction equilibrium is favoured ?
56. Would gaseous HCl be considered as an Arrhenius acid ? (a) in the direction of stronger base and stronger acid
(a) Yes (b) in the direction of formation of stronger base and
(b) No weaker acid
(c) Not known (c) in the direction of formation of weaker base and weaker
(d) Gaseous HCl does not exist acid
57. A base, as defined by Bronsted theory, is a substance which (d) in the direction of formation of weaker base and
can stronger acid
(a) lose a pair of electrons 68. Three reactions involving H2PO4– are given below:
(b) donate protons (i) H3PO4 + H2 H3O+ + H2PO4–
(c) gain a pair of electrons (ii) H2PO4– + H2O HPO42– + H3O+
(d) accept protons (iii) H2PO4– + OH– H3PO4 + O2–
58. BF3 is an acid according to In which of the above does H 2 PO 4 act as an acid ?
(a) Arrhenius concept (b) Bronsted-Lowry concept (a) (ii) only (b) (i) and (ii)
(c) Lewis Concept (d) Both (b) and (c) (c) (iii) only (d) (i) only
116 EQUILIBRIUM
69. The value of the ionic product of water 82. Which of the following has highest pH ?
(a) depends on volume of water
M M
(b) depends on temperature (a) KOH (b) NaOH
4 4
(c) changes by adding acid or alkali
(d) always remains constant M M
70. A base when dissolved in water yields a solution with a (c) NH 4 OH (d) Ca (OH) 2
4 4
hydroxyl ion concentration of 0.05 mol litre–1. The solution 83. A weak acid, HA, has a Ka of 1.00 × 10–5. If 0.100 mole of
is this acid dissolved in one litre of water, the percentage of
(a) basic (b) acidic acid dissociated at equilbrium is closest to
(c) neutral (d) either (b) or (c) (a) 1.00% (b) 99.9%
71. pH scale was introduced by : (c) 0.100% (d) 99.0%
(a) Arrhenius (b) Sorensen 84. A monobasic weak acid solution has a molarity of 0.005 and
(c) Lewis (d) Lowry pH of 5. What is the percentage ionization in this solution?
72. pH of solution is defined by expression (a) 2.0 (b) 0.2
1 (c) 0.5 (d) 0.25
(a) log [H ] (b) log
H 85. Calculate the pH of a solution obtained by diluting 1 mL of
0.10 M weak monoacidic base to 100 mL at constant
1 1 temperature if Kb of the base is 1 × 10–5 ?
(c) (d) (a) 8 (b) 9
log [H ] log [H ]
(c) 10 (d) 11
73. The pH of a 10–3 M HCl solution at 25°C if it is diluted 1000
86. The ionisation constant of an acid, Ka, is the measure of
times, will be –
strength of an acid. The K a values of acetic acid,
(a) 3 (b) zero hypochlorous acid and formic acid are 1.74 × 10–5, 3.0 × 10–
(c) 5.98 (d) 6.02 8 and 1.8 × 10–4 respectively. Which of the following orders
74. How many litres of water must be added to 1 litre an aqueous of pH of 0.1 mol dm–3 solutions of these acids is correct?
solution of HCl with a pH of 1 to create an aqueous solution (a) acetic acid > hypochlorous acid > formic acid
with pH of 2 ?
(b) hypochlorous acid > acetic acid > formic acid
(a) 0.1 L (b) 0.9 L
(c) formic acid > hypochlorous acid > acetic acid
(c) 2.0 L (d) 9.0 L
(d) formic acid > acetic acid > hypochlorous acid
75. What is the approximate pH of a 1 × 10–3 M NaOH solution?
87. The first and second dissociation constants of an acid H2 A
(a) 3 (b) 11
are 1.0 × 10–5 and 5.0 × 10–10 respectively. The overall
(c) 7 (d) 1 × 10–11 dissociation constant of the acid will be
76. Calculate the pOH of a solution at 25°C that contains
(a) 0.2 × 105 (b) 5.0 × 10–5
1× 10– 10 M of hydronium ions, i.e. H3O+.
(c) 5.0 × 1015 (d) 5.0 × 10–15.
(a) 4.000 (b) 9.0000
88. Equimolar solutions of HF, HCOOH and HCN at 298 K have
(c) 1.000 (d) 7.000
the values of Ka as 6.8 × 10–4 and 4.8 × 10–9 respectively.
77. The pH value of a 10 M solution of HCl is
What is the observed trend of dissociation constants in
(a) less than 0 (b) equal to 0 successive stages ?
(c) equal to 1 (d) equal to 2
+
(a) HF > HCN > HCOOH (b) HF > HCOOH > HCN
78. What is the H ion concentration of a solution prepared by
(c) HCN > HF > HCOOH (d) HCOOH > HCN > HF
dissolving 4 g of NaOH (Atomic weight of Na = 23 amu) in
89. At 25 C, the dissociation constant of a base, BOH, is
1000 ml?
1.0 10 12 . The concentration of hydroxyl ions in
(a) 10–10 M (b) 10–4 M
–1 0.01 M aqueous solution of the base would be
(c) 10 M (d) 10–13 M
(a) 1.0 10 5 mol L 1 (b) 1.0 10 6 mol L 1
79. Calculate the pOH of a solution at 25°C that contains 1× 10– 10
(c) 2.0 10 6 mol L 1 (d) 1.0 10 7 mol L 1
M of hydronium ions, i.e. H3O+.
90. Which of the following pKa value represents the strongest
(a) 4.000 (b) 9.0000
acid ?
(c) 1.000 (d) 7.000
(a) 10–4 (b) 10–8
80. The pH of 0.005 molar solution of H 2 SO 4 is approximately: (c) 10 –5 (d) 10–2
(a) 0.010 (b) 1 91. The dissociation constant of two acids HA1 and HA2 are
(c) 2 (d) 0.005 3.14 × 10– 4 and 1.96 × 10– 5 respectively. The relative
81. Which solution has pH equal to 10 ? strength of the acids will be approximately
(a) 10–4 M KOH (b) 10–10 M KOH (a) 1 : 4 (b) 4 : 1
–10
(c) 10 M HCl (d) 10–4 M HCl (c) 1 : 16 (d) 16 : 1
EQUILIBRIUM 117
92. Given (b) solubility product to AgI is less than that of NaI
Ka (c) of common ion effect
HF H 2 O H 3O F
(d) AgI forms complex with NaI
Kb 100. When sodium acetate is added to an aqueous solution of
F H 2O HF OH
acetic acid :
Which of the following reaction is correct (a) The pH of the solution decreases
1 (b) The pH of the solution increases
(a) Kb = Kw (b) Kb
Kw (c) The pH of the solution remains unchanged
Ka (d) An acid salt is produced
(c) Ka × Kb = Kw (d) Kw 101. Which of the following statements about pH and H+ ion
Kb
concentration is incorrect?
93. At 298K a 0.1 M CH3COOH solution is 1.34% ionized. The
ionization constant Ka for acetic acid will be (a) Addition of one drop of concentrated HCl in NH4OH
(a) 1.82 × 10– 5 (b) 18.2 × 10 –5 solution decreases pH of the solution.
(c) 0.182 × 10 –5 (d) None of these (b) A solution of the mixture of one equivalent of each of
CH3COOH and NaOH has a pH of 7
94. For dibasic acid correct order is
(c) pH of pure neutral water is not zero
(a) K a1 K a 2 (b) K a1 K a 2 (d) A cold and concentrated H2SO4 has lower H+ ion
(c) K a1 K a 2 (d) not certain concentration than a dilute solution of H2SO4
95. For a polybasic acid, the dissociation constants have a 102. H2 S gas when passed through a solution of cations
different values for each step, e.g., containing HCl precipitates the cations of second group
of qualitative analysis but not those belonging to the
H 3A H H2A ; K K a1 fourth group. It is because
H 2A H HA 2
;K Ka2 (a) presence of HCl decreases th e sulph ide ion
concentration.
HA 2 H A3 ; K Ka3 (b) solubility product of group II sulphides is more than
that of group IV sulphides.
What is the observed trend of dissociation constants in
(c) presence of HCl increases th e sulphide ion
successive stages ?
concentration.
(a) K a1 K a 2 K a 3 (b) K a1 K a 2 K a 3 (d) sulphides of group IV cations are unstable in HCl.
(c) K a1 Ka2 K a3 (d) K a1 Ka2 Ka3 103. A salt ‘X’ is dissolved in water of pH = 7. The salt is made
resulting solution becomes alkaline in nature. The salt is
96. K a1 , Ka2 and K a3 are the respective ionisation constants made
for the following reactions. (a) A strong acid and strong base
H 2S H HS (b) A strong acid and weak base
(c) A weak acid and weak base
HS H S2 (d) A weak acid and strong base
H 2S 2H S2 104. Aqueous solution of ferric chloride is acidic due to
(a) ionization (b) polarization
The correct relationship between K a1 , Ka2 and Ka3 is
(c) dissociation (d) hydrolysis
(a) K a3 K a1 K a2 (b) K a3 K a1 K a2 105. The pKa of a weak acid, HA, is 4.80. The pKb of a weak base,
BOH, is 4.78. The pH of an aqueous solution of the
(c) K a3 K a1 K a2 (d) K a3 K a1 / K a2 correspondng salt, BA, will be
97. Cationic hydrolysis gives the following solution: (a) 9.58 (b) 4.79
(a) acidic (b) basic (c) 7.01 (d) 9.22
(c) neutral (d) amphoteric 106. The pKa of a weak acid (HA) is 4.5. The pOH of an aqueous
98. In qualitative analysis, in III group NH4Cl is added before buffer solution of HA in which 50% of the acid is ionized is
NH4OH because (a) 7.0 (b) 4.5
(a) to increase the concentration of NH4+ions (c) 2.5 (d) 9.5
(b) to increase concentration of Cl– ions 107. A buffer solution is prepared in which the concentration of
(c) to reduce the concentration of OH– ions NH3 is 0.30M and the concentration of NH4+ is 0.20 M. If
(d) to increase concentration of OH– ions the equilibrium constant, Kb for NH3 equals 1.8 × 10–5,
99. The solubility of AgI in NaI solution is less than that in pure what is the pH of this solution ? (log 2.7 = 0.433).
water because : (a) 9.08 (b) 9.43
(a) the temperature of the solution decreases (c) 11.72 (d) 8.73
118 EQUILIBRIUM
108. What is [H+]
in mol/L of a solution that is 0.20 M in (a) Solubility product of As2S3 is less than that of ZnS
CH3COONa and 0.10 M in CH3COOH ? Ka for CH3COOH (b) Enough As+3 are present in acidic medium
= 1.8 × 10–5. (c) Zinc salt does not ionise in acidic medium
4 5 (d) Solubility product changes in presence of an acid
(a) 3.5 × 10 (b) 1.1 × 10
119. Solid Ba(NO 3 ) 2 is gradually dissolved in a
(c) 1.8 × 10 5 (d) 9.0 × 10 6 1.0 × 10–4 M Na2CO3 solution. At which concentration of
109. Which of the following pairs constitutes a buffer? Ba2+, precipitate of BaCO3 begins to form ? (Ksp for BaCO3
(a) NaOH and NaCl (b) HNO3 and NH4NO3 = 5.1 × 10–9)
(c) HCl and KCl (d) HNO2 and NaNO2 (a) 5.1 × 10–5 M (b) 7.1 × 10–8 M
110. Buffer solutions have constant acidity and alkalinity (c) 4.1 × 10 M–5 (d) 8.1 × 1–7 M
because 120. Solubility product of silver bromide is 5.0 × 10–13. The
(a) these give unionised acid or base on reaction with quantity of potassium bromide (molar mass taken as
added acid or alkali. 120 g mol–1) to be added to 1 litre of 0.05 M solution of
(b) acids and alkalies in these solutions are shielded from silver nitrate to start the precipitation of AgBr is
attack by other ions. (a) 1.2 × 10–10 g (b) 1.2 × 10–9 g
(c) they have large excess of H+ or OH– ions (c) 6.2 × 10–5 g (d) 5.0 × 10–8 g
(d) they have fixed value of pH 121. At 25°C, the solubility product of Mg(OH) 2 is
111. The buffering action of an acidic buffer is maximum when 1.0 × 10–11. At which pH, will Mg2+ ions start precipitating
its pH is equal in the form of Mg(OH) 2 from a solution of
(a) 5 (b) 7 0.001 M Mg2+ ions?
(c) 1 (d) pKa (a) 9 (b) 10
112. When a buffer solution, sodium acetate and acetic acid is (c) 11 (d) 8
diluted with water :
(a) Acetate ion concentration increases STATEMENT TYPE QUESTIONS
(b) H+ ion concentration increases 122. Read the following statements carefully and choose the
(c) OH– ion conc. increases correct answer
(d) H+ ion concentration remains unaltered (i) Water and water vapour remain in equilibrium position
113. The product of ionic concentration in a saturated solution at atmospheric pressure (1.013 bar) and at 100°C in a
of an electrolyte at a given temperature is constant and is closed vessel.
known as (ii) The boiling point of water is 100°C at 1.013 bar pressure
(a) Ionic product of the electrolyte (iii) Boiling point of the liquid depends on the atmospheric
(b) Solubility product pressure.
(c) Ionization constant (iv) Boiling point depends on the altitude of the place; at
(d) Dissociation constant high altitude the boiling point increases.
114. The Ksp for Cr(OH)3 is 1.6 × 10–30. The solubility of this (a) (i), (ii) and (iv) are correct
compound in water is : (b) (i), (iii) and (iv)
(a) 4 30 (b) 4 30 (c) (i), (ii) and (iii) are correct
1.6 10 1.6 10 / 27
(d) only (iii) is correct
(c) 1.6 10 30/ 27 (d) 1.6 10 30 123. You must have seen that when a soda water bottle is opened,
115. At 25°C, the solubility product of Mg(OH)2 is 1.0 × 10–11. some of the carbon dioxide gas dissolved in it fizzes out
At which pH, will Mg2+ ions start precipitating in the form rapidly. There is equilibrium between the molecules in the
of Mg(OH)2 from a solution of 0.001 M Mg2+ ions? gaseous state and the molecules dissolved in the liquid
(a) 9 (b) 10 under pressure i.e.,
(c) 11 (d) 8 CO2(gas) CO2(in solution)
116. pH of a saturated solution of Ba(OH)2 is 12. The value of Which of the following statements is/are correct regarding
solubility product (Ksp) of Ba(OH)2 is : this?
(a) 3.3 × 10– 7 (b) 5.0 × 10–7 (i) The phenomenon arises due to difference in solubility
(c) 4.0 × 10 –6 (d) 5.0 × 10–6 of carbon dioxide at different pressures.
117. If s and S are respectively solubility and solubility product (ii) This equilibrium is governed by Henry's law.
of a sparingly soluble binary electrolyte then : (iii) The amount of CO2 gas dissolved in liquid increases
(a) s = S (b) s = S2 with decrease of temperature.
(iv) The amount of CO2 gas dissolved in liquid decreases
1
(c) s S1/ 2 (d) s S with increase of temperature.
2 (a) (i), (ii) and (iv) are correct
118. Why only As+3 gets precipitated as As2S3 and not Zn+2 as (b) (i) , (iii) and (iv)
ZnS when H2S is passed through an acidic solution (c) (i), (ii) and (iii) are correct
containing As+3 and Zn+2? (d) only (iii) is correct
EQUILIBRIUM 119
124. Identify the CORRECT statements below regarding chemical 128. Which of the following statement(s) is/are correct ?
equilibrium: (i) G is negative, then the reaction is spontaneous and
(i) All chemical reactions which are in equilibrium are proceeds in the forward direction.
irreversible. (ii) G is positive, then reaction is non-spontaneous
(ii) Equilibrium is achieved when the forward reaction rate (iii) G is 0, then reaction is at equilibrium
equals the reverse reaction rate. (a) (i), (ii) and (iii) are correct
(iii) Equilibrium is achieved when the concentrations of (b) (i) and (ii)
reactants and product remain constant. (c) (ii) and (iii) are correct
(iv) Equilibrium is dynamic in nature (d) only (iii) is correct
(a) (i), (ii) and (iv) are correct 129. Read the following statements and choose the correct option
(b) (i), (ii), (iii) and (iv) are correct (i) Most of the acids taste sour
(c) (i), (ii) and (iii) are correct (ii) Acids turns blue litmus paper into red
(d) only (ii) is correct (iii) Bases turns red litmus paper blue
(iv) Bases taste bitter and feel soapy
125. Nobel gas is added to a reaction at equilibrium involving
(a) (i), (ii) and (iv) are correct
gaseous reactant and gaseous product.
(b) (i), (iii) and (iv)
Which of the following statement is true for above reaction?
(c) (i), (ii) and (iii) are correct
Statement 1 : Reaction will proceed forward, as total
(d) All statements are correct
pressure has increased due to addition of Nobel gas.
130. Which of the following statements are correct ?
Statement 2 : Reaction will proceed backward, if Nobel gas
(i) Strong acids have very weak conjugate bases
react with reactant.
(ii) Weak acids have very strong conjugate bases
(a) Statement 1 and 2 are both correct. (iii) Strong bases have strong conjugate acids
(b) Statement 1 is correct but statement 2 is incorrect. (iv) Weak bases have weak conjugate acids
(c) Statement 1 is incorrect but statement 2 is correct. (a) (i) and (ii) (b) (i) and (iii)
(d) Statement 1 and 2 both are incorrect. (c) (ii) and (iv) (d) (iii) and (iv)
126 Read the following statements and choose the correct 131. Which of the following statement(s) is/are correct ?
option. (i) Water has ability to act both as an acid and a base
(i) The value of equilibrium constant is independent of (ii) In pure water one H2O molecule donate proton and
initial concentrations of the reactants and products. acts an acid and another water molecule accepts a
(ii) Equilibrium constant is temperature dependent proton and acts as a base.
(iii) The equilibrium constant for the reverse reaction is (a) Both (i) and (ii) (b) Neither (i) nor (ii)
equal to the inverse of the equilibrium constant for the (c) Only (i) (d) Only (ii)
forward reaction. 132. Which of the following statements are correct ?
(iv) The equilibrium constant for the reverse reaction is (i) Ionic product of water (Kw) = [H+] [OH–] = 10–14M2
equal to the equilibrium constant for the forward (ii) At 298K [H+] = [OH–] = 10–7
reaction. (iii) Kw does not depends upon temperature
(a) (i), (ii) and (iv) are correct (iv) Molarity of pure water = 55.55M
(b) (i), (iii) and (iv) (a) (i), (ii) and (iii) (b) (i), (ii) and (iv)
(c) (i), (ii) and (iii) are correct (c) (i) and (iv) (d) (ii) and (iii)
(d) only (iii) is correct 133. Read the following statements and choose the correct option
127. Read the following statements and choose the correct option (i) Ka (ionization constant) is a measure of the strength
(i) The numerical value of the equilibrium constant for a of the acids
reaction indicates the extent of the reaction. (ii) Smaller the value of Ka, the stronger is the acid
(ii) An equilibrium constant give information about the (iii) Ka is a dimensionless quantity
rate at which the equilibrium is reached. (a) Statements (i) and (ii) are correct
(iii) If Kc > 103, products predominate over reactants, i.e., (b) Statements (ii) and (iii) are correct
if Kc is very large, the reaction proceeds nearly to (c) Statements (i), (ii) and (iii) are correct
completion. (d) Statements (i) and (iii) are correct
(iv) If Kc < 10–3, reactants predominate over products, 134. Which of the following statement(s) is/are correct ?
i.e., if Kc is very small, the reaction proceeds rarely. (i) In a tribasic acid 2nd and 3rd (Ka , Ka ) ionization
2 3
(a) (i), (ii) and (iv) are correct constants are smaller than the first ionisation (Ka )
1
(b) (i) , (iii) and (iv) (ii) It is difficult to remove a positively charged proton
from a negative ion due to electrostatic force.
(c) (i), (ii) and (iii) are correct
(a) Both (i) and (ii) (b) Neither (i) nor (ii)
(d) only (iii) is correct
(c) Only (i) (d) Only (ii)
120 EQUILIBRIUM
135. Which of the following statements are correct ? 139. Match the columns :
(i) The extent of dissociation of an acid depends on the Column-I Column-II
strength and polarity of the H –– A bond (where A is (A) N2(g) + 3H2(g) (p) n>0
an electronegative element.)
2NH3(g) (t = 300ºC)
(ii) As the strength of H–A bond increases, the energy
required to break the bond decreases. (B) PCl5(g) PCl3(g) (q) KP < KC
(iii) As the electronegativity difference between the atoms + Cl2(g) (t = 50ºC)
H and A increases, acidity increases (C) C(s) + H2O(g) (r) KP not defined
(a) (i) and (ii) (b) (ii) and (iii) CO(g) + H2(g)
(c) (i) and (iii) (d) (i), (ii) and (iii) (D) CH3COOH(l) + C2H5OH(l) (s) n=1
CH3COOC2H5(l)
MATCHING TYPE QUESTIONS
+ H2O(l)
136. Match the columns (a) A – (q), B – (p), C – (s), D – (r)
Column-I Column-II (b) A – (p), B – (q), C – (r), D – (s)
(A) H2O (l) H2O (vap) (p) rate of melting = rate of (c) A – (r), B – (p), C – (s), D – (q)
freezing (d) A – (s), B – (q), C – (p), D – (r)
(B) I2 (solid) (q) rate of evaporation 140. Match the columns :
I2 (vapour) = rate of condensation Column-I Column-II
(C) Ice water (r) rate of sublimation= rate (A) For the equilibrium NH4I(s) (p) Forward shift
of condensation NH3(g) + HI(g),
(a) A – (p), B – (q), C – (r) if pressure is increased
(b) A – (r), B – (q), C – (p) at equilibrium
(c) A – (p), B – (r), C – (q) (B) For the equilibrium (q) No change
(d) A – (q), B – (r), C – (p)
N2 + 3H2 2NH3
137. Match the Column-I with Column-II and mark the appropriate
If volume is increased
choice.
at equilibrium
Column-I Column-II
(C) For the equilibrium (r) Backward shift
(A) Liquid Vapour (p) Saturated solution
(B) Solid Liquid (q) Boiling point H2O(g) + CO(g)
(C) Solid Vapour (r) Sublimation point H2(g) + CO2 (g) inert gas is
(D) Solute (s) Solute (s) Melting point added at constant pressure
(solution) at equilibrium
(a) A – (p) ; B – (r) ; C – (q) ; D – (s) (D) For the equilibrium (s) More N2 and H2 is
(b) A – (q) ; B – (s) ; C – (r) ; D – (p) PCl5 PCl3 + Cl2 formed.
(c) A – (s) ; B – (q) ; C – (p) ; D – (r) what happens if more
(d) A – (r) ; B – (s) ; C – (q) ; D – (p) PCl5 is added
138. Match the columns. (a) A – (p), B – (q), C – (r), D – (s)
Column-I Column-II (b) A – (r), B – (s), C – (q), D – (p)
(Reactions) (Effect of increase in (c) A – (s), B – (p), C – (q), D – (r)
pressure)
(d) A – (q), B – (s), C – (r), D – (p)
(A) H2(g) + I2(g) 2HI(g) (p) Reaction proceed 141. Match the columns
backward. Column-I Column-II
1 (A) Qc < Kc, (p) Net reaction goes from
(B) CO(g) + O (g) (q) No effect on right to left.
2 2
CO2(g) reaction. (B) Qc > Kc, (q) Net reaction goes from
left to right.
(C) N2O4(g) 2NO2(g) (r) Reaction proceed
(C) Qc = Kc, (r) No net reaction occurs.
forward
(a) A – (p), B – (q), C – (r)
(a) A – (q), B – (r), C – (p)
(b) A – (r), B – (q), C – (p) (b) A – (r), B – (q), C – (p)
(c) A – (p), B – (r), C – (q) (c) A – (p), B – (r), C – (q)
(d) A – (q), B – (p), C – (r) (d) A – (q), B – (p), C – (r)
EQUILIBRIUM 121
142. Match the columns
CRITICAL THINKING TYPE QUESTIONS
Column-I Column-II
(A) Hydrochloric acid (p) Lemon and orange 148. N2(g) + 3H2(g) 2NH3(g), K1 (1)
(B) Acetic acid (q) Tamarind paste. N2(g) + O2(g) 2NO(g), K2 (2)
(C) Citric and ascorbic (r) Digestive juice
1
acids H2(g) + O (g) H2O(g), K3 (3)
2 2
(D) Tartaric acid (s) Constituent of
vinegar The equation for the equilibrium constant of the reaction
(a) A – (q), B – (r), C – (p), D – (s) 5
2NH3(g) + O2 (g) 2NO(g) + 3H2O(g), (K4) in terms
(b) A – (r), B – (s), C – (p), D – (q) 2
(c) A – (s), B – (p), C – (q), D – (r) of K1, K2 and K3 is :
(d) A – (r), B – (p), C – (s), D – (q)
143. Match the columns K1.K 2 K1.K 23
(a) K3 (b)
Column-I Column-II K2
(A) HClO4 (p) Strong base
(B) HNO2 (q) Strong acid K 2 .K 33
(C) NH2– (r) Weak base (c) K1 K2 K3 (d)
K1
(D) HSO4 – (s) Weak acid
(a) A – (s), B – (q), C – (p), D – (r) 149. Two equilibria, AB A B and
(b) A – (q), B – (s), C – (p), D – (r) AB B AB2 are simultaneously maintained in a
(c) A – (r), B – (p), C – (q), D – (s) solution with equilibrium constants, K1 and K2 respectively.
(d) A – (s), B – (q), C – (p), D – (r) The ratio of [A+] to [AB2–] in the solution is
(a) directly proportional to [B–]
ASSERTION-REASON TYPE QUESTIONS (b) inversely proportional to [B–]
Directions : Each of these questions contain two statements, (c) directly proportional to the square of [B–]
Assertion and Reason. Each of these questions also has four (d) inversely proportional to the square of [B–]
alternative choices, only one of which is the correct answer. You 150. Equilibrium constant (K) for the reaction
have to select one of the codes (a), (b), (c) and (d) given below. Ni(s) + 4CO(g) Ni(CO)4(g) can be written in terms of
(a) Assertion is correct, reason is correct; reason is a correct
(1) Ni(s) + 2CO2 (g) + 2C(s) Ni(CO)4(g);
explanation for assertion.
(b) Assertion is correct, reason is correct; reason is not a equilibrium constant = K1.
correct explanation for assertion (2) CO2(g) + C(s) 2CO(g);
(c) Assertion is correct, reason is incorrect equilibrium constant = K2.
(d) Assertion is incorrect, reason is correct. What is the relation between K, K2 and K2 ?
144. Assertion : Kp can be less than, greater than or equal to Kc. (a) K = (K1)/(K2)2 (b) K = (K1 . K2)
Reason : Relation between Kp and Kc depends on the (c) K = (K1) (K2) 2 (d) K = K1/K2
change in number of moles of gaseous reactants and
151. K1, K2 and K3 are the equilibrium constants of the following
products ( n).
reactions (I), (II) and (III) respectively:
145. Assertion : If a volume is kept constant and an inert gas
such as argon is added which does not take part in the (I) N2 + 2O2 2NO2
reaction, the equilibrium remains undisturbed. (II) 2NO2 N2 + 2O2
Reason : It is because the addition of an inert gas at constant
volume does not change the partial pressure or the molar 1
(III) NO2 N 2 + O2
concentrations of the substance involved in the reaction. 2
146. Assertion : Buffer system of carbonic acid and sodium The correct relation from the following is
bicarbonate is used for the precipitation of hydroxides of
third group elements. 1 1 1 1
(a) K1 (b) K1 2
Reason : It maintains the pH to a constant value, about 7.4. K2 K3 K2 K3
147. Assertion : Addition of silver ions to a mixture of aqueous
sodium chloride and sodium bromide solution will first 1
precipitate AgBr rather than AgCl. (c) K1 K2 K3 (d) K1 K3
K2
Reason : Ksp of AgCl > Ksp of AgBr.
122 EQUILIBRIUM
152. For the following three reactions a, b and c, equilibrium are in the ratio of 9 : 1. If degree of dissociation of X and A
constants are given: be equal, then total pressure at equilibrium (1) and (2) are in
(i) CO(g) + H 2O(g) CO 2 (g) + H 2 (g); K1 the ratio :
(a) 3 : 1 (b) 1 : 9
(ii) CH4 (g) + H2O(g) CO(g) + 3H2 (g); K 2 (c) 36 : 1 (d) 1 : 1
(iii) CH4 (g) 2H2O(g) CO2 (g) 4H2 (g);K3 159. The dissociation equilibrium of a gas AB2 can be represented
as :
(a) K1 K 2 K3 (b) K 2 K3 K1
2AB2 (g) 2AB(g) B2 (g)
(c) K3 = K1 K2 (d) K3 .K 23 K12
The degree of dissociation is ‘x’ and is small compared to 1.
153. The value of equilibrium constant of the reaction The expression relating the degree of dissociation (x) with
1 1 equilibrium constant Kp and total pressure P is :
HI g H 2 (g) I 2 is 8.0
2 2 (a) (2Kp/P) (b) (2Kp/P) 1/3
The equilibrium constant of the reaction (c) (2Kp/P) 1/2 (d) (Kp/P)
H2 g I2 (g) 2HI(g) will be: 160. On increasing the pressure, the gas phase reaction proceed
forward to re-establish equilibrium, as predicted by applying
1 1 the Le Chatelier’s principle. Consider the reaction.
(a) (b)
16 64 N 2 (g) 3H 2 (g) 2NH3 (g)
1 Which of the following is correct, if the total pressure at
(c) 16 (d)
8 which the equilibrium is established, is increased without
154. For the reversible reaction, changing the temperature?
N2(g) + 3H2(g) 2NH3(g) at 500°C, the value of Kp is (a) K will remain same
(b) K will decrease
1.44 10 5 when partial pressure is measured in
(c) K will increase
atmospheres. The corresponding value of K C , with
(d) K will increase initially and decrease when
concentration in mole litre–1, is
pressure is very high
5 5
1.44 10 1.44 10 161. The exothermic formation of ClF3 is represented by the
(a) 2
(b) 2 equation :
0.082 500 8.314 773
Cl 2 (g) 3F2 (g) 2ClF3 (g) ;
5 5
1.44 10 1.44 10
(c) (d) H = – 329 kJ
0.082 773 2 0.082 773 2
Which of the following will increase the quantity of ClF3 in
155. Two moles of PCl5 were heated in a closed vessel of 2L. At
an equilibrium mixture of Cl 2 , F2 and ClF3 ?
equilibrium 40% of PCl5 is dissociated into PCl3 and Cl2.
The value of equilibrium constant is (a) Adding F2
(a) 0.53 (b) 0.267 (b) Increasing the volume of the container
(c) 2.63 (d) 5.3 (c) Removing Cl2
156. PCl5 is dissociating 50% at 250°C at a total pressure of (d) Increasing the temperature
P atm. If equilibrium constant is Kp, then which of the 162. When hydrochloric acid is added to cobalt nitrate solution
following relation is numerically correct ? at room temperature, the following reaction takes place out
(a) Kp = 3P (b) P = 3Kp the reaction mixture becomes blue. On cooling the mixture it
2K P 2P becomes pink. On the basis of this information mark the
(c) P = (d) Kp =
3 3 correct answer.
157. For the decomposition of the compound, represented as 3
CO H 2 O 6 (aq) 4Cl (aq)
NH 2 COONH 4 ( s ) 2NH 3 ( g ) CO 2 ( g )
(pink)
the Kp = 2.9 × 10–5 atm3.
2
If the reaction is started with 1 mol of the compound, the COCl4 (aq) 6H 2 O(l )
total pressure at equilibrium would be : (blue)
(a) 1.94 × 10–2 atm (b) 5.82 × 10–2 atm (a) H > 0 for the reaction
–2
(c) 7.66 × 10 atm (d) 38.8 × 10–2 atm (b) H < 0 for the reaction
158. The values of Kp1 and Kp2 for the reactions (c) H = 0 for the reaction
X Y Z ...(1) (d) The sign of H cannot be predicted on the
basis of this information.
and A 2B ...(2)
EQUILIBRIUM 123
163. In HS–, I–,
RNH2 and NH3, order of proton accepting 172. The dissociation constants for acetic acid and HCN at 25°C
tendency will be are 1.5 × 10–5 and 4.5 × 10–10 respectively. The equilibrium
(a) I– > NH3 > RNH2 > HS– constant for the equilibrium
(b) HS– > RNH2 > NH3 > I– CN– + CH3COOH HCN + CH3COO– would be:
(c) RNH2 > NH3 > HS– > I– (a) 3.0 × 10– 5 (b) 3.0 × 10– 4
(d) NH3 > RNH2 > HS– > I– (c) 3.0 × 10 4 (d) 3.0 × 105
164. Which equilibrium can be described as an acid-base reaction 173. If degree of dissociation of pure water at 100°C is
using the Lewis acid-base definition but not using the 1.8 × 10–8, then the dissociation constant of water will be
Bronsted-Lowry definition? (density of H2O = 1 gm/cc)
(a) 2NH3 + H2SO4 2NH4+ + SO42– (a) 1 × 10–12 (b) 1 × 10–14
(c) 1.8 × 10 –12 (d) 1.8 × 10–14
(b) NH3 + CH3COOH NH4+ + CH3COO–
174. Ionisation of weak acid can be calculated by the formula
(c) H2O + CH3COOH H3O+ + CH3COO–
Ka 100
(d) [Cu(H2O)4]2– + 4 NH3 [Cu(NH3)4]2+ + 4H2O (a) 100 (b) ( pK a pH )
c 1 10
165. Equal volumes of three acid solutions of pH 3, 4 and 5 are (c) Both (a) and (b) (d) None of these
mixed in a vessel. What will be the H+ ion concentration in 175. Equimolar solutions of the following were prepared in water
the mixture ? separately. Which one of the solutions will record the highest
(a) 1.11 × 10–4 M (b) 3.7 × 10–4 M pH ?
(c) 3.7 × 10– 3 M (d) 1.11× 10–3 M (a) SrCl2 (b) BaCl2
–10
166. The pH of 10 M NaOH solution is nearest to: (c) MgCl2 (d) CaCl2
(a) 6 (b) – 10 176. Solubility product constant (Ksp) of salts of types MX, MX2
(c) 4 (d) 7 and M3X at temperature T are 4.0 × 10–8, 3.2 × 10–14 and
167. 100 mL of 0.04 N HCl aqueous solution is mixed with 100 mL 2.7 × 10–15, respectively. Solubilities (mol dm–3) of the salts
of 0.02 N NaOH solution. The pH of the resulting solution at temperature 'T' are in the order –
is: (a) MX > MX2 > M3X (b) M3X > MX2 > MX
(a) 1.0 (b) 1.7 (c) MX2 > M3X > MX (d) MX > M3X > MX2
(c) 2.0 (d) 2.3 177. In qualitative analysis, the metals of Group I can be separated
168. Equal volumes of three acid solutions of pH 3, 4 and 5 are from other ions by precipitating them as chloride salts. A
mixed in a vessel. What will be the H+ ion concentration in solution initially contains Ag+ and Pb2+ at a concentration
the mixture ? of 0.10 M. Aqueous HCl is added to this solution until the
(a) 1.11 × 10–4 M (b) 3.7 × 10–4 M Cl– concentration is 0.10 M. What will the concentrations
of Ag+ and Pb2+ be at equilibrium?
(c) 3.7 × 10– 3 M (d) 1.11× 10–3 M
(Ksp for AgCl = 1.8 × 10–10, Ksp for PbCl2 = 1.7 × 10–5)
169. At 100°C the Kw of water is 55 times its value at 25°C. What
(a) [Ag+] = 1.8 × 10–7 M ; [Pb2+] = 1.7 × 10–6 M
will be the pH of neutral solution? (log 55 = 1.74)
(b) [Ag+] = 1.8 × 10–11 M ; [Pb2+] = 8.5 × 10–5 M
(a) 6.13 (b) 7.00
(c) [Ag+] = 1.8 × 10–9 M ; [Pb2+] = 1.7 × 10–3 M
(c) 7.87 (d) 5.13
(d) [Ag+] = 1.8 × 10–11 M ; [Pb2+] = 8.5 × 10–4 M
170. Ionisation constant of CH3 COOH is 1.7 × 10 –5 if
178. The solubility product (Ksp) of the following compounds
concentration of H+ ions is 3.4 × 10–4M, then find out initial
are given at 25°C.
concentration of CH3COOH molecules
Compound Ksp
(a) 3.4 × 10–4M (b) 3.4 × 10–3M
–3 AgCl 1.1 × 10–10
(c) 6.8 × 10 M (d) 6.8 × 10–4M
AgI 1.0 × 10–16
171. Values of dissociation constant, Ka are given as follows :
PbCrO4 4.0 × 10–14
Acid Ka Ag2CO3 8.0 × 10–12
HCN 6.2 × 10–10 The most soluble and least soluble compounds are
HF 7.2 × 10–4 respectively.
HNO2 4.0 × 10–4 (a) AgCl and PbCrO4 (b) AgI and Ag2CO3
Correct order of increasing base strength of the base CN–, (c) AgCl and Ag2CO3 (d) Ag2CO3 and AgI
_
F– and NO 2 will be : 179. What is the molar solubility of Fe(OH)3 if
(a)
_
(b)
_ Ksp = 1.0 ×10–38 ?
F CN NO2 NO2 CN F
_ _ (a) 3.16×10–10 (b) 1.386×10–10
(c) F NO2 CN (d) NO2 F CN –9
(c) 1.45×10 (d) 1.12×10–11
124 EQUILIBRIUM

FACT / DEFINITION TYPE QUESTIONS

[AB]2
16. (c) A2 + B2 2AB Kc
1. (c) 2. (c) 3. (b) [A 2 ][B2 ]
4. (d) The time taken for complete evaporation depends on
(i) the nature of the liquid, (ii) the amount of the liquid (2.8 10 3 ) 2 (2.8) 2
and (iii) the temperature. Kc 3 3
0.62
3 10 4.2 10 3 4.2
5. (c) When the watch glass is open to the atmosphere, the
rate of evaporation remains constant but the molecules 17. (c) A+ B C +D
are dispersed into large volume of the room. As a At eqb. x x 2x 2x
consequence the rate of condensation from vapour to
liquid state is much less than the rate of evaporation. 2x.2x
Kc = 4
6. (c) Ice melts with a reduction in volume. So Increase in x.x
pressure shifts equilibrium to water side, result in
melting of ice according to Lechatelier's principle. 18. (a) For A B C, n 1 2 1
7. (a) A reaction is said to be in equilibrium when rate of
n 1
forward reaction is equal to the rate of backward mol mol
Unit of K c
reaction. litre litre
8. (c)
= Litre mole–1
9. (b) The reaction mixtures starting either with H2 or D2
reach equilibrium with the same composition, except P 2 CO 4 4
that D2 and ND3 are present instead of H2 and NH3. 19. (c) Kp = ;K p 8; C(s) 1;
PCO 2 2
10. (a) Equilibrium can be attained by either side of the
reactions of equilibrium. The concentration of solids and liquids are taken as
11. (d) According to the idea of dynamic equilibrium there is unity.
possibility of formation of all product. 20. (d) 2C(s) +O 2 ( g ) 2 CO2 ( g )
12. (b) At equilibrium, the rate of forward and backward
n =2–1=+1
reactions is equal.
Kc and Kp are not equal.
13. (a) For reation (1)
21. (b) For a gaseous phase reaction Kp and Kc are related as
[NO]2 ng
K1 = Kp K c ( RT )
[N 2 ][O2 ]
For the given reaction,
and for reaction (2) 1
CO(g) + O2 ( g ) CO2(g)
[N 2 ]½ [O 2 ]½ 1 2
K2 = therefore K1 =
[NO] K 22 1
ng = 1– (1 + 0.5) = – 0.5 or
2
14. (c) N2 + 3H2 2NH3
1
K = [NH3]2 / [N2] [H2]3 .... (i) 2
Kp = Kc ( RT )
1 3
N2 H2 NH3 1
2 2 Kp
or = ( RT ) 2
K ' [NH3 ]/[N 2 ]1/ 2 [H 2 ]3/ 2 .... (ii) Kc
Dividing equation (i) by equation (ii), we get K' = 22. (c) Using the relation KP = KC. (RT) n, we get
K KP
( RT ) n
15. (b) Given reaction, 2A B C KC
[B][C]
Kc KP
[A]2 Thus K will be highest for the reaction having
C
3 3
2 10 3 10
Kc =6 highest value of n.
(10 3 ) 2
EQUILIBRIUM 125
The n values for various reactions are Since [CaCO3 (s)] and [CaO(s)] are both constant,
therefore modified equilibrium constant for the thermal
1 1
(a) n 1– 1 – decomposition of calcium carbonate will be
2 2 Kć = [CO2(g)]
(b) n = 2 – (1 + 1) = 0 K p = [p CO2(g)]
(c) n = (1 +1) – 1= 1 31. (d) Equilibrium constant (K) is independent of
(d) n = (2 + 4) – (7 + 2) = – 3 concentrations of reactions and products.
Thus maximum value of n = 1 32. (a) Equilibrium constant is not effected by change in
n conditions like P and V. These changes can change
23. (c) As Kp = Kc RT g
only the time required to attain equilibrium.
Here ng = 1
33. (b) Reaction proceed forward according to Le-chatelier’s
So, Kp = Kc when RT = 1
principle.
Thus T = 12.5 K
34. (b)
24. (b) 3Fe(s) + 4H2O (steam) Fe3O4 (s) + 4 H2 (g) 35. (d) For reaction to proceed from right to left
(p H 2 ) 4 Q K c i.e the reaction will be fast in backward
Kp = 4 only gaseous products and reactants. direction i.e r b > rf.
(p H 2 O )
36. (b) The equilibrium constant helps in predicting the
25. (b) C(s) + CO2(g) 2CO(g) direction in which a given reaction will proceed at any
Apply law of mass action, stage. For this purpose, we calculate the reaction
quotient Q. The reaction quotient Q (Qc with molar
(PCO )2 (10PCO2 )2
KP or 63 concentration and Qp with partial pressures) is defined
PCO2 PCO2 in the same way as the equilibrium constant Kc except
that the concentrations in Qc are not necessary
(Given KP = 65) and PCO = 10PCO2 equilibrium values.
37. (d)
100(PCO2 ) 2 38. (c) Both (a) and (b) are correct for the equation,
or 63 or 63 100 PCO2
PCO2 K = e G /RT
39. (c) G = –2.303 RT log K
63
PCO 2 0.63 atm –nFE° = –2.303 RT log K
100
nFE (I)
log K
PCO 10PCO2 = 10 × 0.63 = 6.3 atm 2.303 RT
nFE
Ptotal = PCO2 PCO = 0.63 + 6.3 = 6.93 atm. 0.4342 ........ (i)
RT
26. (d) Rate constant of forward reaction (Kf) = 1.1 × 10–2 and
rate constant of backward reaction (Kb) = 1.5 × 10–3 nFE
ln K
per minute. RT
2 nFE
Equilibrium constant (Kc) Kf 1.1 10 ....... (ii)
3
7.33 K e RT
Kb 1.5 10
40. (d) Solid Liquid
27. (a) MgCO3 (s) MgO(s) CO 2 (g) It is an endothermic process. So when temperature is
MgO & MgCO3 are solid and they donot exert any raised, more liquid is formed. Hence adding heat will
pressure and hence only pressure exerted is by CO2. shift the equilbrium in the forward direction.
Therefore K P PCO2 41. (d) According to Le-chatelier's principle" whenever a
constraint is applied to a system in equilibrium, the
28. (a) All the reactants and products are in same physical
system tends to readjust so as to nullify the effect of
state.
the constraint.
1 42. (b) The most favourable conditions are :
[Ni(CO) 4 ] mol l
29. (a) K (mol l 1) 3 (i) High pressure ( n < 0)
[CO]4 (mol l 1 )4 (ii) Low temperature (Exothermic reaction)
30. (b) For the reaction (iii) Catalyst Fe is presence of Mo.
CaCO3 (s) CaO (s) + CO2 (g) 43. (c) As in this no. of moles are increasing hence low
On the basis of the stoichiometric equation, we can pressure will favour the forward direction.
write, n = (1 + 1) – 1 = 1
Kc =[CaO(s)] [CO2(g)/[CaCO3(s)] 44. (a) For n = 0, no effect of pressure.
126 EQUILIBRIUM
45. (a) Melting of ice involve absorption of heat i.e 60. (b) Because NH3 after losing a proton (H+) gives NH2–
Endothermic hence high temperature favour the NH3 + H2O NH 2– H 3O
process.
(Conjugate acid-base pair differ only by a proton)
Further for a given mass volume of water is less than
61. (c) Lewis acid is that compound which have electron
ice thus high pressure favour the process. High
deficiency. eg. BF3, SnCl2.
pressure and high temperature convert ice into liquid.
62. (d) (CH3)3 B - is an electron deficient, thus behave as a
46. (d)
lewis acid.
47. (b) Le chatelier principle is not applicable to solid-solid
equilibrium. 63. (c) Boron in B2H6 is electron deficient
48. (c) Effect of increase of temperature on equilibrium 64. (b) BF3 is Lewis acid (e– pair acceptor)
constant depends on the fact that whether the reaction 65. (c) HSO4– accepts a proton to form H2SO4.
is exothermic, or endothermic. If the reaction is Thus H2SO4 is the conjugate acid of HSO4–.
exothermic, it is favoured by low temperature and if HSO4
H
H 2SO 4
the reaction is endothermic, it is favoured by high base conjugate acid
temperature. of HSO 4

49. (d) A2 (g) B2(g) 3C(g) D(g) 66. (a) Bronsted base is a substance which accepts proton.
step-1 step-2 In option (a), H2O is accepting proton, i.e., acting as a
since the steps 1 and 2 are exothermic hence low base.
temprature will favour both the reactions. In step - 1 67. (c)
moles are increasing hence low pressure will favour it. 68 (a) (i) H 3PO 4 H 2O H 3O H 2PO 4
In step 2 moles are decreasing, hence high pressure acid1 base 2 acid 2 base1
will favour it.
(ii) H 2PO4 H2O HPO 4 H 3O
50. (a) On adding inert gas at constant volume the total acid1 base 2 base1 acid 2
pressure of the system is increased, but the partial
pressure of each reactant and product remains the (iii) Hbase
2 PO 4 OH
acid 2
H 3 PO 4 O
acid1 base 2
1
same. Hence no effect on the state of equilibrium.
51. (c) The backward reaction is not favoured at high pressure. Hence only in (ii) reaction H2PO4– is acting as an acid.
52. (c) A catalyst increases the rate of the chemical reaction 69. (b) The value of ionic product of water changes with the
by making available a new low energy pathway for the temperature.
conversion of reactants to products. It increases the 70. (a) Given : Hydroxyl ion concentration
rate of forward and reverse reaction that pass through [OH–] = 0.05 mol L–1. We know that
the same transition state and does not affect 14
[H ][OH ] 1 10
equilibrium.
14
Catalyst lowers the activation energy for the forward or [H ] 1 10 2 10 13 mol L–1
and reverse reactions by exactly the same amount. 0.05
53. (c) An aqueous solution of sodium chloride is comprised We also know that
entirely of sodium ions and chloride ions, while that of 13
acetic acid mainly contains unionized acetic acid pH log[H ] log [2 10 ]
molecules and only some acetate ions and hydronium = 13
log 2 log 10 log 2 ( 13) log 10
ions. This is because there is almost 100% ionization
in case of sodium chloride which is a strong electrolyte 0.3010 13.0000 12.6990.
as compared to less than 5% ionization of acetic acid Since the value of pH > 7, therefore the solution is
which is a weak electrolyte. basic.
54. (c) The hydronium ion has a trigonal pyramidal geometry 71. (b)
and is composed of three hydrogen atoms and one
1
oxygen atom. There is a lone pair of electrons on the 72. (b) pH = – log [H+] = log
oxygen giving it this shape. The bond angle between H
the atoms is 113°. 73. (c) On dilution [H+] = 10–6 M
= 10–6 mol
55. (d) Now dissociation of water cannot be neglected,
56. (b) According to Arrhenius, acids are those substances Total [H+] = 10–6 + 10–7 = 11 × 10–7
which give proton in aqueous solution, hence gaseous pH = –log [H+]
HCl is not an Arrhenius acid. = –log (11× 10–7) = 5.98
57. (d) Base accepts protons and acid donates protons. 74. (d) pH = 1 ; H+ = 10–1 = 0.1 M
58. (c) Lewis concept. pH = 2 ; H+ = 10–2 = 0.01 M
59. (c) H2CO3 H+ + HCO3– H+ + CO3–. M1 = 0.1 V1 = 1
HCO 3 can donate and accept H+. M2 = 0.01 V2 = ?
EQUILIBRIUM 127
From 83. (a) Given Ka = 1.00×10–5,
C= 0.100 mol
M1V1 = M2V2 for a weak electrolyte,
0.1 × 1 = 0.01 × V2 degree of dissociation
V2 = 10 litres
Volume of water added = 10 – 1 = 9 litres Ka 1 10 –5
( ) 10 2 1%
75. (b) Given [OH–] = 10–3 C 0.100
pOH = 3 84. (b) HA H+ + A–
pH + pOH = 14
pH = 14 – 3 = 11 [H ][A ]
Ka , [H+] = 10–pH
76. (a) Given [H3O+] = 1 × 10–10 M [HA]
at 25º [H3O+] [OH–] = 10–14 [H+] = 10–5 ; and at equilibrium [H+] = [A– ]
14
10 4
[OH ] 10 10 5 10 5
8
10 10 Ka 2 10
0.0015
OH OH
Now, [OH ] 10 p 10 4 10 p
Ka 2 10 8 6 3
pOH = 4 4 10 2 10
C .005
77. (a) Molarity (M) = 10M. HCl is a strong acid and it is
Percentage ionization = 0.2
completely dissociated in aqueous solutions as : HCl
(10) H+(10) + Cl–. 85. (c) M1V1 = M2V2
1 × 0.10 = M2 × 100
So, for every moles of HCl, there is one H+. Therefore
[H+] = [HCl] or [H+] = 10. M2 = 0.001 = 10–3
pH = – log[H+] = – log [10] = – 1. BOH B OH
4 C 0 0
78. (d) No. of moles of NaOH = 0.1 C(1 ) C C
40
[Molecular weight of NaOH = 40] C C
Kb
No. of moles of OH– = 0.1 C(1 )

0.1 Kb = C 2 ( 1 1)
Concentration of OH– = 1 litre 0.1Mole / L

14
Kb / C
As we know that, [ H ] [OH ] 10
13 Kb
[H ] 10 ( OH – 10 –1 ) [OH ] C C K bC
C
79. (a) Given [H3 O+] = 1 × 10–10 M
at 25º [H3O+] [OH–] = 10–14 10 5
10 3
10 4

10 14 pH + pOH = 14
4
[OH ] 10 pH = 14 – 4 = 10
10
10
86. (d)
OH OH
Now, [OH ] 10 p 10 4 10 p 87. (d) H 2A H+ + HA-
pOH = 4
80. (c) H2SO4 2H+ + SO42– [H ][HA ]
K1 = 1.0 × 10–5 = (Given)
Given concentration of H2SO4 = 0.005 M [H 2 A]
[H+] = 0.005 × 2 = 0.01 = 10–2
HA H A
pH = – log [H+] = – log 10–2 = 2
81. (a) pOH = – log [OH–] 10 [H ][A ] (Given)
pH + pOH = 14 K2 5.0 10
[HA ]
For 10–4 KOH, [OH–] = 10–4
pOH = – log [OH–] = – log 10–4 = 4
[H ]2 [A 2 ]
pH = 14 – pOH = 10 K K1 K2
82. (d) Among M/4 KOH, M/4 NaOH, M/4 NH4OH and [H 2 A]
M/4 Ca(OH)2, Ca(OH)2 furnishes highest number of = (1.0 × 10–5) × (5 × 10–10) = 5 × 10–15
OH– ions ( Ca(OH)2 Ca2+ + 2OH–).
88. (b) Acidic strength Ka
So pH of M/4 Ca(OH)2 is highest.
128 EQUILIBRIUM
89. (d) Given Kb = 1.0 × 10–12 101. (b) CH3COOH is weak acid while NaOH is strong base, so
[BOH] = 0.01 M [OH] = ? one equivalent of NaOH can not be neutralized with
one equivalent of CH3COOH. Hence the solution of one
BOH B OH equivalent of each does not have pH value as 7. Its pH
t o c 0 0
teq c(1 x) cx cx will be towards basic side as NaOH is a strong base
hence conc. of OH– will be more than the conc. of H+.
c 2 x2 cx 2 0.01x 2 102. (a) IVth group needs higher S2– ion concentration. In
Kb 1.0 × 10–12 = presence of HCl, the dissociation of H2 S decreases
c (1 x) (1 x ) (1 x )
hence produces less amount of sulphide ions due
On calculation, we get, x = 1.0 × 10–5 to common ion effect, thus HCl decreases the
Now, [OH–] = cx = 0.01 × 10–5 = 1 × 10–7mol L–1 solubility of H2 S which is sufficient to precipitate
90. (b) pKa = –log Ka IInd group radicals.
Smaller the value of pKa, stronger will be acid 103. (d) A salt of strong base with weak acid undergoes anionic
Acid having pKa value of 10–8 is strongest acid. hydrolysis to give basic solution.
4 104. (d) Ferric chloride is the salt of a strong acid and a weak
Ka1 3.14 10
91. (b) 1
4 :1 base, hence on hydrolysis it yields a mixture of weak
K a2 5
2 1.96 10 base and strong acid
FeCl3 3H2O Fe OH 3 3HCl
[H3O ][F ] weak base strong acid
92. (c) Ka ...(i)
[HF] Due to this, there is predominance of H+ ions in
solution, hence the solution is acidic.
[HF][OH ] 105. (c) In aqueous solution BA(salt) hydrolyses to give
Kb ...(ii)
[F ] BA + H2O BOH + HA
From (i) and (ii), KaKb = [H3O+][OH–]=Kw Base acid
(ionic product of water) Now pH is given by
2 1 1 1
1.34 pH pK w pKa pK b
93. (a) K c 2 0.1 1.8 10 5 2 2 2
100
94. (b) In polyprotic acids the loss of second proton occurs substituting given values, we get
much less readily than the first. Usually the Ka values 1
pH = (14 4.80 4.78) 7.01
for successive loss of protons from these acids differ 2
by at least a factor of 10–3 i.e., K a1 K a2 salt
106. (d) For acidic buffer pH = pKa + log
H+ + HX- (K a1 )
acid
H2 X
H+ + X2- (K a 2 )
A
HX- or pH pK a log
HA
95. (a) The values of dissociation constants for successive
stages decrease. Given pKa = 4.5 and acid is 50% ionised.
96. (a) [HA] = [A–] (when acid is 50% ionised)
97. (a) NH 4 Cl H 2 O NH 4OH HCl pH = pKa + log 1
pH = pKa = 4.5
or
pOH = 14 – pH = 14 – 4.5 = 9.5
Cl H 2O HCl H i.e., acidic 107. (b) Given [NH3] = 0.3 M, [NH4+] = 0.2 M, Kb = 1.8 × 10–5 .
98. (c) Due to common ion effect addition of NH4Cl in group
[salt]
(III) suppresses the ionisation of NH4OH with the pOH = pK b log [pKb = –log Kb;
result concentration of OH– decreases. [base]
99. (c) Solubility of weak electrolyte decreases in solvent pKb = –log 1.8 × 10–5]
having common ion. So solubility of AgI in NaI solution pKb = 4.74
is less than in pure water because of common ion effect. 0.2
100. (b) Dissociation of CH 3COOH is suppressed by the 4.74 log = 4.74 + 0.3010 – 0.4771 = 4.56
0.3
addition of sodium acetate (CH 3COONa ) due to pH = 14 – 4.56 = 9.436
common ion (CH3COO ) effect. The [ H ] decreases Salt
108. (d) pH p Ka+ log
raising the pH of the acid solution. Acid
Note : After the addition of CH3COONa to CH3COOH, Salt
a buffer solution is formed which has reserved pH log H log Ka – log
Acid
value.
EQUILIBRIUM 129
[OH–] = 10–2
Acid
log H = log Ka + log 2s = 10–2
Salt
10 2
Acid s
H = Ka 2
Salt Ksp = 4s3
0.15 3
= 1.8 × 10 = 9 × 10 6 M 10 2
0.2 = 4
2
109. (d) HNO2 is a weak acid and NaNO2 is salt of that weak
acid and strong base (NaOH). = 5 × 10–7
110. (a) Lets take an example of an acidic buffer CH3COOH 117. (c) Let binary electrolyte be AB
and CH3COONa.
AB A B
CH3COOH CH3COO – + H + ; s s s
CH3COONa CH3COO– + Na+ Hence, solubility product of AB
when few drops of HCl are added to this buffer, the H+ Ksp = [A+] [B–]
of HCl immediatly combine with CH3COO– ions to S = [s.] [s] s = S½
form undissociated acetic acid molecules. Thus there 118. (a) Ksp of As2 S3 is less than ZnS. In acid medium
will be no appreciable change in its pH value. Like ionisation of H2S is suppresed (common ion effect)
wise if few drops of NaOH are added, the OH – ions and Ksp of ZnS does not exceed.
will combine with H+ ions to form unionised water 119. (a) Given Na2CO3 = 1.0 × 10–4 M
molecule. Thus pH of solution will remain constant. [CO3– – ] = 1.0 × 10–4 M
111. (d) Buffering action is maximum when i.e. S = 1.0 × 10–4 M
[Salt] = [Acid] At equilibrium
i.e., pH = pKa [Ba++] [CO3– –] = Ksp of BaCO3
112. (d) pH or [H+] of a buffer does not change with dilution. 9
Ksp 5.1 10
113. (b) Solubility product is the product of ionic concentration [Ba++] = = 5.1 × 10–5 M
4
in a saturated solution of an electrolyte at a given [CO3 ] 1.0 10
temperature.
120. (b) AgBr Ag+ + Br-
114. (b) Cr(OH)3 (s) Cr 3 (aq.) 3OH (aq.)
s 3s Ksp = [Ag+] [Br–]
(s) (3s)3 = Ksp For precipitation to occur
Ionic product > Solubility product
27 S 4 K sp
K sp 5´10-13
[Br- ] = = = 10-11
K sp
1/ 4 30 1/ 4 [Ag + ] 0.05
1.6 10
s
27 27 i.e., precipitation just starts when 10–11 moles of KBr
is added to 1 AgNO3 solution
115. (b) Mg(OH) 2 Mg 2 OH Number of moles of Br– needed from
Ksp = [Mg++][OH–]2 KBr = 10–11
1.0 × 10–11 = 10–3 × [OH–]2 Mass of KBr = 10–11 × 120 = 1.2 × 10–9 g
121. (b) Mg(OH)2 Mg 2OH
10-11
[OH- ] = = 10-4 ++
Ksp = [Mg ][OH ] – 2
10-3
1.0 × 10–11 = 10–3 × [OH–]2
pOH = 4
pH + pOH = 14 10-11
[OH- ] = = 10-4
pH = 10 10-3
116. (b) Given pH = 12 pOH = 4
or [H+] = 10–12 pH + pOH = 14 pH = 10
Since, [H+] [OH–] = 10–14
14 STATEMENT TYPE QUESTIONS
10
[OH–] = = 10–2
10 12 122. (c) Boiling point depends on the altitude of the place; at
high altitude the boiling point decreases.
Ba(OH)2 Ba 2+ + 2OH 123. (a)
s 2s
130 EQUILIBRIUM
124. (b) Chemical reactions which are in equilibrium are (B) As n < 0 therefore if V , P reaction will go in
reversible the direction in which more number of gaseous
125. (c) Since equilibrium constant is related to the partial moles are formed i.e. backward direction.
pressure of reactant and product therefore if nobel (C) As n = 0 hence no effect.
gas is added, no change is observed, Statement 1 is (D) If concentration of reactant is increased reaction
incorrect. will go in the forward direction.
If Nobel gas react with reactant, concentraction of 141. (d) 142. (b)
reactant will decrease and therefore reaction will 143. (b) HClO4 is a strong acid
proceed backword according to Le– chatelier ’s HNO2 is a weak acid.
principle. NH2– is a very good proton acceptor and thus, it is a
126. (c) Equilibrium constant is temperature dependent having base.
one unique value for a particular reaction represented H2SO4 is a strong acid hence its conjugate base (HSO4–)
by a balanced equation at a given temperature. will be a weak base.
127. (b) An equilibrium constant does not give any information
about the rate at which the equilibrium is reached. ASSERTION-REASON TYPE QUESTIONS
128. (a) 129. (d)
130. (a) As strong acid dissociate completely in water hence 144. (a) Kp = Kc(RT) n
resulting base formed would be very weak. On the 145. (a) If the volume is kept constant and an inert gas such as
other hand a weak acid is only partially dissociated in argon is added which does not take part in the reaction,
aqueous solution, hence resulting base formed would the equilibrium remains undisturbed. It is because the
be strong. addition of an inert gas at constant volume does not
131. (a) H2O(l) + H2O(l) H3O+(aq) + OH–(aq) change the partial pressure or the molar concentration
acid base conjugate acid conjugate base of the substance involved in the reaction. The reaction
132. (c) Kw depends upon temperature as it is an equilibrium quotient changes only if the added gas is reactant or
constant. product involved in the reaction.
133. (d) Larger the value of Ka, the stronger is the acid. 146. (d) In biological systems buffer system of carbonic acid
134. (a) and sodium bicarbonate is found in our blood. It
135. (c) Bond energy being directly related to bond strength maintains the pH of blood to a constant value of about
increases with increase in bond strength 7.4.
147. (a) Ionic product of AgBr is greater than that of AgCl in
MATCHING TYPE QUESTIONS comparison with there solubility product AgBr will
precipitate first rather than that of AgCl.
136. (d)
137. (b) (A) Liquid Vapour equilibrium exists at the CRITICAL THINKING TYPE QUESTIONS
boiling point.
(B) Solid Liquid equilibrium exists at the 148. (d) To calculate the value of K4 in the given equation we
melting point. should apply :
eqn. (2) + eqn.(3) × 3 – eqn. (1)
(C) Solid Vapour equilibrium exists at the
sublimation point. K 2 K33
(D) Solute Solute (solution) equilibrium exists hence K4 =
K1
in a saturated solution.
149. (d) Given,
138. (a) In case of A no. of moles of product and reactant are K1 1
same, in case of B no. of moles of reactant are greater AB A B
so reaction go forward, in case of C the no. of moles of [A ] [B ]
K1
product are greater than no. of moles of reactant. [AB]
139. (a) K2
(A) KP = KC (RT) n AB B AB 2
KP [AB2 ]
= (RT) n as n = –ve KP < KC K2
KC [AB] [B ]
(B) n > 0
Dividing K1 and K2, we get
(C) n = 2 – 1 = 1
(D) As the reaction is not containing any gaseous K1 [A ] [B ]2
K
component therefore KP is not defined for this. K2 [AB2 ]
140. (b)
(A) As n > 0 therefore if P , reaction will go in the [A ] K
backward direction. [AB2 ] [B ]2
EQUILIBRIUM 131

Ni(CO)4 [CO]2 Kp
150. (a) K1 = ; K2 = 154. (d) Kc
2
[CO 2 ] [CO2 ] (RT) n
[Ni(CO) 4 ] 1.44 10 5
K= (R in L. atm. K–1 mole–1).
[CO]4 (0.082 773) 2

[Ni(CO)4 ] [CO 2 ]
2 155. (b) PCl5 PCl3 + Cl2
K= × a (1-x) ax ax
[CO2 ]2 [CO]2
a = 2, x = 0.4, V = 2 L
K1 2 1 0.4
K PCl5 0.6 mol L 1
K 22 2
K1 2 0.4 1
151. (b) (I) N 2 2O 2 2NO 2 PCl3 Cl2 0.4 mol L
2
[NO 2 ]2
K1 ...(i) 0.4 0.4
[N 2 ][O 2 ]2 Kc 0.267
K2 0.6
(II) 2NO 2 N2 2O 2 156. (b) PCl5 PCl3 + Cl2
[N 2 ] [O2 ] 2 Moles at equilibrium
K2 ...(ii) 1 1 1
[NO 2 ]2
2 2 2
K3 1 Mole fraction at equilibrium
(III) NO2 N2 O2
2 1 1 1
[N 2 ]1/2 [O2 ] 3 3 3
K3
[NO 2 ] Partial pressure at equilibrium
2 [N 2 ][O 2 ]2 P P P
K3 ...(iii) 3 3 3
[NO2 ]2
P P
from equations (i), (ii) and (iii)
1 1 3 3 P
K1 Kp
K 2 ( K3 )2 P/3 3
152. (c) Reaction (c) can be obtained by adding reactions (a) 157. (b) NH 2 COONH 4 ( s ) 2NH 3 ( g ) CO 2 ( g )
and (b) therefore K3 = K1. K2 2
Hence (c) is the correct answer. PNH3 PCO2 2
153. (b) Given: Equilibrium constant (K1) for the reaction KP = PNH3 PCO2
PNH 2COONH 4 ( s)
K1 1 1
HI(g) H 2 (g) I 2 (g); K1 = 8; .........(i) As evident by the reaction, NH3 and CO2 are formed
2 2
in molar ratio of 2 : 1. Thus if P is the total pressure of
To find equilibrium constant for the following reaction
the system at equilibrium, then
H 2 (g) I2 (g) 2HI(g); K2 = ? .....(ii) 2 P 1 P
For this multiply (i) by 2, we get PNH3 PCO2
3 3
2HI(g) H 2 (g) I2 (g); K1 = 82 = 64 .....(iii) 2
[Note: When the equation for an equilibrium is 2P P 4 P3
KP =
multiplied by a factor, the equilibrium constant must 3 3 27
be raised to the power equal to the factor] Given KP = 2.9 × 10–5
Now reverse equation (iii), we get
4 P3
1 2.9 10 5
H 2 (g) I 2 (g) 2HI(g); K .....(iv) 27
64
[Note: For a reversible reaction, the equilibrium 5
2.9 10 27
constant of the backward reaction is inverse of the P3
4
equilibrium constant for the forward reaction.]
1
Equation (iv) is the same as the required equation (ii), 2.9 10 5
27 3
1 P = 5.82 × 10–2 atm
thus K2 for equation (ii) is i.e. option (b) is correct. 4
64
132 EQUILIBRIUM
158. (c) Given reaction are Total number of moles
X Y Z ..... (i) = 2 (1–x) + 2x + x = (2 + x)
and A 2B ......(ii) 2(1 x)
PAB = P where P is the total pressure.
2 (2 x)
Let the total pressure for reaction (i) and (ii) be P1 and
P2 respectively, then 2x x
PAB = P , PB P
K P1 (2 x) 2 (2 x)
9
(given) Since x is very small so can be neglected in denominator
KP2 1 Thus, we get
After dissociation, PAB = (1 – x) × P PAB = x × P
2
X Y Z x
PB P
2 2
At equilibrium (1– )
2
[Let 1 mole of X dissociate with as degree of PAB PB2
dissociation ] Now, K P
2
Total number of moles = 1– + + PAB2
= (1+ ) x
(x)2 P 2 .P
1 = 2
Thus PX = . P1 ; PY = P1 ; (1 x) 2 P 2
1 1
x 3 .P3
= [ 1–x 1]
PZ = .P1 2 1 P2
1 1
x 3 .P 2.K p 2K p 3
= or x3 = or x =
K P1 .P1 . 2 P P
1 1 160. (a) Justification : According to Le-Chatelier’s principle, at
constant temperature, the equilibrium composition will
1 change but K will remain same.
P1 / .P1 ... (i)
1 161. (a) The reaction given is an exothermic reaction thus
Similarly for A 2B according to Lechatalier’s principle lowering of
temperature, addition of F2 and / or Cl2 favour the for
At equilibrium (1– ) 2
ward direction and hence the production of ClF3 .
We have,
162. (a)
2 P2
2
1 163. (c) Strong base has higher tendency to accept the proton.
K P2 / P2 ...(ii) Increasing order of base and hence the order of
1 1
accepting tendency of proton is
Dividing (i) by (ii), we get I HS NH3 RNH 2
2
K P1 .P1 K P1 1 P1
or . 164. (d) [Cu(H2O)4]2+ + 4NH3 [Cu(NH3)4]2+ + 4H2O
K P2 2 K P2 4 P2
4 .P2 involves lose and gain of electrons. H2O is coordinated
to Cu by donating electrons (LHS). It is then removed
1 P1 K P1 9 by withdrawing electrons.
or 9 .
4 P2 K P2 1 165. (b) [H3O]+ for a solution having pH = 3 is given by
[H3O]+ = 1×10–3 moles/litre
P1 36 [ [H3O]+ = 10–pH]
or or P1 : P2 = 36 : 1
P2 1 Similarly for solution having pH = 4,
[H3O]+ = 1 × 10–4 moles/ litre and for pH = 5
159. (b) For the reaction
[H3O+] = 1×10–5 moles/ litre
2AB2 (g) 2AB(g) B2 (g) Let the volume of each solution in mixture be IL, then
at equi 2(1 x) 2x x
total volume of mixture solution L = (1 + 1 + 1) L = 3L
2 Total [H3 O] + ion present in mixture solution
AB B2 (2x) 2 x = (10–3 + 10–4 + 10–5) moles
Kc or K c
AB2
2
{2(1 x)}2 Then [H3O]+ ion concentration of mixture solution
3
= x3 [(1–x) can be neglected in denominator (1– x) 1] 10 10 4 10 5 0.00111
= M= M
The partial pressure at equilibrium are calculated on 3 3
the basis of total number of moles at equilibrium. = 0.00037 M = 3.7 ×10–4 M.
EQUILIBRIUM 133

10 On taking log on both side

166. (d) Given concentration of NaOH = 10 M
– log [H+] = –log (55 × 10–14)1/2
NaOH Na OH
1
10 10 M
10 10 pH = – log 55 7 log10
2
10
[OH ] from NaOH = 10 pH = – 0.87 + 7
We have to consider dissociation of H2O = 6.13
7 – +
[OH ] from H 2 O = 10 170. (c) CH3COOH CH3COO + H
7 10
Total [OH ] = 10 10 [ CH 3COO ][ H ]
Ka
1001 [ CH 3COOH ]
= 10 7 (0.001 1) = 10 7
= 10 10
1001 Given that,
1000
pOH = – log [OH ] [CH 3 COO ] [H ] 3.4 10 4 M
= (log1001 10 10 ) = – 3.004 + 10 = 6.9996 Ka for CH3COOH = 1.7 × 10–5
CH3COOH is weak acid, so in it [CH3COOH] is equal
pH = 14 – pOH = 14 – 6.996 = 7.004
to initial concentration. Hence
pH of 10–10 M NaOH solution is nearest to 7.
167. (c) Number of meq. of the acid = 0.04 × 100 = 4 (3.4 10 4 )(3.4 10 4 )
1.7 10 5
Number of meq. of the base = 0.02 × 100 = 2 [CH 3 COOH ]
Number of meq. of the acid left on mixing = 4 – 2 = 2
Total volume of the solution = 200 mL 4 4
3.4 10 3.4 10
No. of meq of the acid present in 1000 mL of the [ CH 3 COOH ]
1.7 10 5
solution = 10
= 6.8 × 10–3M
or No. of eq. of the acid in 1000 mL of the solution
171. (c) Higher the value of Ka lower will be the value of pKa
10
= = 0.01 i.e. higher will be the acidic nature. Further since
1000 CN–, F– and NO2– are conjugate base of the acids
Since the acid is monobasic and completely ionises in HCN, HF and HNO2 respectively hence the correct
solution order of base strength will be
0.01 N HCl = 0.01 M HCl F– < NO2– < CN–
Thus [H ] = 0.01 ( stronger the acid weaker will be its conjugate base)
pH = – log (0.01) = – (– 2) = 2
172. (c) Given, CH3COOH CH3COO– + H+ ;
168. (b) [H3O]+ for a solution having pH = 3 is given by
[H3O]+ = 1×10–3 moles/litre Ka1 , = 1.5 × 10– 5 ....(i)
[ [H3O]+ = 10–pH]
Similarly for solution having pH = 4, HCN H++ CN–; K a 2 = 4.5 × 10–10
[H3O]+ = 1 × 10–4 moles/ litre and for pH=5 or H+ + CN– HCN;
[H3O+] = 1×10–5 moles/ litre
1 1
Let the volume of each solution in mixture be IL, then K 'a 2 ...(ii)
total volume of mixture solution L = (1 + 1 + 1) L =3L Ka 2 4.5 10 –10
Total [H3O]+ ion present in mixture solution From (i) and (ii), we find that the equilibrium constant
= (10–3 + 10–4 + 10–5) moles (Ka) for the reaction,
Then [H3O]+ ion concentration of mixture solution CN– + CH3COOH CH3COO– + HCN, is
3
10 10 4 10 5 0.00111 Ka K a1 K a' 2
= M= M
3 3
= 0.00037 M = 3.7 ×10–4 M. 1.5×10 –5 1
= –10
105 3.33 10 4
169. (a) Kw at 25°C = 1 × 10–14 4.5×10 3
At 25ºC
wt. of solute per litre of solution
Kw = [H+] [OH–] = 10–14 173. (d) As, molarity,
At 100°C (given) Mol. wt. of solute
Kw = [H+] [OH–] = 55 × 10–14 1000
Molarity of H2O = mole/litre
for a neutral solution 18
[H+] = [OH–] H2O H+ + OH–
[H ] = 55 × 10–14
+ 2
c (1 – c c
or [H+] = (55 × 10–14)1/2
pH = – log [H+] c 2
Thus, K a c 2 = 1.8 × 10–14
1
134 EQUILIBRIUM
174. (c) For weak acid dissociation equilibria, degree of 1 1
é 3.2 ´10-14 ù 3
ú or éê 32 ´10-15 ùú 3
dissociation is given as :
Solubility of MX 2 = êê ú
êë 4 úû êë 4 úû
Ka Ka
% 100
c c 1
= éê8´10-15 ùú 3 or 2´10-5
ë û
[H ][A ] [H ]c [H ]
Also, K a 1
[HA] c (1 ) (1 )
é 2.7 ´10-15 ù 4
Solubility of M 3 X = êê ú
ú
log K a log H log
1 ëê 27 ûú
1
or pK a pH log
1 = éê10-16 ùú 4 or 10–4
ë û
Thus the solubilities are in the order MX > M3 X> MX2
1
pK a pH log i.e the correct answer is (d).
177. (c) Ksp = [Ag+] [Cl–]
1 1.8 × 10–10 = [Ag+] [0.1]
10pK a pH
[Ag+] = 1.8 × 10–9 M
Ksp = [Pb+2] [Cl–]2
1
or, 10pK a pH
1 1.7 × 10–5 = [Pb+2] [0.1]2
[Pb+2] = 1.7 × 10–3 M
1 178. (d) The solubility equilibrium for AgI is
pKa pH
[1 10 ] AgI (aq) Ag aq + I aq ;
175. (b) The highest pH will be recorded by the most basic Ksp = [Ag+][I–]
solution. The basic nature of hydroxides of alkaline Let solubility of AgI be S moles per litre,
earth metals increase as we move from Mg to Ba and [Ag+] = S, [I–] = S
thus the solution of BaCl2 in water will be most basic Ksp = [Ag+][I–]
and so it will have highest pH. 1 × 10–16 = (S) × (S) = S2
1
176. (d) MX M X (Where s is the solubility)
s s S = 1 10 16 2 1 10 8
On calculating solubility of all given compounds
Then Ksp s 2 or s K sp
Compound Solubility
® M 2+ + 2X -
Similarly for MX 2 ¾¾ AgCl 1 10 5

s 2s AgI 1 10 8

7
1 PbCrO4 2 10
K sp 3 Ag 2 CO3 1.26 10 4

K sp s (2 s ) 2 4 s3 or s
4
Ag2CO3 is most soluble and AgI is least soluble.
and for M 3 X 3M X 3 179. (b) Ksp = [Fe3+].[3OH–]
3s s So molar solubility of Fe3+ = S and [3OH–] = 3S
1 Fe(OH)3 Fe3 3OH
Ksp 4 [S] [3S]
Ksp (3s )3 s 27 s 4 or s 1.0 ×10–38 = [S] [3S]3
27
1.0 ×10–38 = S4 × 27
From the given values of Ksp for MX, MX2 and 1.0 10 38
M3 X, we can find the solubilities of those salts at S4 =
27
temperature, T.
S4 = 3.703×10–40
Solubility of MX = 4´10 -8 -4
= 2´10 40 1/ 4
S = 3.703 10 = 1.386 × 10–10