Chemical Thermodynamics and Thermochemistry

Choose the correct answers :

1. A gas occupies 2 litre at STP. It is provided 300 joule 9. A gas on subjecting to adiabatic expansion gets cooled
heat so that its volume becomes 2.5 litre at 1 atm. due to :
The change in its internal energy is (1) Fall in temperature
(1) 249.37 joule (2) 500 joule (2) Loss of kinetic energy
(3) 143.27 joule (4) 623 joule (3) Decrease in velocity
2. The work done when system raises a column of water (4) Energy used in doing work
of radius 5.0 mm through 10 cm is
10. The total entropy change for a system and its
(1) +3.85 ×10–3 J (2) –3.85 ×10–3 J
surroundings increases, if the process is :
(3) +38.5 ×10–8 J (4) –38.5 ×10–8 J
(1) Reversible (2) Irreversible
3. The work done when 50 g of Iron reacts with
(3) Exothermic (4) Endothermic
Hydrochloric acid in an open beaker at 25ºC
(1) – 22.12 joule (2) + 22.12 joule 11. The exchange of heat energy during chemical reaction
(3) + 2212.22 joule (4) – 2212.22 joule at constant temperature and pressure occurs in the
4. Work done in expansion of an ideal gas from 4 litre to form of :
6 litre against a constant external pressure of 2.5 atm (1) Free energy (2) Internal energy
was used to heat up 1 mole of water at 293 K. If (3) Enthalpy (4) Bond energy
specific heat of water is 4.184 J g –1, the final 12. Which plot represents for an exothermic reaction :
temperature of water is
R
(1) 273 K (2) 500 K P
H H
(3) 299.7 K (4) 298 K
(1) (2)
5. 1 mole of an ideal gas undergoes reversible isothermal P R
expansion from an initial volume V1 to a final volume Time Time

10 V1, and does 10 kJ of work. The initial pressure

was 1 × 107 Pa. If there were 2 moles of gas, its
H R P H R P
temperature must have been
(3) (4)
(1) 261.13 K (2) 300 K
Time Time
(3) 515 K (4) 1925 K
6. Change in entropy is negative for : 13. Which value of heat of formation indicates that the
(1) Bromine(l)   Bromine (g) product is the least stable :
(2) C(s) + H2O(g)   CO(g) + H2(g) (1) – 94 kcal (2) – 231.6 cal
(3) N2(g, 10 atm)   N2(g, 1 atm) (3) + 21.4 kcal (4) + 64.8 kcal
(4) Fe(1 mol, 400 K)   Fe(1 mol, 3.0 K)
14. A gaseous reaction was carried out, first keeping the
7. For the process, melting of ice at 260 K, the H is :
(1) Negative (2) Positive volume constant and next keeping the pressure
(3) Zero (4) Cannot be predicted constant. In the second experiment, there was an
8. Select the correct limitations of III law of increase in volume. The heats of reaction were
thermodynamics : different, because :
(1) Glassy solids at zero Kelvin has entropy greater (1) In the first case the energy was spent to keep
than zero the volume constant
(2) Solids having mixtures of isotopes do not have (2) In the second case energy was spent to expand
entropy zero at zero Kelvin
the gases
(3) Crystals of CO, N2O, NO, H2O etc., do not have
(3) Specific heats of compressed gases is more
zero entropy at zero kelvin
(4) Specific heats of liquified gases is more
(4) All of the above

[144]
 Chemical Thermodynamics and Thermochemistry

15. The enthalpy changes of formation of the gaseous 22. The dissociation energy of CH4 is 400 Kcal / mol and
oxides of Nitrogen (N 2 O and NO) are positive that of C2H6 is 670 Kcal/mole. C–C Bond energy
because of : will be
(1) The high electron affinity of Oxygen atoms
(1) 270.0 Kcal (2) 70.0 Kcal
(2) The high electron of Oxygen atoms
(3) 200 Kcal (4) 240 Kcal
(3) The high electron affinity of Nitrogen atoms
23. The units of entropy are
(4) The tendency of Oxygen to form O2–
(1) JK–1 mole–1 (2) KJ–1 mole–1
16. What is the difference between heats of a reaction
(3) KJ mole–1 K–1 (4) JK mole
at constant pressure and constant volume for the
24. The latent heat of vaporisation of a liquid at 500 K
reaction at 25ºC in kilo joules.
2 C6 H6 (l) + 15 O2 (g)  12 CO2 (g) + 6 H2O (l) and one atmospheric pressure is 10.0 Kcal/mole.
(1) – 7.4 kJ (2) – 9.4 kJ What will be the change in energy (E) of 3 mole of
(3) – 15.0 kJ (4) – 8.0 kJ a liquid at the same temperature.
(1) 13.0 Kcal (2) – 13.0 Kcal
17. The Bond Dissociation energies of gases H2, Cl2 and
(3) 27.0 Kcal (4) –27.0 Kcal
HCl and 104, 58, 103 kJ/mol respectively. What is
25. Which represents extensive property
the enthalpy of formation of HCl gas ?
(1) Temperature (2) Pressure
(1) + 22.0 Kcal (2) – 22.0 Kcal
(3) Refractive index (4) Entropy
(3) 44.0 Kcal (4) – 44.0 Kcal
26. Internal energy does not include
18. Heat of neutralisation for the reaction
NaOH + HCl  NaCl + H2O (1) Nuclear energy
is 57.1 kJ mole–1. What will be the heat released when (2) Vibrational energy
0.25 mole of NaOH is titrated against 0.25 mole of (3) Rotational energy
HCl. (4) Energy of gravitational pull
(1) 22.5 kJ (2) 57.1 kJ
1
(3) 14.3 kJ (4) 28.6 kJ 27. Enthalpy of CH4 + O2  CH3OH is negative. If
2
19. H represents the enthalpy of an endothermic
enthalpy of combustion of CH4 and CH3OH are x
reaction in kJ/mole. The minimum value for energy
and y respectively, then which relation is correct ?
of activation will be
(1) x > y (2) x < y
(1) Less than H (2) Zero
(3) x = y (4) x  y
(3) More than H (4) Equal to H
20. A spontaneous reaction is impossible if 28. In the reaction : S + 3/2 O2  SO3 + 2x kcal and
(1) Both H and S are negative SO2 + 1/2 O2  SO3 + y kcal, the heat of formation
of SO2 is
(2) Both H and S are positive
(1) (x + y) (2) (x – y)
(3) H is negative and S is positive
(3) (2x + y) (4) (2x – y)
(4) H is positive and S is negative
21. For a gaseous reaction 29. C (diamond) 
 C (graphite), H = –ve. This shows
A (g) + 3B (g)  3C (gas) + 3D (g) that
E = 17 Kcal at 27ºC, R = 2 Cals. (1) Graphite is more stable than diamond
then H will be (2) Diamond is more stable than graphite
(1) 15.8 (2) 18.2 (3) Both are equally, stable
(3) 20.4 (4) 16.4 (4) Stability cannot be predicted

[145]
 Chemical Thermodynamics and Thermochemistry

30. The heat required to raise the temperature of a body Equal volumes of C2H2 and H2 are combusted under
by 1 K is called identical condition. The ratio of heats evolved in two
(1) Specific heat (2) Thermal capacity cases is
(3) Water equivalent (4) Molar heat capacity (1) 5.37/1 (2) 1/5.37
31. The enthalpy of vaporization of liquid water using the (3) 1/1 (4) None of these
data
1 36. The heat of neutralisation of HCl by NaOH is –55.9
H2 (g) + O2 (g)  H2O (l); kJ/mole. If the heat of neutralisation of HCN by NaOH
2
H = –285.77 kJ/mole
is –12.1 kJ/mole, the energy of dissociation of HCN
1
H2 (g) + O2 (g)  H2O (g); is
2
H = –241.84kJ/mole (1) – 43.8 kJ (2) 43.8 kJ
(1) + 43.93 kJ/mol (2) – 43.93 kJ/mol (3) 68 kJ (4) –68 kJ
(3) + 527.61 kJ/mol (4) – 527.61 kJ/mol 37. Heats of combustion of CH4, C2H4, C2H6 are –890,
32. One mole of a non-ideal gas undergoes a change of –1411 and –1560 kJ/mole respectively. Which has the
state (2.0 atm, 3.0 L, 95 K)  (4.0 atm, 5.0 L, 245 lowest fuel value in kJ/g?
K) with a change in internal energy, U = 30.9 L (1) CH4 (2) C2H4
atm. The change in enthalpy (H) of the process in L (3) C2H6 (4) All are same
atm is 38. Heat of neutralisation of a strong acid by a strong
(1) 40.0 base is equal to H of :
(2) 42.3
(1) H+ + OH– H2O
(3) 44.0
(4) Not defined because pressure is not constant (2) H2O + H+ H3O+
33. In thermodynamics, a process is called reversible when
(1) Surroundings and system change into each other (3) 2H2 + O2 2H2O
(2) There is no boundary between system and
surroundings (4) CH3COOH+NaOH CH3COONa+ H2O
(3) The surroundings are always in equilibrium with
39. In which case of mixing of a strong acid and a base,
the system each of 1 N concentration, temperature increase is
(4) The system changes into the surroundings the highest ?
spontaneously (1) 20 ml acid and 30 ml alkali
34. The enthalpy change for a given reaction at 298 K is (2) 10 ml acid and 40 ml alkali
– x cal/mol. If the reaction occurs spontaneously at (3) 25 ml acid and 25 ml alkali
298 K, the entropy change at that temperature (4) 35 ml acid and 15 ml alkali
(1) can be negative but numerically larger than 40. 2.1 gm of Fe combines with S evolving 3.77 kJ. The
x 298 cal K–1 heat of formation of FeS in kJ/mole is :
(2) can be negative, but numerically smaller than (1) – 3.77 (2) – 1.79
x 298 K–1 (3) – 100.5 (4) None of these
. (3) cannot be negative 41. The heat capacity of liquid water at constant pressure,
(4) cannot be positive Cp, is 18 cals deg–1 mol–1. The value of heat capacity
of water at constant volume, Cv, is approximately
1
35. H2(g) + O2 (g) H2O (g), H = –241.8 kJ (1) 18 cal deg–1 mol–1
2
5 (2) 16 cal deg–1 mol–1
C 2 H 2 (g) O 2 (g) 2CO 2 (g) + H 2 O (g), (3) 10.8 cal deg–1 mol–1
2
H = 1300 kJ (4) Cannot be predicted

[146]
 Chemical Thermodynamics and Thermochemistry

42. Molar heat capacity of water in equilibrium with ice then the enthalpy of formation of H2SO4 at 298 K
at constant pressure is will be
(1) Zero (2)  (1) –814.4 kJ (2) +320.5 kJ
–1 –1 –1 –1
(3) 40.45 kJ K mol (4) 75.48 JK mol (3) –650.3 kJ (4) –933.7 kJ
43. A mixture of 2 mol of Carbon monoxide and 1 mol of 49. Which of the following statements is correct about
Oxygen in a closed vessel is ignited to get Carbon the heat of combustion ?
dioxide, then : (1) It may be exothermic in some cases and
(1) H > E (2) H < E endothermic in other cases
(3) H = E (4) Not definite (2) It is applicable to gaseous substances only
44. H f 0 of CO2(g), CO(g), N2O(g) and NO2(g) in kJ/ (3) It is always an exothermic reaction
mol are respectively –393, –110, 819 and 34. Calculate (4) Its value does not change with temperature
the H in kJ of the following reaction : 50. Based on the following thermochemical equation :
2NO2(g) + 3CO(g)  N2O(g) + 3CO2(g) 1. H2O(g) + C(s)  CO(g) + H2(g);H = 131 kJ
(1) 836 (2) 1,460 1
(3) –836 (4) None of these 2. CO(g) + O2(g)  CO2(g); H = –282 kJ
2
1
45. The standard enthalpies of formation of CO2(g) and 3. H2(g) + O2(g)  H2O(g); H = –242 kJ
2
H2O(l) are –393.5 and –286.2 kJ respectively. The heat
4. C(s) + O2(g)  CO2(g); H = x kJ
of combustion of liquid ethanol is –1398.2 kJ at 25ºC.
The standard enthalpy of formation of liquid ethanol is the value of X will be :
(1) –247.4 kJ/mol (2) +247.4 kJ/mol (1) –393 kJ (2) –655 kJ
(3) –528.6 kJ/mol (4) None of these (3) +393 kJ (4) +655 kJ

46. Given that heats of combustion of Ethylene, Hydrogen 51. Given that :
and ethane are –337.0, –68.4 and –373.0 kcal C + O2 CO2; H0 = –x kJ
respectively at 25ºC, the heat of reaction 2 CO + O2 2 CO2; H0 = –y kJ
C2H4(g) + H2(g)  C2H6(g) the enthalpy of formation of CO will be
at 25ºC will be (1) (y – 2x)/2 (2) y – 2x
(1) –32.4 kcal (2) –36.3 kcal (3) 2x – y (4) (x – y)/y
(3) –37.8 kcal (4) None of these 52. The heat of neutralization of aqueous Hydrochloric
47. A solution of 500 mL of 1 M KOH is added to 500 mL acid by NaOH is x kcal/mole of HCl. Calculate the
of 1 M HCl and the mixture is well stirred. The rise in heat of neutralization per mole of aqueous Acetic acid
temperature T 1 is noted. The experiment is then
(1) 0.5x kcal (2) x kcal
repeated using 250 mL of each solution and the rise in
(3) 2x kcal
temperature T2 is noted. Then T1 will be equal to :
(4) Cannot be calculated from the given data
(1) 4T2 (2) 2T2
53. If H is the enthalpy change and E is the internal
(3) T2 (4) T2/2 energy change accompanying a gaseous reaction, then
(1) H is always greater than E
48. If :
(2) H < E only if number of mol of gaseous
S + O2  SO2; H = –298.2 kJ
products is greater than the number of mol of
1
SO2 + O2  SO3; H = –98.7 kJ gaseous reactants
2
(3) H < E only if number of mol of gaseous
SO3 + H2O  H2SO4; H = –130.2 kJ
products is less than the number of mol of
1
H2 + O2  H2O; H = –287.3 kJ gaseous reactants
2
(4) None of these

[147]
 Chemical Thermodynamics and Thermochemistry

54. If the specific heat of a gas at constant pressure and 59. The Joule-Thomson co-efficient of an ideal gas is zero
specific heat of a gas at constant volume are Cp and because
Cv respectively, then (1) The molecules move in straight lines
(1) Cp – Cv = R (2) The volume of molecules is negligible
(2) Cv – Cp = R (3) There are no attractive forces between molecules
(3) (Cp – Cv)  (molecular mass of gas) = R (4) The molecules make elastic collisions
(4) (Cv – Cp)  (molecular mass of gas) = R 60. If P1, T1 and V represent the initial state and P2, T2
1 and V the final state of an ideal gas then entropy
55. In the reaction : P(s) + O2(g)  PO(g) the amount
2 change may be expressed as
of heat evolved is x kJ. Consider the following T2 P2
statements in this regard : (1) S = Cp ln T + R ln P
1 1
The x can be termed as :
T1 P1
1. Heat of reaction (2) S = Cv ln T – RT
T2 ln P
2 2
2. Heat of combustion of P
3. Heat of formation of PO T2 P1
(3) S = Cp ln T + R ln P
Of these statements : 1 2

(1) 1, 2 and 3 are correct (4) None of these

(2) 1 and 3 are correct 61. Which of the following statements is false ?
(3) 1 and 2 are correct
(1) Heat of solution is the heat exchanged when
(4) 2 and 3 are correct 1 mole of a substance dissolves in an infinitely
56. A system changes its position from state A to large volume of solvent say water
state B. The change in internal energy is given by (2) Heat of neutralisation is the heat change
E = EB – EA. This relationship is valid if involved when 1 mole of water is formed during
(1) The change is brought about in a reversible neutralisation e.g., NaOH (aq) + HCl (aq) 
manner NaCl (aq) + H2O, H = –57 kJ mol–1
(2) The change is brought about in an irreversible (3) The heat of neutralisation for a strong acid and
manner strong base is always –57 kJ mole–1 or 13.7 kcals
(3) The change is brought about at constant pressure (4) The heat of neutralisation of all acids and bases
(4) The change is brought about in any manner are constant and is 13,700 cals
62. Which of the following statements is false?
57. The heat capacity of air at room temperature and (1) When one compound is converted into another
1 atm pressure is 25 J K–1 mol–1. How much heat is with higher heat content, energy is absorbed
required to heat the room through 10 kelvin at room (2) If heat is absorbed during the course of a
temperature if 144 kg of air is present in room and reaction, the temperature of the system is likely
vapour density of air = 14.4 ? to fall
(1) 250 kJ (2) 25 kJ (3) If an exothermic reaction is isolated from its
(3) 50 kJ (4) None of these surroundings, the temperature of the system will
rise
58. The temperature below which a gas becomes cooler (4) None of these
on expansion is called the 63. Two 10 gm bars of different metals are heated to
(1) Critical temperature 60°C and then immersed in identical, insulated
(2) Reduced temperature containers each containing 200 gm of water at 20°C.
(3) Transition temperature The metal that causes higher rise in temperature will
(4) Inversion temperature have :

[148]
 Chemical Thermodynamics and Thermochemistry

(1) Higher atomic weight (4) Whether the reaction is carried out at constant
(2) Lower atomic weight pressure or constant temperature
(3) May have higher or lower atomic weight
71. When a certain amount of ethylene was combusted,
(4) None of the above 6226 kJ heat was evolved. If heat of combustion of
64. Select the correct alternate about entropy
ethylene is 1411 kJ, the volume of O2 (at NTP) that
(1) Tlim

S=0 (2) lim
T0
S=  entered into the reaction is
(1) 296.5 ml (2) 296.5 L
(3) lim
T0
S=0 (4) S(liquid) > S(vapour)
(3) 6226  22.4 L (4) 22.4 L
65. G at 298 k for the reaction
72. Standard heat of formation at 25°C of CH4(g), CO2(g)
A(g) + B(g) E(g)
and water (l) are 17.9 kcal/mole, –94.1 kcal/mole and
for which E = – 3.00 kcal and S = – 10.0 cal/K is
–68.3 kcal/mole respectively. Calculate the heat
(1) –3592 cal (2) –616 cal
change in the following reaction at 25°C (in k cal)
(3) 3592 cal (4) 616 cal
CH4(g) + 2O2(g) = CO2(g) + 2H2O(l)
66. Which of the following process is spontaneous?
(1) –144.5 (2) –180.3
(1) Diffusion of perfume molecules from one side (3) –248.6 (4) –212.8
of the room to the other
73. Given H°ioniz (HCN) = 45.2 kJ mol–1 and H°ioniz
(2) Decomposition of solid CaCO3 (CH3COOH) = 2.1 kJ mol–1. Which one of the
(3) Heat flow from a cold object to a hot object following facts is true?
(4) Climbing of a mountain (1) pKa (HCN) = pKa(CH3COOH)
67. AB, A2 and B2 are diatomic molecules. If the bond
(2) pKa (HCN) > pKa(CH3COOH)
enthalpies of A2, AB and B2 are in the ratio 1 : 1 : 0.5
(3) pKa (HCN) < pKa(CH3COOH)
and the enthalpy of formation of AB from A2 and B2
is –100 kJ mol-1, what is the bond enthalpy of A2 ? (4) pKa (HCN) = (45.17/2.07) pKa(CH3COOH)
(1) 400 kJ mol-1 (2) 200 kJ mol-1 74. The correct decreasing order of calorific values is
(3) 100 kJ mol-1 (4) 300 kJ mol-1 (1) C2H2 > C4H10 > C3H8 > C2H4
68. The lattice energy of solid NaCl is 180 kcal per mol. (2) C4H10 > C3H8 > C2H4 > C2H2
The dissolution of the solid in water in the form of (3) C2H4 > C3H8 > C4H10 > C2H2
ions is endothermic to the extent of 1 kcal per mol. If (4) None of these
the solvation energies of Na+ and Cl– ions are in the 75. When would the temperature of the system decrease?
ratio of 6 : 5, what is the enthalpy of hydration of (1) Adiabatic compression
Sodium ions ? (2) Isothermal expansion
(1) –85.6 kcal/mol (2) –97.5 kcal/mol (3) Isothermal compression
(3) 82.6 kcal/mol (4) +100 kcal/mol (4) Adiabatic expansion
69. Assuming the petrol is octane (C8H18) and has density
of 0.8 g/ml, 1.425 litre of petrol on complete CBSE – PMT
combustion will consume. 1. From the following bond energies
(1) 100 moles of O2 (2) 125 moles of O2 (1) H–H bond energy: 431.37 kJ mol–1
(3) 150 moles of O2 (4) 170 moles of O2 (2) C = C bond energy: 606.10 kJ mol–1
70. The factor which does not influence the heat of (3) C – C bond energy: 336.49 kJ mol–1
reaction is (4) C – H bond energy: 410.50 kJ mol–1
Enthalpy for the reaction;
(1) The physical state of reactants and products
(2) The temperature of the reaction H H H H
(3) The method by which the final products are | | | |
C  C H  H  H  C C H
obtained | | | | will be
H H H H
[149]
 Chemical Thermodynamics and Thermochemistry

(1) 553.0 kJ mol–1 (2) 1523.6 kJ mol–1 (4) If Gsystem = 0 the system has attained equilibrium
(3) –243.6 kJ mol–1 (4) –120.0 kJ mol–1 9. The enthalpy and entropy change for the reaction
2. The values of H and S for the reaction C(graphite) Br2(l) + Cl2(g)  2BrCl(g)
+CO2(g)  2CO(g) are 170 kJ a 170 JK–1 respec- are 30 kJ mol–1 and 105 J K–1 mol–1 respectively.
tively. This reaction will spontaneous at: The temperature at which the reaction will be in
equilibrium is
(1) 510 K (2) 710 K (1) 450 K (2) 300 K
(3) 910 K (4) 1110 K (3) 285.7 K (4) 273 K
3. Which of the following are not state functions? 10. The enthalpy of hydrogenation of cyclohexene is
(I) q + w (II) q – 119.5 kJ mol–1. If resonance energy of benzene is
(III)w (IV)H – TS – 150.4 kJ mol–1, its enthalpy of hydrogenation would
(2) (II), (III) and (IV) be
(3) (I), (II) and (III) (1) – 269.9 kJ mol–1 (2) – 358.5 kJ mol–1
(4) (II) and (III) (3) – 508.9 kJ mol–1 (4) – 208.1 kJ mol–1
4. Bond dissociation enthalpy of H2, Cl2 and HCl are 11. A reaction occurs spontaneously if
434, 242 and 431 kJ mol–1 respectively. Enthalpy of (1) TS > H and H is +ve and S is –ve
formation of HCl is (2) TS = H and both H and S are –ve
(1) 93 kJ mol–1 (2) –245 kJ mol–1 (3) TS < H and both H and S are +ve
(3) –93 kJ mol–1 (4) 245 kJ mol–1 (4) TS > H and both H and S are +ve
5. Consider the following reactions [ 12. The absolute enthalpy of neutralisation of the reaction
(a) H+(aq) + OH–(aq) = H2O(l); H = – X1kJ mol–1 MgO(s) + 2HCl(aq)  MgCl2(aq) + H2O(l) will be
1
(b) H2(g) + O = H2O(l); H = – X2kJ mol–1 (1) 57.33 kJ mol–1
2 2(g)
(c) CO2(g) + H2(g) = CO(g) + H2(l) – X3kJ mol–1 (2) –57.33 kJ mol–1
(3) Greater than –57.33 kJ mol–1
5 (4) Less than –57.33 kJ mol–1
(d) C2H2(g) + O = 2CO2(g)+H2O(l)+X4kJ mol–1
2 2(g) 13. Which of the following pairs of a chemical reaction
Enthalpy of formation of H2O(l) is is certain to result in a spontaneous reaction?
(1) + X3 kJ mol–1 (2) – X4 kJ mol–1
(3) + X1 kJ mol–1 (4) – X2 kJ mol–1 (1) Endothermic and decreasing disorder
6. Given the bond energies of H – H and Cl – Cl are
(2) Exothermic and increasing disorder
430 kJ mol–1 and 240 kJ mol–1 respectively and f H
(3) Endothermic and increasing disorder
for HCl is – 90 kJ mol–1, Bond enthalpy of HCl is
(4) Exothermic and decreasing disorder
(1) 380 kJ mol–1 (2) 425 kJ mol–1 14. Considering entropy (S) as a thermodynamic
(3) 245 kJ mol –1
(4) 290 kJ mol–1 parameter, the criterion for the spontaneity of any
7. Assume each reaction is carried out in an open process is
(1) Ssurroundings > 0 only
container. For which reaction will  H =  E?
(2) Ssystem + Ssurroundings > 0
(3) Ssystem – Ssurroundings > 0
(1) PCl5(g)  PCl3(g) + Cl2(g)
(4) Ssystem > 0 only
(2) 2CO(g) + O2(g)  2CO2(g)
15. If the bond energies of H – H, Br – Br, and H – Br
(3) H2(g) + Br2(g)  2HBr (g)
are 433, 192 and 364 kJ mol–1 respectively, the Hº
(4) C (s) + 2H2O (g)  2H2(g) + CO2(g)
for the reaction : H2 (g) + Br2 (g)  2 HBr (g) is
8. Identify the correct statement for change of Gibbs
energy for a system (G system) at constant
(1) –103 kJ (2) –261 kJ
temperature and pressure:
(3) +103 kJ (4) +261 kJ
(1) If Gsystem = 0, the system is still moving in a
16. Standard enthalpy and standard entropy changes for
particular direction.
the oxidation of ammonia at 298 K are –382.64
(2) If Gsystem < 0, the process is not spontaneous
kJ mol–1 and –145.6 J K–1 mol–1, respectively.
(3) If Gsystem > 0, the process is spontaneous
Standard Gibbs energy change for the same reaction
at 298 K is
(1) – 523.2 kJ mol–1
[150]
 Chemical Thermodynamics and Thermochemistry

(2) – 221.1 kJ mol–1 (3) –10.3 kJ (4) +6.2 kJ

(3) – 339.3 kJ mol–1 21. If the enthalpy change for the transition of liquid
(4) – 439.3 kJ mol–1 water to steam is 30 kJ mol–1 at 27ºC, the entropy
17. Match List - I (Equations) with List - II (Type of change for the process would be
processes) and select the correct option (1) 10 j mol–1 K–1 (2) 1.0 J mol–1 K–1
–1 –1
(3) 0.1 J mol K (4) 100 J mol–1 K–1
List - I List - II 22. Enthalpy change for the reaction,
(Equations) (Type of Process) 4H(g)  2H2(g) is –869.6 kJ
The dissociation energy of H – H bond is
(a) Kp > Q (i) Non spontaneous
(1) –434.8 kJ (2) –869.6 kJ
(b) G0 < RT ln Q (ii) Equilibrium (3) +434.8 kJ (4) +217.4 kJ
(c) Kp = Q (iii) Spontaneous and 23. Which of the following is correct option for free
endothermic expansion of an ideal gas under adiabatic condition?
H
(d) T (iv) Spontaneous (1) q = 0, T  0, w = 0
S
(2) q  0, T = 0, w = 0
Options
(3) q = 0, T = 0, w = 0
(a) (b) (c) (d) (4) q = 0, T < 0, w  0
24. The value of H for the reaction
(1) (i) (ii) (iii) (iv)
X2(g) + 4Y2(g) 2XY4(g) is less than zero.
(2) (iii) (iv) (ii) (i)
Formation of XY4(g) will be favoured at
(3) (iv) (i) (ii) (iii) (1) High temperature and high pressure
(4) (ii) (i) (iv) (iii) (2) Low pressure and low temperature
18. Three moles of an ideal gas expanded spontaneously (3) High temperature and low pressure
into vacuum. The work done will be: (4) High pressure and low temperature
25. Consider the following processes:
H (kJ/mol)
(1) Infinite (2) 3 Joules
(3) 9 Joules (4) Zero 1
A B + 150
19. For vaporization of water at 1 atmospheric pressure, 2
3B 2C + D – 125
the values of H and S are 40.63 kJ mol–1 and
E + A 2D +350
108.8 JK–1 mol–1 , respectively. The temperature
For B + D E + 2C, H will be
when Gibbs energy change (G) for this
transformation will be zero, is: [CBSE 2010 mains]
(1) 325 kJ/mol (2) 525 kJ / mol
(1) 273.4 K (2) 393.4 K
(3) –175 kJ/mol (4) –325 kJ/mol
(3) 373.4 K (4) 293.4 K
20. The following two reactions are known: 26. Which of the following statements is correct for a
reversible process in a state of equilibrium?

Fe 2 O3 (s)  3CO(g) 
 2Fe(s)  3CO 2 (g) ;
(1) G0 = –2.30 RT log K
H = –26.8 kJ
(2) G0 = 2.30 RT log K
FeO(s)  CO(g) 
 Fe(s)  CO 2 (g) ;
(3) G = –2.30 RT log K
H = –16.5 kJ
(4) G = 2.30 RT log K
The value of H for the following reaction
27. Given :
Fe 2 O3 (s)  CO(g) 
 2FeO(s)  CO 2 (g) is:
(1) +10.3 kJ (2) –43.3 kJ
[151]
 Chemical Thermodynamics and Thermochemistry

temperature reaction will be spontaneous

(I) (II) (1) 10000 K (2) 100 K

(3) 1000 K (4) 273 K
6. 5 g of ice at 0ºC is heated to convert in steam at
100ºC. Latent heat of fusion 80 calories per gram
(III) latent heat of vaporisation is 540 calories per gram,
specific heat of water is 1 calorie per gram per ºC.
The enthalpy of hydrogenation of these compounds Calculate heat evolved in the process?
will be in the order as:
(1) II > III > I (2) II > I > III (1) 3600 calories (2) 4500 calories
(3) I > II > III (4) III > II > I (3) 1800 calories (4) 7200 calories
28. The heat of combustion of carbon to CO2 is –393.5 7. In which of the following  Hf would not be zero?
kJ/mol. The heat released upon formation of 35.2 g
of CO2 from carbon and oxygen gas is:
(1) C(graphite) (2) I2 (s)
(1) –3.15 (3) Br 2(l) (4) red P
kJ (2) –315 kJ
8. For spontaneous reaction or the reaction at
(3) +315 kJ (4) – 630 kJ
equilibrium which of the following is wrong

DPMT
(1) H < TS reaction is exothermoic and TS
is +ve
1. The enthalpy of neutralization of oxalic acid by a
strong base is – 25.4 kcal mol–1. The enthalpy of (2) H = –ve, TS = 0
neutralization of strong acid and strong base is –13.7 (3) H = TS
kcal equiv–1. The enthalpy of dissociation of H2C2O4 (4) H = –ve, TS = –ve
 2H+ + C2O42– is
9. How many grams of ice at 0°C can be melted by
(1) 1.0 kcal mol–1 (2) 2.0 kcal mol–1
the addition of 500 J of heat? (The molar heat of
(3) 18.55 kcal mol–1 (4) 11.7 kcal mol–1
fusion for ice is 6.02 kJ mol–1)
2. An endothermic reaction has a positive internal
energy change U. In such a case, what is the (1) 0.0831 g (2) 1.50 g
minimum value that the activation energy can have? (3) 3.01 g (4) 12.0 g
10. A 1.0 g sample of substance A at 100°C is added
(1) U to 10 mL of H2O at 25°C. Using separate 100 mL
(2) U = H + nRT portions of H2 O, the procedure is repeated with
(3) U = H – nRT substance B and then with substance C. How will
(4) U = Ea + RT the final temperatures of the water compare?
3. Which of the following is true at equilibrium
Substance Specific Heat
(1) G = 0 (2) H = TS A 0.60 Jg–1 °C–1
(3) G = H + TS(4) both (a) and (b) B 0.40 Jg–1 °C–1
4. Which of the following is state function?
C 0.20 Jg–1 °C–1
]
(1) H (2) PV (1) TC  TB  TA (2) TB  TA  TC
(3) CV (4) W (3) TA  TB  TC (4) TA = TB = TC
5. H = 30 kJ and S = +3 J, then beyond which 11. Which of these species has a standard enthalpy of

[152]
 Chemical Thermodynamics and Thermochemistry

formation equal to zero?

(1) F2(g) (2) F(g)
(3) HF (aq) (4) F– (aq)
12. As O2(l) is cooled at 1 atm pressure, it freezes to
form solid I at 54.5 K. At a lower temperature,
Solid I rearranges to Solid II, which has a different
crystal structure. Thermal measurements show that
for the phase transition Solid I to Solid II, H = –
743.1 J mol–1 and S = –17.0 JK–1 mol–1. At what
temperature are solids I and II in equilibrium?

(1) 2.06 K (2) 31.5 K

(3) 43.7 K (4) 53.4 K
13. Which reaction, with the following values of H,
S at 400K is spontaneous and endothermic?

(1) H = – 48 kJ; S = + 135 J/K

(2) H = – 48 kJ; S = – 135 J/K
(3) H = + 48 kJ; S = + 135 J/K
(4) H = + 48 kJ; S = – 135 J/K

AIIMS
1. For a spontaneous process the correct statement is
andd w correspond to

(1) U < 0, w = 0 (2) U < 0, w < 0

(3) U > 0, w = 0 (4) U > 0, w > 0

[153]
 Chemical Equilibrium
Choose the correct answers :

1. The KC for A2(g) + B2(g) 2AB(g) at 100ºC is K is

50. If 1L flask containing one mole of A2 is connected (1) 0.1 (2) 0.008
with a 2L flask containing 2 moles of B2, the no. of (3) 0.8 (4) 0.08
moles of AB formed at 100ºC will be 8. The equilibrium constant for the reaction
+
(1) 2.86 (2) 1.86 CH3COOH + C2H5OH H CH3COOC2H5 + H2O
(3) 0.52 (4) 3.56 is 4.0 calculate the number of moles of ester that will
2. At 700 K Hydrogen and Bromine react to form be obtained when 120 gms of CH3COOH are reacted
Hydrogen bromide. The value of equilibrium constant with 9.2 grams of C2H5OH
8 (1) 2.33 moles (2) 1.33 moles
for this reaction is 5 × 10 . Calculate the amount of
Br2 at equilibrium if a mixture of 0.6 moles of H2 and (3) 2.9 moles (4) 4.9 moles
0.2 moles of Br2 is heated to 700 K 9. At certain temperature, KC is 16 for the reaction
(1) 0.2 (2) 0.4 SO2 (g) + NO2 (g) SO3 (g) + NO (g)
(3) 0.6 (4) Zero If we take one mole each of all the four gases in a
3. At 627ºC and 1 atm pressure, SO 3 is partially one litre container, what would be the concentration
dissociated into SO2 and O2 by: SO3(g) SO2 of NO2 at equilibrium ?
1
(g) + O2 (g). The density of the equilibrium mixture (1) 0.4 moles (2) 1.4 moles
2
is 0.925 g L–1 and the degree of dissociation is (3) 2.8 moles (4) 3.4 moles
(1) 0.18 (2) 0.86 10. What would be the effect of pressure on ?
(3) 0.52 (4) 0.34 N2 (g) + O2 (g) 2 NO (g)
4. At 273 K and 1 atm ‘a’ litre of N2O4 decomposes to (1) Reaction moves forward
NO2 according to equation N2O4(g) 2NO2(g). (2) Reaction moves backward
To what extent, has the decomposition proceeded, (3) No effect
when the original volume is 25% less than that of (4) Product [NO] increases
existing volume 11. KP value for the reaction
(1) 66% (2) 33% H2 + I2 2HI at 460ºC is 49. If the initial
(3) 28% (4) 72% pressure of H2 and I2 is 0.5 atmosphere. What is the
1 3 partial pressure of HI at equilibrium ?
5. Gº for N 2 (g) + H 2 (g) NH 3 (g) is (1) 0.788 (2) 2.84
2 2
–16.5 KJ mol–1. Kp for the reaction is (3) 1.9 (4) 0.12
(1) 779.4 atm–1 (2) 999 atm–1 12. What would be units of KP for the reaction
(3) 259 atm–1 (4) 508 atm–1 PCl5 PCl3 + Cl2
2
6. A graph is plotted between log KC and 1/T is straight (1) (atm) (2) (atm)1
line with intercept 10 and slope equal to 0.5. The heat (3) (atm)3 (4) None of these
13. At constant volume, the addition of an inert gas in the
of reaction is
formation of NH3, would cause
(1) + 2.303 cal mol–1 (2) – 2.303 cal mol–1
N2(g) + 3H2 2 NH3
(3) + 2.303 J mol–1 (4) – 2.303 J mol–1
(1) No effect
7. The standard Gibb’s free energy change for the
(2) Favours the forward rate of reaction
reaction: 2 AB A2 + B2 is 11.8 KJ at 230 K
(3) Favours the backward rate of reaction
and 1 atm. The degree of dissociation of AB at 230
(4) Favours equally both sides

[154]
 Chemical Equilibrium

14. The variations of equilibrium constant with N2O4 2 NO2 is expressed by Kp = (4x2 P) /
temperature (1 – x 2 ) where P = pressure, x = extent of
K2 H  T2  T1  decomposition. Which one of the following statements
log   
K1 2.303 R  T1. T2  was given by is true ?
(1) Kp increases with increase of P
(1) Arrhenius (2) Van’t Hoff
(3) Lewis (4) Boltzmann (2) Kp increases with increase of x
(3) Kp increases with decrease of x
15. A vessel at 1000 K contains CO2 with a pressure of
(4) Kp remains constant with change in P and x
0.5 atm: some of the CO2 is converted into CO on
addition of graphite. What is the value of KP if total 20. The equilibrium
pressure at equilibrium is 0.8 atmosphere. SO2Cl2(g) SO2 (g) + Cl2 (g)
(1) 0.8 (2) 1.8 is attained at 25ºC in a closed container and inert gas
(3) 2.84 (4) 3.84 Helium is introduced. Which of the following
16. Kp/Kc for the reaction statement/s is/are correct ?
1 (1) Concentrations of SO2, Cl2 and SO2Cl2 change
CO(g) + O2(g) CO2 (g) is
2 (2) Concentration of SO2 is reduced
(1) 1 (2) RT (3) More Chlorine is formed
(3) 1 / RT (4) (RT)1/2
(4) More SO2Cl2 is formed
17. For the equilibrium
21. Consider the following equilibrium in a closed
MgCO3(s) MgO(s) + CO2 (g) which of the container :
following expressions is correct ? N2O4 (g) 2 NO2 (g)
PMgO  PCO2 At a fixed temperature, the volume of the reaction
(1) K p  PMgCO3 container is halved. For this change, which of the
following statements, holds true regarding the
[MgO ] [CO 2 ] equilibrium constant (Kp) and degree of dissociation
(2) K p 
[MgCO 3 ] () ?
PMgO  PCO2 (1) Neither Kp nor  change
(3) K p  (2) Both Kp and change
[MgCO3 ]
(3) Kp changes but  does not change
(4) Kp = PCO2 (4) Kp does not change but  changes
18. 9.2 grams of N2O4 (g) is taken in a closed one litre 22. Pure Ammonia is placed in a vessel at a temperature,
vessel and heated till the following equilibrium is when its dissociation constant () is appreciable. At
reached equilibrium
N2O4 (g) 2 NO2 (g) (1) Kp does not change significantly with pressure
At equilibrium, 50% N2O4 (g) is dissociated. What is (2)  does not change with pressure
the equilibrium constant (in mol lit–1) (Molecular weight (3) Concentration of NH 3 does not change with
of N2O4 = 92) pressure
(1) 0.1 (2) 0.2 (4) Concentration of Hydrogen is less than that of
(3) 0.4 (4) 2 Nitrogen
19. At constant temperature, the equilibrium constant (Kp) 23. The oxidation of SO2 by O2 to SO3 is an exothermic
for the decomposition reaction reaction. The yield of SO3 will be maximum if

[155]
 Chemical Equilibrium

(1) Temperature is increased and pressure is kept equilibrium, in which direction, left to right, or right to
constant left, will reaction occur to reach equilibrium.
(2) Temperature is reduced and pressure is (1) Yes
increased (2) No, left to right
(3) Both temperature and pressure are increased (3) No, right to left
(4) Both temperature and pressure are reduced (4) There is not enough information to tell
24. A one litre vessel initially contains 2.0, 0.5 and 0.0
29. Kc for the reaction : N2(g) + O2(g) 2 NO(g) at
moles of N2, H2 and NH3 respectively. The system –6
300 K is 4.0  10 . Kp for this reaction would be
after attaining equilibrium has 0.2 mole of NH3. The (1) 4.0  10–6 (RT)2 (2) 4.0  10–6
number of moles of H2 in the vessel under equilibrium (3) 2.4  10–3 (4) 1.6  10–22
is
(1) 0.3 (2) 0.4 30. A cylinder fitted with a movable piston contains liquid
(3) 0.2 (4) 1.8 water in equilibrium with water vapour at 25ºC. Which
one of the following operations results in a decrease
25. 56 g of N2 and 6 g of H2 were kept at 400ºC in 1-litre
in the equilibrium vapour pressure ?
vessel. The equilibrium mixture contained 27.54 g of
NH3. The approximate value of Kc for the above (1) Moving the piston downwards through a short
reaction in mol2 L–2 is distance
(1) 10 (2) 20 (2) Removing a small amount of vapour
(3) 30 (4) None of these (3) Removing a small amount of the liquid water
(4) Dissolving salt in the water
26. The equilibrium constant for the reaction :
H2(g) + I2(g) 2 HI(g), at reaction temperature is 31. For reaction, PCl3(g) +Cl2(g) PCl5(g), the value
49. Then, the equilibrium constant for the of K c at 250ºC is 26. The value of Kp at this
reaction : temperature will be
HI(g) ½ H2(g) + ½I2(g) at the same temperature (1) 0.61 (2) 0.57
is (3) 0.83 (4) 0.46
(1) 7 (2) 1/7
32. Consider the reaction : PCl5(g) PCl3(g) + Cl2(g) in
(3) 24.5 (4) None of these
a closed container at equilibrium. At a fixed
27. The equilibrium constant for the reaction : temperature, what will be the effect of adding more
N2(g) + O2(g) 2 NO(g) is 4  10–4 at 2,000 K. PCl5 on the equilibrium concentration of Cl2(g) ?
In presence of catalyst, the equilibrium is attained ten (1) It decreases
times faster. Therefore, the equilibrium constant, in (2) It increases
the presence of catalyst, at 2,000 K is (3) It remains unaffected
(1) 4  10–5 (4) It cannot be predicted without the value of Kp
(2) 4  10–4
(3) 4  10–3 33. For the reaction :
(4) Difficult to compute without more data. 2SO2(g) + O2(g) 2SO3(g); H = – 45.2 kcals
The number of moles of SO3 will increase on
28. At 700 K, the reaction :
(1) Removing O2 from the reaction mixture
2SO2(g)+O2(g) 2 SO 3 (g) has an equilibrium
(2) Increasing the temperature of the system
constant, K c = 4.3 10 6 , and the following
concentrations are present: (3) Increasing the pressure of the system by
[SO2] = 0.01 M; [SO3] = 10 M; [O2] = 0.01 M adding an inert gas
Is the mixture at equilibrium, yes or no ? If not at (4) Decreasing the volume of the reaction mixture.

[156]
 Chemical Equilibrium

34. At high temperature, the following reaction occurs: (1) High pressure, high temperature and low
4 CuO(s) 2Cu2O(s) + O2(g) pressure, low temperature
Consider the following statements regarding reaction (2) Low pressure, low temperature and high
and identify the correct statement. pressure, low temperature
(3) High pressure, low temperature and low
(1) Kp = PO2
pressure, high temperature
(2) Kp depends upon the amounts of CuO and (4) Low pressure, high temperature and high
Cu2O pressure, high temperature
(3) Kp << Kc
(4) None of these 39. Sodium carbonate, Na 2CO 3(s), can be made by
heating sodium bicarbonate, NaHCO3(s) :
35. The equilibrium constant for gaseous reaction. 2 NaHCO3(s) Na2CO3(s) + CO2(g) + H2O(l)
A+B C+D Kp = 0.23 atm2 at 100ºC. If a sample of NaHCO3 is
is 100 at 25ºC. Consider the following statements in placed in an evacuated flask and allowed to achieve
this regard. If the initial concentration of all four equilibrium at 100ºC, what will the total gas pressure be ?
species were 1.0 M each, then the equilibrium (1) 0.46 atm (2) 0.96 atm
concentration of (3) 0.23 atm (4) 0.48 atm
(1) A would be 0.182 mol/L
40. Consider the following gas phase equilibrium system:
(2) C would be 0.818 mol/L PCl5 PCl3 + Cl2: Hº = 87.8 kJ
(3) B would be 1.818 mol/L Which of the following statements is false ?
(4) None of these (1) Increasing the concentration of PCl5 causes
the system to reach an equilibrium that has
36. If K1 is the equilibrium constant for the reaction :
more product
2NO(g) + O2(g) 2 NO2(g) and
(2) Increasing the temperature shifts the
K2 is the equilibrium constant for the reaction : equilibrium to the right
2 NO2(g) N2O4(g) (3) A catalyst speeds up the approach to
Then K3, the equilibrium constant for the reaction : equilibrium and shifts the position of equilibrium
2 NO(g) + O2(g) N2O4(g) is given by to the right
(1) K3 = K1 / K2 (2) K3 = K1  K2 (4) When the total pressure of the system is
decreased, the equilibrium is shifted to the right
K1
(3) K3 = K1 + K2 (4) K3 =
K2 41. For the reaction : A(g) + B(g) C(g),
the equilibrium partial pressures, pA = 0.15 atm,
37. Two moles of NH3 gas are introduced into a previously
pB = 0.10 atm and pC = 0.30 atm. When the volume
evacuated 1.0 L container in which it undergoes of the reaction vessel was reduced to such an extent
dissociation at high temperature : that on re-establishing the equilibrium, the partial
2NH3(g) N2(g) + 3 H2(g) pressures of A and B were doubled. The new partial
At equilibrium, 1.0 mol of NH3(g) is left. The value pressure of C would be
of equilibrium constant (Kc) in units of mol2 L–2 is (1) 0.30 atm (2) 0.60 atm
(3) 1.20 atm (4) None of these
(1) 0.75 (2) 1.00
(3) 1.50 (4) None of these 42. 1.0 mole of PCl3(g) and 2.0 moles of Cl2(g) were
placed in a 3 litre flask and heated to 400 K. At
38. In a two step exothermic reaction : equilibrium, 0.70 mole of PCl3(g) remained. The value
A2(g) + B2(g) 3C(g) D(g); H = –ve of equilibrium constant for the reaction :
Steps 1 and 2 are favoured respectively by PCl3(g) + Cl2(g) PCl5(g) at 400 K is

[157]
 Chemical Equilibrium

(1) 0.756 (2) 1.515 (1) 4.33  10–1 (2) 3.33  10–2
(3) 0.378 (4) None of these (3) 3.33  10–1 (4) 4.33  10–2

43. Which of the following statements is not true regarding 48. For an equilibrium reaction, which of the following
chemical equilibrium ? statement is not true.
(1) If the reaction quotient of the reaction is
(1) At equilibrium, the concentrations of all the
greater than K eq, the reaction moves in the
reactants and products becomes stationary
backward direction
(2) The rate of the forward reaction is equal to
(2) If the reaction quotient of the reaction is lesser
the rate of the backward reaction
than Keq the reaction moves in the forward
(3) The product of the concentrations of the direction
reactants should be equal to the product of (3) If the reaction quotient of the reaction is equal
the concentrations of the products to Keq the reaction is at equilibrium
(4) The reaction appears to have come to stop (4) There is no correlation between the reaction
44. In an experiment, carried out in a 500 cm3 vessel, on quotient and Keq in predicting the direction in
analysis of the equilibrium mixture revealed that there which reaction proceeds.
was 0.3 mol of Phosgene, 0.1 mol of CO and 0.1 mol 49. In the reaction at equilibrium x moles of the reactant
of Chlorine. CO + Cl2 COCl2 A decompose to give 1 mole each of C and D. If the
The equilibrium constant is equal to fraction of A decomposed at equilibrium is independent
(1) 30 (2) 15 of initial concentration of A, then the value of x is :
(3) 5 (4) None of these (1) 1 (2) 3
45. In the Haber ’s process for the industrial (3) 2 (4) 4
manufacture of Ammonia involving the reaction : 50. At temperature T a compound AB2(g) dissociates
N2 + 3H2 2 NH3 at 200 atm in presence of a according to the reaction 2AB2(g) 2AB(g) +
catalyst, a temperature of about 500ºC is used. This B2(g) with a degree of dissociation x, which is small
is considered as the optimum temperature for the compared to unity. The expression for Kp in terms of
process because the x and the total pressure p, is
(1) yield is maximum at this temperature px 3 px 2
(1) (2)
(2) catalyst is active at this temperature 2 3
(3) energy needed for this reaction is easily px 3
(3) (4) None of these
obtained at this temperature 3
(4) the rate of catalytic reaction is fast enough, 51. In a system A(s) 2B(g) + 3C(g), if the
while the yield is also appreciable for this concentration of C at equilibrium is increased by a
exothermic reaction at this temperature factor of 2, it will cause the equilibrium concentration
of B to change to :
46. Ammonium carbamate dissociates as :
(1) Two times the original value
NH2COONH4(s) 2NH3(g) + CO2(g)
(2) One half of its original value
In a closed vessel containing Ammonium carbamate
in equilibrium, Ammonia is added such that the partial (3) 2 2 times its original value
pressure of NH3 now equals to the original total 1
pressure. The ratio of the total pressure now to the (4) times the original value
2 2
original pressure is
52. Given the following reaction at equilibrium :
(1) 27/31 (2) 31/27
N2(g) + 3H2(g) 2NH3(g)
(3) 4/9 (4) 5P/9
Some inert gas is added at constant pressure. In doing so,
47. Kp for a reaction at 25ºC is 10 atm. The activation (1) more NH3 gas is produced
energy for forward and reverse reactions are 12 and (2) less NH3 gas is produced
20 kJ/mole, respectively. The Kc for the reaction at (3) no effect on equilibrium
40ºC will be (4) Kp of the reaction is decreased

[158]
 Chemical Equilibrium

53. Kc for the reaction [Ag(CN)2]– Ag+ + 2CN–, (3) Higher than the lower layer
the equilibrium constant at 25ºC is 4.0  10–19 then (4) In fixed ratio with that in the lower layer
the Ag+ ion concentration in a solution which was
originally 0.1 M in KCN and 0.03 M in AgNO3 is : 60. At 300 K, Kp for the reaction
(1) 7.5  1018 (2) 7.5  10–18 SO2(g) + O2(g) SO3(g) is 1.7  1012.
19
(3) 7.5  10 (4) 7.5  10–19 The value of Kp for the reaction
54. The reaction A + B   C + D is endothermic in
 2SO3(g) 2SO2(g) + O2(g) at 300 K is
the forward direction. What will happen to the rate of (1) 3.6  10 –12
(2) 3.9  10–18
backward reaction if the temperature of the reaction (3) 3.5  10–23 (4) None of these
mixture of above reaction at equilibrium is raised.
(1) Rate of backward reaction will decrease 61. A reaction CaF2 Ca2+ + 2F– is at equilibrium.
(2) Rate of backward reaction will increase If the concentration of Ca2+ ion is increased by 4
(3) Rate of forward reaction will increase but rate times, what is the change in F– ion concentration when
of backward reaction will remain unchanged compared to initial concentration of F– ions ?
(4) Rate of forward reaction will remain (1) ¼ times (2) ½ times
unchanged and rate of backward reaction will (3) 4 times (4) None of these
decrease 62. At equilibrium in a reversible reaction, there occurs
55. The equilibrium constant for the reaction (1) A change in the total number of molecules
Br2 2Br at 500 K and 700 K are 1  10–10 and (2) A change in the energy of the reacting molecules
1  10–5 respectively. The reaction is : (3) A change in the energy of the reaction products
(1) Endothermic (2) Exothermic (4) No change in the total energy of the system
(3) Fast (4) Slow
63. The KC for A2(g) + B2(g) 2AB(g) at 100ºC is
56. N2O4 dissociates as N2O4 2NO2. As 55ºC and 50. If 1L flask containing one mole of A2 is connected
one atmosphere, the percentage decomposition of with a 2L flask containing 2 moles of B2, the moles of
N2O4 is 50.3%. The pressure at which the ratio of AB formed at 100ºC will be
N2O4 : NO2 is 1 : 8 Keeping temperature constant is
(1) 2 atms (2) 1 atm (1) 2.86 (2) 1.86
(3) 0.2 atm (4) 0.5 atm
(3) 0.52 (4) 3.56
57. A and B are mixed in the ratio 5 : 3 and they react in
the ratio 2 : 1 to form C and D in the ratio 1 : 4. At 64. The equilibrium constant X(g) Y(g) is 1.1.
equilibrium, conc. of B and C are equal. The Kc for Which gas has a molar concentration greater than 1.
the reaction is (1) X only (2) Y only
(1) 50 (2) 144 (3) X and Y both (4) None of these
(3) 190 (4) None of these 65. In a reaction ‘X’ moles of the reactant A decomposes
58. The vapour density of PCl5 at 250ºC when it is 80% to give 1 mole each of C and D. It has been found
dissociated is that the fraction of A decomposed at equilibrium is
(1) 75 (2) 58 independent of initial concentration of A. The value
(3) 78 (4) None of these of ‘X’ is
59. In a pair of immiscible liquids, a common solute (1) 1 (2) 2
dissolves in both and the equilibrium is reached. The (3) 3 (4) None of these
concentration of these gases is suddenly reduced to CBSE – PMT
1/4th of the initial volume. The rate of reaction (relative
1. For the gas phase reaction PCl5(g) PCl3(g) +
to original rate) would be
(1) Same as in lower layer Cl2(g)
which of the following conditions are correct?
(2) Lower than the lower layer

[159]
 Chemical Equilibrium

(1) H = O and S < O (4) The equilibrium constant for the reaction is given
(2) H > O and S > O [CO2 ]
(3) H < O and S < O by Kp = [CH ][O ]
4 2
(4) H > O and S < O
7. Equilibrium constants K1 and K2 for the following
2. The dissociation equilibrium of a gas AB2 can be
equilibria
represented as
1 K1
2AB2(g) 2AB(g) + B2(g) NO  O 2 NO 2 (g) and
2
The degree of dissociation is ‘x’ and is small compared K2

to 1. The expression relating the degree of dissociation 2NO 2 (g) 2NO(g)  O 2 (g)
(x) with equilibrium constant KP and total pressure P are related as
is 1 K1
(1) (2KP/P) (2) (2KP/P) 1/3 (1) K 2  K (2) K 2 
1/2 1 2
(3) (2KP/P) (4) (K P/P)
3. The values of Kp1 and Kp2 for the reactions 1
X Y+ Z ......(1) (3) K 2  K 2 (4) K 2  K12
1

A 2B ......(2)
8. The reaction
are in ratio of 9 : 1. If degree of dissociation of X and
A be equal, then total pressure at equilibrium (1) and 2A(g)  B(g) 3C(g)  D(g)
(2) are in the ratio:
(1) 3 : 1 (2) 1 : 9 is begun with the concentrations of A and B both
(3) 36 : 1 (4) 1 : 1 at an initial value of 1.00 M. When equilibrium is
4. The value of equilibrium constant of the reaction reached, the concentration of D is measured and
1 1 found to be 0.25M. The value for the equilibrium
HI (g) H (g) + I2 is 8.0
2 2 2 constant for this reaction is given by the
The equilibrium constant of the reaction H2(g) + I2(g) expression.
2HI (g) will be (1) [(0.75)3(0.25)  [(1.00)2 (1.00)]
1 1 (2) [(0.75)3(0.25)  [(0.50)2 (0.75)]
(1) (2)
16 64 (3) [(0.75)3(0.25)  [(0.50)2 (0.25)]
1 (4) [(0.75)3(0.25)  [(0.75)2 (0.25)]
(3) 16 (4)
8 9. If the value of an equilibrium constant for a particular
5. The following equilibrium constants are given
N2 + 3H2 2NH3; K1 reaction is 1.6 × 1012, then at equilibrium the system
N2 + O2 2NO; K2 will contain: (1) mostly
H2 + 1/2O2 H2O; K3 products
The equilibrium constant for the oxidation of NH3 by (2) similar amounts of reactants and products
oxygen to given NO is (3) all reactants
(1) K 2 K 32 / K1 (2) K 22 K 3 / K1 (4) mostly reactants

(3) K1K 2 / K 3 (4) K 2 K 33 / K1

6. For the reaction
DPMT
CH4 + 2 O2(g) CO2(g) + 2H2O (l),
rH = – 170.8 kJ mol–1. 1. At the equilibrium of the reaction 2X(g) + Y(g) 
Which of the following statements is not true? X2Y(g), the number of moles of X2Y at equilibrium
(1) Addition of CH4(g) or O2(g) at equilibrium will is affected by the
cause a shift to the right (1) temperature and pressure
(2) The reaction is exothermic (2) temperature only
(3) At equilibrium, the concentrations of CO2(g) and (3) pressure only
H2O (l) are not equal (4) temperature, pressure and catalyst used

[160]
 Chemical Equilibrium

2. In the equilibrium (2) rate of backward reaction

2NH3 N2 + 3H2. 6 moles of NH3 is taken in (3) time required to reach the equilibrium
10 litre flask. If concentration of N2 at equilibrium (4) spontaneity
is x, then concentration of NH3 at equilibrium is 10. For a chemical reaction of the type
(1) 0.6 – x (2) 0.6 – 2x 
A  B, K  2.0 and B 
  C, K  0.01

x Equilibrium constant for the reaction 2C 2A
(3) 0.6 – (4) none is correct
2 is:
3. For the reaction N2 + 3H2 2NH3 + energy,, (1) 25 (2) 50
increase of temperature will result into (3) 2500 (4) 4 × 10–4
11. Given a gas phase reaction
(1) increase of NH3 (2) increase of N2 2A(g) + B(g) C(g) + D(g)
(3) decrease of N2 (4) decrease of H2 Which one of the following changes will affect the
4. NH 4 COONH 2 (s) 2NH 3 (g) + CO 2 (g) if value of Kc?
equilibrium pressure is 3 atm for the above reaction (1) Addition of inert gas
Kp for the reaction is (2) Addition of catalyst
(1) 4 (2) 27 (3) Addition of reactants
(3) 4/27 (4) 1/27 (4) Increasing in temperature
5. The free energy of formation of NO is 78 kJ mol–
1 at the temperature of an automobile engine
AIIMS
(1000K). What is the equilibrium constant for this
reaction at 1000K?
1. For a phase change H2O(l) H2O(s)
1 1 0° C, 1 bar
N 2(g)  O 2(g)  NO(g)
2 2
(1) 8.4 × 10–5 (2) 7.1 × 10–9 (1) G = 0 (2) S = 0
(3) 4.2 × 10–10 (4) 1.7 × 10–19 (3) H = 0 (4) U = 0
6. A 0.010 M solution of maleic acid, a monoprotic 2. For reaction 2 NOCl(g) = 2 NO(g) + Cl2(g), KC at
organic acid, is 14% ionized. What is Ka for maleic 42.7°C is 3 × 10–6 L mol–1. The value of Kp is nearly
acid?
(1) 2.3 × 10–3 (2) 2.3 × 10–4
(3) 2.0 × 10 –4 (4) 2.0 × 10–6 (1) 7.50 × 10–5 (2) 2.50 × 10–5
7. For the reactions (3) 2.50 × 10–4 (4) 1.75 × 10–4
3. For the chemical equilibrium,
I2 (aq) I2 (oil) Equilibrium constant is K 1
I 2 (oil) I 2 (ether) Equilibrium constant is K 2 CaCO3 (s) CaO(s) + CO2 (g), H°r can be
for the reaction determined from which one of the following plots?
I 2 (aq) I 2 (ether) Equilibrium constant = K 3
The relation between K1, K2, K3 is:
(1) K3 = K1 + K2 (2) K3 = K1K2
log10 pCO2/p°

log10 pCO2/p°

(3) K3 = K1/K2 (4) K3 = K2/K1

8. Which statement is not correct? (1) (2)
(1) Rate of an exothermic reaction increases with
1/T T
temperature
(2) Solubility of NaOH increases with temperature
(3) K P for N 2 (g)  3H 2 (g) 2NH 3 (g)
pCO2/p°
lnpCO2/p°

increases with increase in pressure

(4) For gaseous reaction 2B A KP is smaller (3) (4)
than Kc
Log10T 1/T
9. For the following reaction
C6 H12 O 6 (aq)  H 2 (g) C6 H14 O 6 (aq)
Which one of the following is not affected by the
addition of catalyst?
(1) rate of forward reaction
[161]
 Ionic Equilibrium
Choose the correct answers :
1. The pH at the equivalence point when a solution of 9. The molarity of 3 gm CH3COOH in 2L solution is
0.1 M Acetic acid is titrated with a solution of (1) 0.25 (2) 2.5
0.1 N NaOH is (Ka for acid = 1.9 × 10–5) (3) 0.025 (4) 0.0025
(1) 8.71 (2) 9.4 10. The pH of a solution
(3) 2.3 (4) 6.8 (1) Increases regularly with dilution
2. The percentage hydrolysis in 0.003 M aq. solution of (2) Decreases regularly with dilution
(3) Does not change with dilution
NaOCN is (Ka for HOCN = 3.33 × 10–4)
(4) Increases first sharply and then slowly with
(1) 10% (2) 100%
–2
dilution
(3) 10 % (4) 10–1% 11. For equimolar solutions pH is more for
3. An aqueous solution of a metal bromide MBr 2 (1) HNO3 (2) H3PO 4
(0.05 M) is saturated with H2S. What is the minimum (3) HCl (4) HBr
pH at which MS will precipitate ? KSP for MS = 12. Which of the following would not change the pH of
6 × 10–21, concentration of saturated H2S = 0.1M. 50 c.c. of dilute HCl when added to the acid
K1 = 10–7 and K2 = 1.3 × 10–13 for H2S ? (1) 50 cc of pure water
(2) 50 cc of NaOH
(1) 9.8 (2) 0.98
(3) 50 cc of conc. HCl
(3) 7 (4) 0.1
(4) 50 cc of same dilute HCl
4. A particular water sample has 131 ppm CaSO4. What 13. 1 cc. of 0.1 N HCl is added to 999 cc. aqueous solution
fraction of water must be evaporated in a container of NaCl. The pH is
before solid CaSO4 begins to deposit. KSP of CaSO4 (1) 7 (2) 4
= 9 × 10–6 (3) 5 (4) 2
(1) 68% (2) 32% 14. According to Bronsted-Lowry concept the relative
(3) 6.8% (4) 3.2% strength of the bases CH3COO–, OH–, Cl– follows
5. In the following the decreasing order
(1) OH– > CH3COO– > Cl–
[Al(H 2 O) 6] +3 + HCO 3– [Al(H 2O) 5OH) 2+
(2) Cl– > OH– > CH3COO–
(A) (B) (C) + H2CO3 (3) Cl– > CH3COO– > OH–
(D) (4) CH3COO– > OH– > Cl–
Species behaving as Bronsted-Lowry acids are : 15. Which of the following is conjugate acid-base pair
(1) (D) (2) (B), (C) (1) HCl, NaOH (2) NH4Cl, NH4OH
–
(3) (B), (D) (4) (A), (C) (3) H2SO4, HSO4 (4) KCN, HCN
6. 25 ml of a sample of clear saturated solution of 16. Choose the correct statement
PbI2 requires 10 ml of a certain AgNO3 (aq.) for its (1) In CH 3 COOH/CH 3 COO – Na + buffer, the
reserve acidity of the solutionis due to CH3COO–
titration. What is the molarity of this AgNO3 solution.
ions
(KSP for PbI2 = 4 × 10–9)
(2) It is not necessary that an acidic substance must
(1) 10–2 M (2) 5 M contain H+ ions
–2
(3) 5 × 10 M (4) 5 × 10–3 M (3) HCO3– is Bronsted base and does not act as
7. Ka for HCN is 5 × 10–10 at 25ºC. For maintaining a Bronsted acid
constant pH of 9, the volume of 5 M KCN solution (4) Na2CO3 does not contain OH– ions and thus is
not a base
required to be added to 10 ml of 2 M HCN solution is
17. Out of AgCl, AgBr and AgI, the solubility product of
(1) 4 ml (2) 2 ml AgI is least and that of AgCl is maximum. Which of
(3) 7.95 ml (4) 9.3 ml the following reactions is feasible?
8. Ka for Formic acid and Acetic acid are 2.1 × 10–4 (1) AgI + KCl   AgCl + KI
and 1.1 × 10–5 respectively. The relative strengths of (2) AgCl + KI  KCl + AgI
the acids are (3) AgBr + KCl  AgCl + KBr
(1) 2.4 : 3.3 (2) 4.36 : 2.1 (4) AgI + KBr  AgBr + KI
(3) 4.36 : 1 (4) 2.3 : 1
[162]
 Ionic Equilibrium

18. When excess Oxalic acid is added to CaCl2, Ca C2O4 (1) 100 ml of M/10 HCl + 100 ml of M/10 NaOH
is precipitated and the solution still contains some (2) 55 ml of M/10 HCl + 45 ml of M/10 NaOH
unprecipitated Ca2+ for the reason : (3) 10 ml of M/10 HCl + 90 ml of M/10 NaOH
(1) CaC2O4 is a soluble salt (4) 75 ml of M/5 HCl + 25 ml of M/5 NaOH
(2) Solubility product of CaC2O4 is not exceeded
28. Among the following which will have the lowest value
(3) Oxalic acid does not ionise
of KSP (solubility product).
(4) None
(1) Be (OH)2 (2) Mg(OH)2
19. 100 ml of 1M HCl is mixed with 50 ml of 2M HCl. (3) Ca(OH)2 (4) Ba(OH)2
Hence, [H3O+] is
(1) 1.00 M (2) 1.50 M 29. Which of the following has the highest pH ?
(3) 1.33 M (4) 3.00 M (1) CH3COOK (2) Na 2CO3
20. An acidic solution can be prepared by dissolving in (3) NH4Cl (4) NaNO3
water 30. The concentration of [H +] and [OH–] of 0.1 M
(1) Ba2SO3 (2) NaH2PO 4 aqueous solution of 2% ionized weak acid is (ionic
(3) NaHPO4 (4) Na 3PO 4 product of water = 1 × 10–14)
21. For preparing a buffer solution of pH = 6, by mixing (1) 0.2 × 10–3 M and 5 × 10–11 M
(CH 3 COOH + CH 3 COONa), the ratio of (2) 1 × 10–3 M and 3 × 10–11 M
concentration of the salt and acid should be (3) 2 × 10–3 M and 5 × 10–12 M
(Ka = 105) (4) 3 × 10–2 M and 4 × 10–13 M
(1) 1 : 10 (2) 10 : 1
(3) 100 : 1 (4) 1 : 100 31. Which one of the following is true for any diprotic
acid, H2X ?
22. A H2SO4 acid solution has a pH = 2, the molarity is (1) Ka2 > Ka1 (2) Ka1 > Ka2
M M 1
(1)
100
(2)
50 (3) K a 2  K (4) Ka2 = Ka1
a1

M M 32. Solubility of an MX2 type electrolyte is 0.5 × 10–4 mol

(3) (4)
200 2 L–1, then Ksp of the electrolyte is
(1) 5 × 10–12 (2) 25 × 10–10
23. Which of the following is not a Lewis acid ? (3) 1 × 10 –13
(4) 5 × 10–13
(1) CO (2) SiCl4
(3) SO3 (4) Zn+2 33. If pKb for Fluoride ion at 25ºC is 10.83, the ionisation
constant of Hydrofluoric acid at this temperature is
24. On the mixing together the 10 ml of 0.02 N solution (1) 1.7 × 10–5 (2) 3.52 × 10–3
–4
of CaCl2 and 5 ml of 0.1 N solution of K2CrO4 (KSP (3) 6.75 × 10 (4) 5.38 × 10–2
for CaCrO4 = 2.3 × 10–2) decide
(1) Precipitation occurs 34. The pH of a solution is 5.0. To this solution sufficient
acid is added to decrease the pH to 2.0. The increase
(2) Precipitation not occurs
in [H3O+] is
(3) pH changes
(1) 1,000 times (2) 100 times
(4) None of these
(3) 2.5 times (4) 10 times
25. Which of the following on reaction with H2S in the
35. One beaker contains 100 mL of 0.1 M Oxalic acid
acidic medium would precipitate ?
solution and other beaker contains 50 mL of 0.1 M
(1) COCl2 (2) CuCl2
Acetic acid solution. Which one of the following
(3) ZnCl2 (4) MnCl2 statements is correct in this regard ?
26. 0.1 M solution of HCN is 0.01% ionised, the ionisation (1) Both solutions have the same pH
constant of HCN is (2) The pH of oxalic acid solution is double than that
(1) 1 × 10–9 (2) 1 × 10–7 of Acetic acid solution
(3) 1 × 10–5 (4) 1 × 10–3 (3) The pH of Oxalic acid solution is greater, but
not double that of Acetic acid solution
27. Which of the following solution will have pH close to (4) The pH of the Oxalic acid solution is less than
one ? that of Acetic acid solution

[163]
 Ionic Equilibrium

36. Which one of the following mixtures is suitable 42. At 90ºC, pure water has [H3O+] = 10–6 mol litre–1.
for making a buffer solution with an optimum pH of What is the value of Kw at 90ºC ?
9.2 - 9.3 ? (1) 10–6 (2) 10–12
–14
(1) CH3CO2Na/CH3CO2H (Ka = 1.8  10–5) (3) 10 (4) 10–8
(2) NH3/NH4Cl (Ka (NH4+) = 5.6  10–10) 43. Solutions A and B contain one and two moles of
(3) NaNO2/HOCl (Ka = 4.5  10–8) CH3COONH4 in one litre respectively. The hydrolysis
(4) NaNO2/HNO2 (Ka = 4.5  10–4) will be
(1) More in A (2) More in B
37. Ka for HCN is 5  10–10 at 25ºC. For maintaining a (3) Same in A and B (4) Very little in A
constant pH of 9, the volume of 5 M KCN solution
44. The pKa value of Ammonium hydroxide is 4.75. An
required to be added to 10 mL of 2 M HCN solution aqueous solution of Ammonium hydroxide is titrated
is with HCl. The pH of the solution at the point where
(1) 4 mL (2) 7.95 mL half of Ammonium hydroxide has been neutralized will
(3) 2 mL (4) 9.3 mL be
(1) 9.25 (2) 8.25
38. The approximate pH of a solution formed (3) 7.50 (4) 4.75
by mixing equal volumes of solutions of 0.1 M Sodium
45. Which equilibrium can be described as an acid-base
propanoate and 0.1 M Propanoic acid (the dissociation
reaction using the Lewis acid-base definition, but not
constant of Propanoic acid is using Bronsted-Lowry definition ?
–5 –3
1.3  10 mol dm ) will be (1) NH3 + CH3COOH CH3COO– + NH4+
(1) 1.52 (2) 3.62 (2) H2O + CH3COOH H3O+ + CH3COO–
(3) 4.89 (4) 5.52 (3) 4NH3 + [Cu (H2O)4]2+ [Cu (NH3)4]2++4H2O
39. The Hydrogen ion concentration in 0.2 M Ethanoic (4) 2NH3 + H2SO4 2NH4+ + SO42–
acid (Ka = 2  10–5 mol dm–3) is approximately ? 46. Which response places the following acids in order
(1) 2  10–2 (2) 2  10–3 of increasing acid strength (weakest to strongest)?
(3) 2  10–4 (4) 10–5 (a) C6H5COOH (Ka = 6.5  10–5)
(b) HNO2 (Ka = 4.5  10–4)
40. The pKa of acetyl salicylic acid (aspirin) is 3.5. The (c) HCN (Ka = 4.9  10–10)
pH of gastric juice in human stomach is about 2 – 3 (1) b < a < c (2) b < c < a
and the pH in small intestine is about ‘8’. Aspirin will (3) a < b < c (4) c < a < b
be 47. The precipitate of CaF2(Ksp = 1.7 10–10) is obtained
(1) Unionized in the small intestine and in stomach when equal volumes of the following are mixed.
(2) Completely ionized in the small intestine and (1) 10–4 M Ca2+ + 10–4 M F–
in stomach (2) 10–3 M Ca2+ + 10–3 M F–
(3) Ionized in the stomach and almost unionized (3) 10–5 M Ca2+ + 10–3 M F–
in small intestine (4) None of these
48. The solubility product for Ca 3 (PO 4 ) 2 is
(4) Ionized in the small intestine and almost
Ksp =1.310–26. What is the solubility of Ca3(PO4)2 in
unionized in the stomach moles per litre of solution ?
(1) 1.3  10–26 M (2) 1.5  10–7 M
41. Solid AgNO3 is gradually added to a solution containing
(3) 2.6  10–6 M (4) 4.6  10–6 M
equimolar concentration of Cl– and I–. If Ksp of AgCl 49. Will a precipitate form (yes or no), when 10.0 mL
and AgI are 1.7  10–10 and 1.5  10–16 respectively of 1.5  10–3 M Pb(NO3)2 is added to 40.0 mL of
the relative concentration of I– to Cl– just before 3.0 10–4 M Na2SO4 ? Given Ksp (PbSO4)=1.610–8.
(1) No because ion is product < Ksp
precipitation of AgCl
(2) No because ion is product > Ksp
(1) 8.8  10–10 (2) 8.8  10–7 (3) Yes because ion is product > Ksp
(3) 8.8  10–15 (4) None of these (4) Yes because ion is products < Ksp

[164]
 Ionic Equilibrium

50. Silver nitrate solution is gradually added to an aqueous 57. Which anion is weakest base :
solution containing 0.01 M each of the chloride, (1) C2H5O– (2) NO3–
bromide and iodide ions. The correct sequence in (3) F– (4) CH3COO–
which the halides will be precipitated is
(1) Bromide, chloride, iodide 58. Calculate the percent ionization of 0.020 M
(2) Iodide, chloride, bromide CH3COOH (acetic acid) Ka = 1.8  10–5.
(3) Iodide, bromide, chloride (1) 6.0  10–4% (2) 0.03%
(4) Bromide, iodide, chloride (3) 0.09% (4) 3%
51. The solubility product, Ksp, of the sparingly soluble 59. If the maximum concentration of PbCl2 in water is
salt Ag2CrO4 is 4  10–12. The molar solubility of the 0.01 M at 25ºC. Its maximum concentration in 0.1 M
salt is
NaCl will be
(1) 1.0  10–4 mol L–1 (2) 2  10–6 mol L–1
(1) 2  10–3 M (2) 1  10–4 M
(3) 1.0  10–5 mol L–1 (4) 2  10–12 mol L–1
(3) 1.6  10–2 M (4) 4  10–4 M
52. Which is correct alternate for hydrolysis constant of
NH4CN ? 60. The dissociation constant of Acetic acid at a given
temperature is 1.69  10–5. The degree of dissociation
(1) K w / Ka (2) Kw /(Ka  Kb)
of 0.01 M Acetic acid in presence of 0.01 M HCl is
(3) Kb / Ka (4) Ka /Kb equal to
53. In a saturated solution of AgCl (Ksp = 1.6  10–10 at (1) 0.41 (2) 0.13
25ºC), the [Ag+] = 1.3  10–5 mol/L. Then enough (3) 0.169  10–2 (4) 0.013
Potassium chloride is added to this solution so that
61. If the solubility of AgCl in water, in 0.01 M CaCl2, in
[Cl]– = 0.020 M. The solubility of AgCl in this solution
0.01 M NaCl and in 0.05 M AgNO3 be S1, S2, S3 and
of Potassium chloride is
(1) 3.2  10–8 mol/L (2) 8.0  10–11 mol/L S4 respectively. Then
(3) 8.0  10–8 mol/L (4) 8.0  10–9 mol/L (1) S1 > S2 > S3 > S4 (2) S1 > S3 > S2 > S4
(3) S1 > S2 = S3 > S4 (4) S1 > S3 > S4 > S2
54. NaOH is added to sea water containing 0.050 M
Mg2+ ion until the pH reaches 11.0. This causes 62. The compound insoluble in Acetic acid is
Mg(OH) 2 to precipitate. What concentration of (1) Calcium oxide (2) Calcium carbonate
Mg2+ will remain in the solution at this pH ? (3) Calcium oxalate (4) Calcium hydroxide
Ksp Mg(OH)2 = 1.2  10–11
(1) 1.2  10–8 M (2) 1.2  10–17 M 63. In which one of the following solution will the addition
(3) 0.050  10–2 M (4) 1.2  10–5 M of a trace of acid not affect the pH ?
(1) Solution of Sodium chloride
55. Which one of the following statements about strong
(2) Solution of Sodium hydroxide
acids is true ?
(1) All strong acids have H atoms bonded to (3) Solution of Hydrochloric acid
electronegative Oxygen atoms (4) Solution of Ammonium acetate
(2) Strong acids are almost 100% ionized in water
64. The pH range for best buffer action of a mixture of a
(3) The conjugate base of a strong acid is itself a
weak acid HA of dissociation constant Ka and its salt
strong base
(4) Strong acids are very concentrated acids NaA in aqueous solution should be
(1) pKa ± 0.5 (2) pKa ± 1
56. The best indicator for detection of end point in titration (3) pKa ± 1.5 (4) pKa ± 2
of a weak acid and a strong base is
(1) Methyl orange (3 to 4) 65. If pKb for CN– at 25ºC is 4.7, the pH of 0.5 M aq.
(2) Methyl red (5 to 6) NaCN solution is
(3) Bromothymol blue (6 to 7.5) (1) 12 (2) 10
(4) Phenolphthalein (8 to 9.6) (3) 11.5 (4) 11

[165]
 Ionic Equilibrium

66. 50% neutralization of a solution of Formic acid 73. How many moles of NaOH should be added to
–4 a solution containing 0.1 M NH4Cl and 0.1 M NH4OH
(Ka = 2  10 ) with NaOH would result in a solution
having a Hydrogen ion concentration of so that the pH of solution changes by one unit. (Kb
(1) 2  10–4 (2) 3.7 (NH4OH) = 1.8  10–5)
(3) 2.7 (4) 1.85 (1) 0.018 (2) 0.082
(3) 0.16 (4) 0.10
67. 0.1 M solution of Acetic acid is titrated against 0.1 M
74. The solubility of AgCl in water is 1.5  10–5 moles/
NaOH solution. What would be the difference in pH
1 litre and that of AgBr is 7  10–7 moles/litre. If pure
between 4 and 3
4 stages of neutralization of acid
1
water is saturated with AgCl (s) and AgBr (s) what
(1) 2 log 3
4 (2) 2 log 4
is the concentration of Ag+ ion in the solution ?
(3) log 1
3 (4) 1.0  1014
(1) 1.0  10–5 mol litre–1
68. From separate solutions of four Sodium salts NaW, (2) 1.57  10–5 mol litre–1
NaX, NaY and NaZ had pH 7.0, 9.0, 10.0 and 11.0 (3) 2.8  10–4 mol litre–1
respectively, when each solution was 0.1 M. The (4) 5.53  10–6 mol litre–1
strongest acid is 75. The solubility of Benzoic acid in water is 3.4 g per
(1) HW (2) HX litre at 25ºC. If dissociation constant of Benzoic acid
(3) HY (4) HZ is 6  10–5, what is the percentage of degree of
69. The ionization constant of NH 4 + in water is dissociation of Benzoic acid
5.6  10–10 at 25ºC. The rate constant for the reaction (1) 5.23 % (2) 3.40 %
of NH4+ and OH– to form NH3 and H2O at 25ºC is
(3) 2.15% (4) 4.64%
3.4  1010 L mol–1 s–1. The rate constant for proton
transfer from water to NH3 is CBSE – PMT
1. The ionization constant of ammonium hydroxide is
(1) 6.07  105 (2) 6.07  10–10
1.77 ×10–5 at 298 K. Hydrolysis constant of ammo-
(3) 6.07  10–5 (4) 6.07  1010 nium chloride is
(1) 5.65 × 10–12 (2) 5.65 × 10–10
70. pH of pure water is found to be 6.5. It temperature is –12
(3) 6.50 × 10 (4) 5.65 ×10–13
(1) Equal to 0ºC 2. –
What is the [OH ] in the final solution prepared by
(2) More than 25ºC mixing 20.0 mL of 0.050 M HCl with 30.0 mL of
(3) Equal to 25ºC 0.10 M Ba(OH)2?
(4) Between 0ºC and 25ºC (1) 0.12 M (2) 0.10 M
(3) 0.40 M (4) 0.0050 M
71. The decreasing order of strength of following bases 3. The dissociation constants for acetic acid and HCN
NH3, CH3COO– and Cl– is at 25°C are 1.5×10–5 and 4.5×10–10 respectively. The
(1) Cl–, CH3COO–, NH3 equilibrium constant for the equilibrium
(2) CH3COO–, NH3, Cl– CN   CH 3COOH HCN + CH3COO–
(3) NH3, Cl–, CH3COO– would be
(4) NH3, CH3COO–, Cl– (1) 3.0 × 104 (2) 3.0 × 105
–5
(3) 3.0 × 10 (4) 3.0 × 10–4
72. Three sparingly soluble salts M2X, QY2, PZ 3 have 4. Equal volumes of three acid solutions of pH 3, 4 and
same solubilities. Their Ksp values are related as : 5 are mixed in a vessel. What will be the H+ ion
(1) Ksp (M2X) = Ksp (QY2) = Ksp (PZ3) concentration in the mixture?
(2) Ksp (M2X) = Ksp (QY2) > Ksp (PZ3) (1) 1.11 × 10–4 M (2) 3.7 × 10–4 M
(3) 3.7 × 10–3 M (4) 1.11 × 10–3 M
(3) Ksp (M2X) = Ksp (QY2) < Ksp (PZ3)
(4) None of these

[166]
 Ionic Equilibrium

5. If the concentration of OH – ions in the reaction

[In  ]
Fe(OH) 3 (s) Fe 3+ (aq) + 3OH – (aq) is (2) log  pK In  pH
[HIn]
decreased by (1/4) times, then equilibrium
concentration of Fe3+ will increase by [HIn]
(3) log  pK In  pH
[In  ]
(1) 8 times (2) 16 times
(3) 64 times (4) 4 times [HIn]
(4) log  pH  pK In
6. Equimolar solutions of the following were prepared [In  ]
in water separately. Which one of the solutions will 13. The solubility product of a sparingly soluble salt AX2
record the highest pH? is 3.2 × 10–11. Its solubility (in moles/litre) is
(1) SrCl2 (2) BaCl2
(3) MgCl2 (4) CaCl2 (1) 4 × 10– 4 (2) 5.6 × 10– 6
7. A weak acid, HA, has a Ka of 1.00 × 10–5. If 0.100 (3) 3.1 × 10 –4
(4) 2 × 10– 4
mol of this acid is dissolved in one litre of water, the
14. A buffer solution is prepared in which the
percentage of acid dissociated at equilibrium is closest
to concentration of NH 3 is 0.30 M and the
(1) 1.00% (2) 99.9% concentration of NH4+ is 0.20 M. If the equilibrium
(3) 0.100% (4) 99.0% constant, Kb for NH3 equals 1.8 × 10–5, what is the
8. Calculate the pOH of a solution at 25ºC that contains
1 × 10–10 M of hydronium ions, i.e. H3O+ pH of this solution? (log 2.7 = 0.43)

(1) 4 (2) 9 (1) 9.08 (2) 9.43

(3) 1 (4) 7 (3) 11.72 (4) 8.73
9. The hydrogen ion concentration of a 10–8 M HCl
15. Which of the following is least likely to behave as
aqueous solution at 298 K (KW = 10–14) is
[ Lewis base ?
(1) 9.525 × 10–8 M (2) 1.0 × 10–8 M (1) H 2 O (2) NH 3
(3) 1.0 × 10–6 M (4) 1.0525 × 10–7 M (3) BF 3 (4) OH –
10. Which of the following pairs consitutes a buffer? 16. Which one of the following statement is not true ?

(1) HNO3 and NH4NO3

(1) pH of drinking water should be between
(2) HCl and KCl
(3) HNO2 and NaNO2 5.5 – 9.5
(4) NaOH and NaCl (2) Concentration of DO below 6 ppm is good for
11. At 25ºC, the dissociation constant of a base, BOH, is the growth of fish
1.0 × 10–12. The concentration of hydroxyl ions in (3) Clean water would have a BOD value of less
0.01 M aqueous solution of the base would be than 5 ppm
(4) Oxides of sulphur, nitrogen and carbon are the
(1) 1.0 × 10–6 mol L–1 most widespread air pollutant
(2) 1.0 × 10–7 mol L–1
(3) 2.0 × 10–6 mol L–1 17. The Ksp of Ag2CrO4 , AgCl, AgBr and AgI are
(4) 1.0 × 10–5 mol L–1 respectively, 1.1 × 10–12, 1.8 × 10–10, 5.0 × 10–13,
12. The rapid change of pH near the stoichiometric point
8.3 × 10–17. Which one of the following salts will
of an acid-base titration is the basis of indicator
detection. pH of the solution is related to ratio of the precipitate last if AgNO3 solution is added to the
concentrations of the conjugate acid (HIn) and base solution containing equal moles of NaCl, NaBr, NaI
(In–) forms of the indicator by the expression and Na2CrO4 ?
(1) AgBr (2) Ag2 CrO4
[In  ]
(1) log  pH  pK In (3) AgI (4) AgCl
[HIn]

[167]
 Ionic Equilibrium

18. What is the pH of the resulting solution when equal (3) X/233 = Ksp (4) X = Ksp
volumes of 0.1 M NaOH and 0.01 M HCl are 4. pH of 1 litre 0.1 M HCl when 5 gm of HF is added
mixed?
(1) 1.04 (2) 12.65 (3) 0.1 (4) 0.01
5. Solubility of PbI2 is 4 × 10–5. It solubility product is
(3) 2.0 (4) 7.0
19. Which one of the following pairs of solution is not
(1) 6.4 × 10–15 (2) 6.4 × 10–14
an acidic buffer?
(3) 2.56 × 10–13 (4) 6.4 × 10–13
(1) H3PO4 and Na3PO4
6. The Ksp of Mg(OH)2 is 1 × 10–12 0.01 M MgCl2
(2) HClO4 and NaClO4
will precipitate at the limiting pH.
(3) CH3COOH and CH3COONa
(1) 3 (2) 9
(4) H2CO3 and Na2CO3
(3) 5 (4) 8
20. In the equilibrium constant for 7. When solid lead iodide is added to water, the
equilibrium concentration of I – becomes
N 2 (g)  O 2(g) 2NO(g) is K, the equilibrium 2.6 × 10–3M. What is the Ksp for PbI2?
1 1
constant for N 2 (g)  O 2 (g) NO(g) will (1) 2.2 × 10–9 (2) 8.8 × 10–9
2 2
be: (3) 1.8 × 10–8 (4) 3.5 × 10–8
8. What is the [H+] in a 0.40 M solution of HOCl,
(1) K 2 (2) K 1/2 Ka = 3.5 × 10–8?
(1) 1.4 × 10–8M (2) 1.2 × 10–4M
1
(3) K (4) K (3) 1.9 × 10–4M (4) 3.7 × 10–4M
2
9. Which one of the f ollowing is not acid-base
DPMT conjugate pair?
(1) HONO, NO 2
1. Determine the pH of the solution that results from
the addition of 20.00 mL of 0.01 M Ca(OH)2 to (2) CH3 NH3 , CH3 NH 2
30.00 mL of 0.01 M HCl. []
(3) C6H5 – COOH, C6H5COO–
(1) 11.30 (2) 10.53 (4) H3O+, OH–
(3) 2.70 (4) 8.35 10. For preparing a buffer solution of pH = 7.0, which
2. 0.5 g mixture of NaHCO3 and Na2CO3 titrated with buffer system you will choose?
HCl. The change of colour of indicator appears at (1) H 3 PO 4 , H 2 PO 4 (2) H 2 PO 4 , HPO 42 
pH 9 and at pH 5, the reaction corresponding pH 9
will be as
(3) HPO24  , PO34 (4) H3 PO4 , PO34
11. Which one of the following species acts only as a
(1) CO32– + HCO3–  2CO2 + H2O + 3e
1base?
(2) HCO3– + H+  H2O + CO2 (1) H2 S (2) HS –
(3) CO32– + 2H+  H2CO3 (3) S 2– (4) H 2 O
(4) CO32– + H+  HCO3– 12. A solution is 0.1M with respect to Ag+, Ca2+, Mg2+
3. Solubility of BaSO4 in water is X g/ltr, if solubility and Al 3+ which will precipitate at lowest
product constant for BaSO 4 is Ksp then relation concentration of [PO34 ] when solution of Na3PO4
between X and Ksp will be (At. wt. of Ba = 137, is added?
S = 32, O = 16) (1) Ag3PO4 (Ksp = 1 × 10–6)
(1) X = K sp (2) X/233 = K sp (2) Ca3(PO4)2 (Ksp = 1 × 10–33)
(3) Mg3(PO4)2 (Ksp = 1 × 10–24)

[168]
 Ionic Equilibrium

(4) AlPO4 (Ksp = 1 × 10–20) titrated against 10 ml of 0.1 M ammonia solution

(pKb = 5.0), the equivalence point occurs at pH
AIIMS
(1) 5.0 (2) 6.0
1. 40 ml of 0.1 M ammonia solution is mixed with 20 (3) 7.0 (4) 9.0
ml of 0.1 M HCl. What is the pH of the mixture?
(pkb of ammonia solution is 4.74).
(1) 4.74 (2) 2.26
(3) 9.26 (4) 5.00
2. When 10 ml of 0.1 M acetic acid (pKa = 5.0) is

[169]
 Assertion-Reason Type Questions (For AIIMS)
Each of the questions given below consists of two
statements, an assertion (A) and reason (R). Select
the number corresponding to the appropriate
alternative as follows
(1) If both A and R are true and R is the correct
7. A. Calorific value × GMM = Molar enthalpy of
combustion.
R. Combustion processes are exothermie, in
general.
8. A. The effect of temperature on equilibrium
constant is given by Vant Hoff’s equation.
R. Vant Hoff’s equation is

explanation of A, then mark 1 K1 Hº  T2 – T1 

log   
K 2 2.303 R  T1T2 
(2) If both A and R are true but R is not the correct
9. A. For the reaction,
explanation of A, then mark 2
H2 ( g )   2 ( g ) 2Hl(g ), K p  K c
(3) If A is true but R is false, then mark 3
R. Kp of all gaseous reactions is equal to Kc
(4) If both A and R are false, then mark 4 .
10. A. Kp is related to Kc by the relation,
K p  K c (RT) n .
1. A. The abrupt expansion of the compressed gas
always causes heating effect. R. K p has same dimensions are K e .
R. The expansion causes release of energy by the 11. A. pH of a solution of CH3COOH decreases on
gaseous system. dilution.
2. A. Heat capacity of a diatomic gas is higher than R. On dilution, degree of ionization of
that of monoatomic gas. CH3COOH increases.
R. Monoatomic gases are non-polar in nature.
12. A. For a sparingly soluble salt, K sp is the
3. A. Chemical equation
maximum value of ionic product in a solution.
H + (aq) + OH – (aq )  H 2 O(l )H = –x kj
R. K sp corresponds to the ionic product of the
represents enthalpy of formation of water.
R. Hneutralisation of strong acid – strong base is salt in a saturated solution.
never constant. 13. A. pH of pure water increase with increase in
4. A. The chemical reaction, temperature.
R. Degree of dissociation of water decreases with
3H 2 (g ) + N 2 ( g )  2NH 3
increase in temperature.
should be exothermic. 14. A. pH of a buffer solution does not change on
R. The process passes into equlibrium state when dilution.
G T,p becomes zero. R. On dilution the ratio of concentration of salt
5. A. No heat engine has an efficiency of 100%. and acid (or base) remains unchanged.
R. Complete conversion of heat which is a 15. A. pH of 10–2 M HCl is equal to 2.
random form of energy into work is not R. HCl being a strong acid is completely ionized.
possible.
6. A. G fº (graphite)  0
R. For free elements in their standard stae,
G fº may or may not be taken as zero.

[170]
 ANSWERS TO ASSIGNMENT

CHEMICAL THERMODYNAMICS AND THERMOCHEMISTRY

1. (1) 2. (2) 3. (4) 4. (3) 5. (1)

6. (4) 7. (2) 8. (4) 9. (2) 10. (2)
11. (3) 12. (1) 13. (4) 14. (2) 15. (1)
16. (1) 17. (2) 18. (3) 19. (4) 20. (4)
21. (2) 22. (2) 23. (1) 24. (3) 25. (4)
26. (4) 27. (1) 28. (4) 29. (1) 30. (4)
31. (1) 32. (3) 33. (3) 34. (2) 35. (1)
36. (2) 37. (2) 38. (1) 39. (3) 40. (4)
41. (1) 42. (2) 43. (2) 44. (4) 45. (1)
46. (1) 47. (3) 48. (1) 49. (3) 50. (1)
51. (1) 52. (4) 53. (3) 54. (1) 55. (2)
56. (4) 57. (4) 58. (4) 59. (3) 60. (3)
61. (4) 62. (4) 63. (2) 64. (1) 65. (2)
66. (3) 67. (2) 68. (2) 69. (4) 70. (3)
71. (2) 72. (3) 73. (2) 74. (2) 75. (4)

CBSE
1. (4) 2. (4) 3. (4) 4. (3) 5. (4)
6. (2) 7. (3) 8. (4) 9. (3) 10. (4)
11. (4) 12. (3) 13. (2) 14. (2) 15. (1)
16. (3) 17. (3) 18. (4) 19. (3) 20. (4)
21. (4) 22. (3) 23. (3) 24. (4) 25. (3)
26. (1) 27. (4) 28. (2)
DPMT
1. (2) 2. (3) 3. (4) 4. (1) 5. (1)
6. (1) 7. (4) 8. (1) 9. (2) 10. (1)
11. (1) 12. (3) 13. (3)
AIIMS

1. (4) 2. (2) 3. (3) 4. (1)

[171]
 CHEMICAL EQUILIBRIUM

1. (2) 2. (4) 3. (4) 4. (2) 5. (1)

6. (2) 7. (4) 8. (2) 9. (1) 10. (3)
11. (1) 12. (2) 13. (1) 14. (2) 15. (2)
16. (3) 17. (4) 18. (2) 19. (4) 20. (4)
21. (4) 22. (1) 23. (2) 24. (3) 25. (1)
26. (2) 27. (2) 28. (3) 29. (2) 30. (4)
31. (1) 32. (2) 33. (4) 34. (1) 35. (1)
36. (2) 37. (4) 38. (2) 39. (2) 40. (3)
41. (3) 42. (4) 43. (3) 44. (2) 45. (4)
46. (2) 47. (3) 48. (4) 49. (1) 50. (1)
51. (4) 52. (2) 53. (2) 54. (1) 55. (1)
56. (3) 57. (4) 58. (2) 59. (4) 60. (4)
61. (1) 62. (4) 63. (3) 64. (3) 65. (1)

CBSE
1. (4) 2. (2) 3. (3) 4. (2) 5. (4)
6. (4) 7. (3) 8. (2) 9. (1)

DPMT

1. (1) 2. (2) 3. (2) 4. (1) 5. (1)

6. (3) 7. (2) 8. (1) 9. (4) 10. (3)
11. (4)

AIIMS

1. (1) 2. (1) 3. (1)

[172]
 IONIC EQUILIBRIUM

1. (1) 2. (3) 3. (2) 4. (1) 5. (1)

6. (4) 7. (2) 8. (3) 9. (3) 10. (4)
11. (2) 12. (4) 13. (2) 14. (1) 15. (3)
16. (2) 17. (2) 18. (2) 19. (3) 20. (2)
21. (2) 22. (3) 23. (1) 24. (2) 25. (2)
26. (1) 27. (4) 28. (1) 29. (2) 30. (3)
31. (2) 32. (4) 33. (3) 34. (1) 35. (4)
36. (2) 37. (3) 38. (2) 39. (2) 40. (4)
41. (2) 42. (2) 43. (3) 44. (4) 45. (3)
46. (4) 47. (4) 48. (3) 49. (3) 50. (3)
51. (1) 52. (2) 53. (4) 54. (4) 55. (2)
56. (4) 57. (2) 58. (4) 59. (4) 60. (3)
61. (2) 62. (3) 63. (4) 64. (1) 65. (3)
66. (1) 67. (3) 68. (1) 69. (3) 70. (2)
71. (4) 72. (4) 73. (2) 74. (1) 75. (4)

CBSE
1. (2) 2. (2) 3. (1) 4. (4) 5. (3)
6. (2) 7. (1) 8. (1) 9. (4) 10. (3)
11. (2) 12. (1,3) 13. (4) 14. (2) 15. (3)
16. (2) 17. (2) 18. (2) 19. (2) 20. (2)

DPMT

1. (1) 2. (4) 3. (2) 4. (2) 5. (3)

6. (2) 7. (2) 8. (2) 9. (4) 10. (2)
11. (3) 12. (4)

AIIMS
1. (3) 2. (3)

[173]
 ASSERTION-REASON TYPE QUESTIONS (FOR AIIMS)

1. (4) 2. (2) 3. (4) 4. (2) 5. (1)

6. (4) 7. (2) 8. (3) 9. (3) 10. (3)
11. (1) 12. (1) 13. (4) 14. (1) 15. (1)

[174]