CHEMICAL EQUILIBRIUM

EXERCISE # S-I
1. Which of the following reactions goes almost all the way to completion, and which proceeds hardly
at all?
(a) N2(g) + O2(g) l 2NO (g); Kc = 2.7 × 10–18
(b) 2NO(g) + O2(g) l 2NO2 (g); Kc = 6.0 × 1013

2. Write down the expression for equilibrium constant KC and KP for the following reactions :
1 ˆˆ† SO 3 (g)
(a) SO2(g) + O 2 (g) ‡ˆˆ
2
(b) ˆˆ† H2O(g)
H2O(l) ‡ˆˆ

(c) ˆˆ† 2NH3(g) + CO2(g)

NH2COONH4(s) ‡ˆˆ

(d) ˆˆ† CH3COOC2H5(l) + H2O(l)

CH3COOH(l) + C2H5OH(l) ‡ˆˆ

(e) ˆˆ† NH4+(aq) + OH–(aq)

NH3(aq) + H2O(l) ‡ˆˆ
(excess)
(f) ˆˆ† Zn2+(aq) + H2(g)
Zn(s) + 2H+(aq) ‡ˆˆ

3. Write the relationship between Kp and Kc for the following reactions :

(a) ˆˆ† PCl (g) + Cl (g)
PCl5(g) ‡ˆˆ ˆˆ† 2NH (g)
(b) N2(g) + 3H2(g) ‡ˆˆ
3 2 3

(c) ˆˆ†
H (g) + I (g) ‡ˆˆ 2HI(g) ˆˆ †
(d) 2H O(g) ‡ˆˆ 2H (g) + O (g)
2 2 2 2 2

(e) ˆˆ† 2SO (g)

2SO2(g) + O2(g) ‡ˆˆ 3

4. Find stability of reactants for the given equilibrium reaction :

ˆˆˆ†
2XO (g) ‡ˆˆˆ X2(g) + O2(g) ; K1 = 1 × 10
24

ˆˆˆ†
2XO2 (g) ‡ˆˆˆ X2(g) + 2O2(g) ; K2 = 2.5 × 10
10

5. ˆˆ† B + C is 2 × 10–3. At a given time, the composition of

The value of Kc for the reaction 2A ‡ˆˆ
reaction mixture is [A] = [B] = [C] = 3 × 10–4 M. In which direction the reaction will proceed?
6. The ester or ethyl acetate is formed by the reaction between ethanol and acetic acid and equilibrium is
represented as :
ˆˆ†
CH3COOH(l) + C2H5OH(l) ‡ˆˆ CH3COOC2H5(l) + H2O(l).
(a) Write the concentration ratio (reaction quotient), QC for this reaction. (Note that water is not
in excess and is not a solvent in this reaction).
(b) At 293 K, if starts with 1.00 mole of acetic acid and 0.180 moles of ethanol, there is 0.171 moles
of ethyl acetate in the final equilibrium mixture. Calculate the equilibrium constant.
(c) Starting with 0.500 moles of ethanol and 1.000 mole of acetic acid and maintaining it at 293 K,
0.214 moles of ethyl acetate is found after some time. Has equilibrium been reached ?

7. If Kc = 0.5 × 10–9 at 1000 K for the reaction N2 (g) + O2 (g) l 2NO (g), what is Kc at 1000 K for
the reaction 2NO (g) ƒ N2 (g) + O2 (g)?

8. An equilibrium mixture of PCl5, PCl3 and Cl2 at a certain temperature contains 0.5 × 10–3 M PCl5,
1.5 × 10–2 M PCl3, and 3 × 10–2 M Cl2. Calculate the equilibrium constant Kc for the reaction
PCl5 (g) l PCl3 (g) + Cl2 (g).

9. A sample of HI (9.6 × 10–3 mol) was placed in an empty 2.00 L container at 1000 K. After equilibrium
was reached, the concentration of I2 was 4 × 10–4 M. Calculate the value of Kc at 1000 K for the
reaction H2 (g) + I2 (g) ƒ 2HI (g).

10. The vapour pressure of water at 27°C is 0.2463 atm. Calculate the values of Kp and Kc at 27°C for
the equilibrium H2O (l) ƒ H2O (g).

11. The value of Kc for the reaction 3O2 (g) l 2O3 (g) is 8 × 10–55 at 25°C. Do you expect pure air
at 25°C to contain much O3 (ozone) when O2 and O3 are in equilibrium? If the equilibrium concentration
of O2 in air at 25°C is 8 × 10–3 M, what is the equilibrium concentration of O3?

12. One mole of H2O and one mole of CO are taken in a 10 L vessel and heated to 725 K. At equilibrium
40 percent of water (by mass) reacts with carbon monoxide according to the equation.
ˆˆ†
H2O(g) + CO(g) ‡ˆˆ H2(g) + CO2(g)
Calculate the equilibrium constant for the reaction.

13. A vessel at 1000 K contains CO2 with a pressure of 0.6 atm. some of the CO2 is converted into CO on
addition of graphite. Calculate the value of K, if total pressure at equilibrium is 0.9 atm.
14. Calculate the equilibrium concentration of H2, I2 and HI at 300 K if initially 2 mol of H2 and I2 are
taken in a closed container of having volume 10 lit. [Given : H2 + I2 l 2HI ; K = 100 at 300 K]

15. A mixture of SO3, SO2 and O2 gases is maintained at equilibrium in 10 litre flask at a particular
temperature in which Kc for the reaction,
ˆˆ† 2SO3(g) is 100 mol–1 litre.
2SO2(g) + O2(g) ‡ˆˆ
At equilibrium,
(a) If number of mole of SO3 and SO2 in flask are same, how many mole of O2 are present ?
(b) If number of mole of SO3 in flask are twice the number of mole of SO2, how many mole of O2 are
present ?

16. For the given reaction,

ˆˆ† C(g) + D(g)
A(g) + B(g) ‡ˆˆ
the number of moles at equilibrium was found to be 4, 4 , 2 & 8 respectively in 1 L container. Find the
new equilibrium concentration if 18 moles of D are added to above 1 L container.

17. For the given reaction,

ˆˆ† PCl3 + Cl2
PCl5 ‡ˆˆ
the number of moles at equilibrium was found to be 2, 6 & 4 respectively at 10 atm pressure. Find the
new equilibrium moles & partial pressure, if it is restablished at an equilibrium pressure 50 atm.

18. For the dissociation reaction N2O4 (g) ‡ˆˆ ˆˆˆ†ˆ 2NO2 (g) derive the expression for the degree of
dissociation in terms of Kp and total pressure P.

19. ˆˆˆ
†
For the reaction 2SO3(g) ‡ˆˆˆ 2SO2(g) + O2(g)
Initially 5 moles of SO3 is taken and at equillibrium 4 moles of SO3 is dissociated then find out a and
the value of KC (Volume = 2litre)

20. 1.1 mole of A mixed with 2.2 mole of B and the mixture is kept in a 1 litre flask at the equillibrium,
ˆˆˆ
A + 2B ‡ˆˆ †
ˆ 2C + D is reached. At equillibrium 0.2 mole of C is formed then the value of KC will
be.

21. The air pollutant NO is produced in automobile engines from the high temperature reaction
N2(g) + O2(g) l 2NO (g) ; Kc = 16 at 2300 K. If the initial concentrations of N2 and O2 at 2300
K are both 1.5 M, what are the concentrations of NO, N2, and O2 when the reaction mixture reaches
equilibrium?
22. At 700 K, Kp = 0.2 for the reaction ClF3 (g) l ClF (g) + F2(g). Calculate the equilibrium partial
pressure of ClF3, ClF, and F2 if only ClF3 is present initially, at a partial pressure of 0.150 atm.

23. The degree of dissociation of N2O4 into NO2 at 1.5 atmosphere and 40°C is 0.25. Calculate its
Kp at 40°C.Also report degree of dissociation at 10 atmospheric pressure at same temperature.

24. At 46°C, Kp for the reaction N2O4(g) l 2NO2(g) is 0.667 atm . Compute the percent dissociation
of N2O4 at 46° C at a total pressure of 380 Torr .

25. 2 NOBr (g) l 2 NO (g) + Br2 (g). If nitrosyl bromide (NOBr) is 33.33% dissociated at 25° C
& a total pressure of 0.28 atm . Calculate Kp for the dissociation at this temperature.

26. The system N2O4 l 2 NO2 maintained in a closed vessel at 60º C & a pressure of 5 atm has an average
(i.e. observed) molecular weight of 69, calculate Kp. At what pressure at the same
temperature would the observed molecular weight be (230/3) ?

27. In the esterfication C2H5OH (l) + CH3COOH (l) l CH3COOC2H5 (l) + H2O (l) an equimolar mixture
of alcohol and acid taken initially yields under equilibrium, the water with mole fraction = 0.333.
Calculate the equilibrium constant.

28. The equilibrium constant for the reaction is 9 at 900°C S2(g) + C(s) l CS2(g) . Calculate the pressure
of two gases at equilibrium, when 2 atm of S2 and excess of C(s) come to equilibrium.

29. A sample of CaCO 3(s) is introduced into a sealed container of volume 0.821 litre &
heated to 1000K until equilibrium is reached. The equilibrium constant for the reaction
CaCO3(s) l CaO(s) + CO2(g) is 4 × 10-2 atm at this temperature. Calculate the mass of CaO
present at equilibrium.

30. Anhydrous calcium chloride is often used as a dessicant. In the presence of excess of CaCl2,, the
amount of the water taken up is governed by Kp = 6.4 × 1085 for the following reaction at room
temperature, CaCl2(s) + 6H2O(g) l CaCl2 .6H2O(s) . What is the equilibrium vapour pressure of
water in a closed vessel that contains CaCl2(s) ?

31. 20.0 grams of CaCO3(s) were placed in a closed vessel, heated & maintained at 727º C under
equilibrium CaCO3(s) l CaO(s) + CO2(g) and it is found that 75 % of CaCO3 was decomposed.
What is the value of Kp ? The volume of the container was 15 litres.
32. (a) Methanol, a liquid fuel that could possibly replace gasoline, can be prepared from water gas
and additional hydrogen at high temperature and pressure in the presence of a suitable catalyst.
Write the expression for the equilibrium constant for the reversible reaction.
2H2 (g) + CO (g) l CH3OH (g) DH = – 90.2 kJ
(b) Assume that equilibrium has been established and predict how the concentration of H2, CO and
CH3OH will differ at a new equilibrium if (1) more H2 is added. (2) CO is removed. (3) CH3OH
is added. (4) the pressure on the system is increased. (5) the temperature of the system is increased.
(6) more catalyst is added.

33. Ammonia is a weak base that reacts with water according to the equation
NH3 (aq) + H2O (l) l NH4+ + OH– (aq)
Will any of the following increase the percent of ammonia that is converted to the ammonium ion
in water?
(a) Addition of NaOH. (b) Addition of HCl. (c) Addition of NH4Cl.

34. Consider the gas-phase hydration of hexafluoroacetone, (CF3)2CO:

kf
(CF3)2CO (g) + H2O (g) l (CF3)2C(OH)2 (g)
kr

At 76°C, the forward and reverse rate constants are kf = 0.15 M–1s–1 and kr = 6 × 10–4s–1. What is
the value of the equilibrium constant Kc?

35. Listed in the table are forward and reverse rate constants for the reaction 2NO (g) l N2(g) +O2(g)
Temperature (K) kf (M–1s–1) kr (M–1s–1)
1400 0.29 1.1 × 10–6
1500 1.3 1.4 × 10–5
Is the reaction endothermic or exothermic? Explain in terms of kinetics.
 EXERCISE # S-II
1. One mole of N2O4 (g) at 300 K is left in a closed container under one atm . It is heated to
600 K when 20 % by mass of N2O4 (g) decomposes to NO2 (g) . Calculate resultant pressure.

2. Solid Ammonium carbamate dissociates as: NH2 COONH4 (s) l 2NH3(g) + CO2(g). In a closed
vessel solid ammonium carbamate is in equilibrium with its dissociation products. At equilibrium,
ammonia is added such that the partial pressure of NH3 at new equilibrium now equals the original
total pressure. Calculate the ratio of total pressure at new equilibrium to that of original total pressure.

3. A definite amount of solid NH4HS is placed in a flask already containing ammonia gas at a certain
temperature and 0.50 atm pressure. NH4HS decomposes to give NH3 and H2S and at equilibrium
total pressure in flask is 0.84 atm. Calculate equilibrium constant for the reaction :

4. For the reaction A(g) + 2B(g) ƒ C(g) + D(g) ; Kc = 1012 .

If the initial moles of A,B,C and D are 0.5, 1, 0.5 and 3.5 moles respectively in a one litre vessel.
What is the equilibrium concentration of B?

5. Calculate the equilibrium concentration of PCl3 and Cl2 at 300 K if initially 1 mol of PCl5 is taken in a
closed container of having volume 10 lit.
ˆˆˆ
†
[Given : PCl5(g) ‡ˆˆ –2
ˆ PCl3(g) + Cl2(g) ; KC = 10 at 300 K, 41 = 6.4 ]

6. When 36.8g N2O4 (g) is introduced into a 1.0-litre flask at 27°C . The following equilibrium
reaction occurs : N2O4 (g) l 2NO2 (g) ; Kp = 0.1642 atm.
(a) Calculate Kc of the equilibrium reaction.
(b) What are the number of moles of N2O4 and NO2 at equilibrium?
(c) What is the total gas pressure in the flask at equilibrium?
(d) What is the percent dissociation of N2O4?

7. The progress of the reaction

A ƒ nB with time, is presented in figure. Determine

(i) the value of n.

(ii) the equilibrium constant K.

(iii)the initial rate of conversion of A.

8. A mixture of hydrogen & iodine in the mole ratio 1.5 : 1 is maintained at 450º C. After the attainment
of equilibrium H2(g) + I2(g) l 2 HI(g), it is found on analysis that the mole ratio of I2 to HI is 1 : 18.
Calculate the equilibrium constant and the number of moles of each species present under equilibrium,
if initially, 127 grams of iodine were taken.

9. At certain temperature (T) for the gas phase reaction

2H2O(g) + 2Cl2 (g) ƒ 4HCl(g) + O2(g) Kp = 12 × 108 atm
If Cl2, HCl & O2 are mixed in such a manner that the partial pressure of each is 2 atm and the mixture
is brough into contact with excess of liquid water. What would be approximate partial pressure of
Cl2 when equilibrium is attained at temperature (T)?
[Given : Vapour pressure of water is 380 mm Hg at temperature (T)]

10. Two solids X and Y disssociate into gaseous products at a certain temperature as follows
X(s) l A(g) + C(g), and Y(s) l B(g) + C(g). At a given temperature, pressure over excess
solid X is 40 mm and total pressure over solid Y is 60 mm. When they are preset in separate containers.
Calculate
(a) the values of Kp for two reactions (in mm2)
(b) the ratio of moles of A and B in the vapour state over a mixture of X and Y.
(c) the total pressure of gases over a mixture of X and Y.

11. When 1 mole of A(g) is introduced in a closed rigid 1 litre vessel maintained at constant temperature
the following equilibria are established.
A (g) l B(g) + C(g) : KC
1

C (g) l D(g) + B(g) : KC

2

KC [C]eq 1
2
The pressure at equilibrium is twice the initial pressure. Calculate the value of if =
KC [B]eq 5
1

12. Equilibrium constants are given (in atm) for the following reactions at 0° C:
SrCl2×6H2O(s) ƒ SrCl2 × 2H2O (s) + 4H2O(g) Kp = 5 × 10-12
Na2HPO4×12 H2O(s) ƒ Na2HPO4 × 7 H2O (s) + 5H2 O(g) Kp = 2.43 × 10-13
Na2SO4×10 H2O(s) ƒ Na2SO4 (s) + 10 H2O (g) Kp = 1.024 × 10-27
PH2O
(% Relative humidity = ´ 100 )
Vapour pressure of H2O

The vapor pressure of water at 0°C is 4.56 torr.

Out of SrCl2 × 2H2O (s), Na2HPO4 × 7 H2O (s) and Na2SO4 (s),
Which is the most effective drying agent at 0°C?
13. At certain temperature , KC = 1.0 for reaction :
ˆˆ† N O(g) + O (g)
NO2(g) + NO (g) ‡ˆˆ 2 2

equal moles of NO and NO2 are to be placed in 5 litre container until N2O concentration at equilibrium
is 0.5M. How many mole of (NO + NO2) must be placed in the container.

14. In a vessel, two equilibrium are simultaneously established at same temperature as follows,
ˆˆ† 2NH3(g)
N2(g) + 3H2(g) ‡ˆˆ ...........(i)
ˆˆ† N2H4(g)
N2(g) + 2H2(g) ‡ˆˆ ...........(ii)
Initially the vessel contains N2 and H2 in the molar ratio of 9 : 13. The equilibrium pressure is 7 P0 in
which pressure due to ammonia is P0 and due to hydrogen is 2P0. Find the values of equilibrium
constants (Kp's) for both the reactions.

15. If vapour density of equilibrium mixture NO2 and N2O4 is found to be 42 for the reaction
ˆˆˆ
†
N2O4 ‡ˆˆˆ 2NO2. Find :
(a) Abnormal molecular weight
(b) Degree of dissociation
(c) Percentage of NO2 in the mixture
 EXERCISE # O-I
Only one is correct

1. ˆˆˆ
†
x ‡ˆˆ
ˆ y reaction is said to be in equilibrium, when :-

(A) Only 10% conversion of x to y takes place

(B) Complete conversion of x to y has taken place
(C) Conversion of x to y is only 50% complete
(D) The rate of change of x to y is just equal to the rate of change of y to x in the system

2. For which reaction is Kp = Kc :-

ˆˆˆ
†
(A) 2NOCl(g) ‡ˆˆ
ˆ 2NO(g) + Cl2(g) ˆˆˆ
†
(B) N2(g) + 3H2(g) ‡ˆˆ
ˆ 2NH3(g)

ˆˆˆ
†
(C) H2(g) + I2(g) ‡ˆˆ
ˆ 2HI(g) ˆˆˆ
†
(D) 2SO2(g) + O2(g) ‡ˆˆ
ˆ 2SO3(g)

3. For the reaction

ˆˆˆ
†
CuSO4.5H2O(s) ‡ˆˆ
ˆ CuSO4.3H2O(s)+ 2H2O(g)
Which one is correct representation :–
(A) Kp = (P(H2O) )2 (B) Kc = [H2O]2 (C) Kp = Kc(RT)2 (D) All

Kp
4. log + log RT = 0 is true relationship for the following reaction:-
Kc

ˆˆˆ
†
(A) PCl5 ‡ˆˆ
ˆ PCl3 + Cl2 ˆˆˆ
†
(B) 2SO2 + O2 ‡ˆˆ
ˆ 2SO3

ˆˆˆ
†
(C) N2 + 3H2 ‡ˆˆ
ˆ 2NH3 (D) (B) and (C) both

5. ˆˆˆ
†
For a reaction N2 + 3H2 ‡ˆˆ
ˆ 2NH3, the value of KC does not depends upon :-

(a) Initial concentration of the reactants (b) Pressure

(c) Temperature (d) Catalyst
(A) Only c (B) a, b, c (C) a, b, d (D) a, b, c, d

6. ˆˆˆ
†
If some He gas is introduced into the equilibrium PCl5(g) ‡ˆˆ
ˆ PCl3(g) + Cl2(g) at constant pressure

and temperature then equilibrium constant of reaction:

(A) Increase (B) Decrease (C) Unchange (D) Nothing can be said
7. The equilibrium constant for the given reaction :

1
SO3(g) ƒ SO2(g) + O (g) ; Kc = 5 × 10–2
2 2
The value of Kc for the reaction :
2SO2(g) + O2(g) ƒ 2SO3(g), will be
(A) 400 (B) 2.40 × 10–3 (C) 9.8 × 10–2 (D) 4.9 × 10–2

8. For the following three reactions, 1, 2 and 3 equilibrium, constants are given :

ˆˆˆ
†
(1) CO(g) + H2O(g) ‡ˆˆ
ˆ CO2(g) + H2(g) ; K1

ˆˆˆ
†
(2) CH4(g) + H2O(g) ‡ˆˆ
ˆ CO(g) + 3H2(g) ; K2

ˆˆˆ
†
(3) CH4(g) + 2H2O(g) ‡ˆˆ
ˆ CO2(g) + 4H2(g) ; K3
Which of the following relations is correct ?

(A) K1 K 2 = K 3 (B) K 2K 3 = K1 (C) K 3 = K1K 2 (D) K 3 = K32 K12

9. Sulfide ion in alkaline solution reacts with solid sulfur to form polysulfide ions having formulas
S22-, S32-, S42- and so on. The equilibrium constant for the formation of S22- is 12 ( K1) & for the
formation of S32- is 132 (K2 ), both from S and S2-.What is the equilibrium constant for the formation
of S32- from S22- and S?
(A) 11 (B) 12 (C) 132 (D) None of these

10. If 0.5 mole H2 is reacted with 0.5 mole I2 in a ten-litre container at 444° C and at same temperature
value of equilibrium constant Kc is 49, the ratio of [HI] and [I2] will be :-
1 1
(A) 7 (B) (C) (D) 49
7 7

11. ˆˆˆ
In the reaction, N2 + O2 ‡ˆˆ †ˆ 2NO, the moles/litre of N2, O2 and NO respectively 0.25, 0.05 and
1.0 at equilibrium. The initial concentrations of N2 and O2 will respectively be
(A) 0.75 mole/lit., 0.55 mole/lit. (B) 0.50 mole/lit., 0.75 mole/lit.
(C) 0.25 mole/lit., 0.50 mole/lit (D) 0.25 mole/lit., 1.0 mole/lit.

12. How many moles per litre of PCl5 has to be taken to obtain 0.1 mole Cl2, if the value of equilibrium
constant Kc is 0.04 ?
(A) 0.15 (B) 0.25 (C) 0.35 (D) 0.05
13. ˆˆˆ
In the beginning of the reaction, A ‡ˆˆ†ˆ B + C, 2 moles of A are taken, out of which 0.5 mole gets
dissociated. What is the degree of dissociation of A ?
(A) 0.5 (B) 1 (C) 0.25 (D) 4.2

14. In the reaction, PCl5 PCl3 + Cl2, the amount of each PCl5, PCl3 and Cl2 is 2 mole at equilibrium
and total pressure is 3 atmosphere. The value of Kp will be
(A) 1.0 atm. (B) 3.0 atm. (C) 2.9 atm. (D) 6.0 atm.

15. 4 moles of PCl5 are heated at constant temperature in closed container. If degree of dissociation for
PCl5 is 0.5 calculate total number of moles at equilibrium :-
(A) 4.5 (B) 6 (C) 3 (D) 4

16. For the reaction A + 2B 2C + D, initial concentration of A is a and that of B is 1.5 times that
of A. Concentration of A and D are same at equilibrium. What should be the concentration of B at
equilibrium ?
a a 3a
(A) (B) (C) (D) All of the above.
4 2 4

17. For the reaction 3 A (g) + B (g) ƒ 2 C (g) at a given temperature , Kc = 9.0 . What must be
the volume of the flask, if a mixture of 2.0 mol each of A , B and C exist in equilibrium?
(A) 6L (B) 9L (C) 36 L (D) None of these

18. For the following gases equilibrium. N2O4 (g) l 2NO2 (g)
Kp is found to be equal to Kc. This is attained when temperature is
(A) 0°C (B) 273 K (C) 1 K (D) 12.19 K

19. The degree of dissociation of SO3 is a at equilibrium pressure p0.

ˆˆ† 2SO2(g) + O2(g)
Kp for 2SO3(g) ‡ˆˆ

p0a3 p0 a3 p0a 2
(A) (B) (C) (D) None of these
2(1 - a)3 (2 + a)(1 - a)2 2(1 - a)2

20. For the reaction : 2Hl (g) ƒ H2(g) + I2(g), the degree of dissociated (a) of Hl(g) is related to equilibrium
constant KP by the expression

1+ 2 Kp 1 + 2K p 2K p 2 Kp
(A) (B) (C) 1 + 2K p (D) 1 + 2 K
2 2 p
21. The equilibrium constant for the reaction
A(g) + 2B(g) ƒ C(g)
is 0.25 dm6mol–2. In a volume of 5 dm3, what amount of A must be mixed with 4 mol of B to yield
1 mol of C at equilibrium.
(A) 3 moles (B) 24 moles (C) 26 moles (D) None of these

22. A 20.0 litre vessel initially contains 0.50 mole each of H2 and I2 gases. These substances react and
finally reach an equilibrium condition. Calculate the equilibrium concentration of HI if Keq = 49 for
the reaction H2 + I2 ƒ 2HI.
(A) 0.78 M (B) 0.039 M (C) 0.033 M (D) 0.021 M

23. At 675 K, H2(g) and CO2 (g) react to form CO(g) and H2O (g), Kp for the reaction is 0.16.
If a mixture of 0.25 mole of H2(g) and 0.25 mol of CO2 is heated at 675 K, mole % of CO(g) in equilibrium
mixture is :
(A) 7.14 (B) 14.28 (C) 28.57 (D) 33.33

24. The vapour density of N2O4 at a certain temperature is 30. What is the % dissociation of N2O4 at
this temperature?
(A) 53.3% (B) 106.6% (C) 26.7% (D) None

25. The equilibrium constant KP (in atm) for the reaction is 9 at 7 atm and 300 K.
A2 (g) ƒ B2(g) + C2 (g)
Calculate the average molar mass (in gm/mol) of an equilibrium mixture.
Given : Molar mass of A2, B2 and C2 are 70, 49 & 21 gm/mol respectively.
(A) 50 (B) 45 (C) 40 (D) 37.5

26. Vapour density of the equilibrium mixture of the reaction

2NH3 (g) ƒ N2 (g) + 3H2 (g) is 6.0
Percent dissociation of ammonia gas is:
(A) 13.88 (B) 58.82 (C) 41.66 (D) None of these

27. The equilibrium concentration of B [(B)e] for the reversible reaction A B can be evaluated by
the expression:-

kf -1
(A) KC [A]e-1 (B) k [ A ]e (C) k f k -1
b
[A]e (D) kf kb [A]–1
b
28. The equilibrium 2SO2(g) + O2(g) ƒ 2SO3(g) shifts forward if :-
(A) A catalyst is used.
(B) An adsorbent is used to remove SO3 as soon as it is formed.
(C) Small amounts of reactants are removed.
(D) None of these

29. In manufacture of NO, the reaction N2(g) + O2(g) ƒ 2NO(g), DH +ve is favourable if :-
(A) Pressure is increased (B) Pressure is decreased
(C) Temperature is increased (D) Temperature is decreased

30. In which of the following reactions, increase in the pressure at constant temperature does not affect
the moles at equliibrium :
1
(A) 2NH3(g) ƒ N2(g) + 3H2(g) (B) C(g) + O (g) ƒ CO(g)
2 2

1
(C) H2(g) + O (g) ƒ H2O(g) (D) H2(g) + I2(g) ƒ 2HI(g)
2 2

31. Change in volume of the system does not alter the number of moles in which of the following equilibrium
(A) N2(g) + O2(g) ƒ 2NO(g) (B) PCl5(g) ƒ PCl3(g) + Cl2(g)
(C) N2(g) + 3H2(g) ƒ 2NH3(g) (D) SO2Cl2(g) ƒ SO2(g) + Cl2(g)

32. The conditions favourable for the reaction :

2SO2(g) + O2(g) ƒ 2SO3(g) ; DH° = – 198 kJ
are :
(A) low temperature, high pressure (B) any value of T and P
(C) low temperature and low pressure (D) high temperature and high pressure

33. Densities of diamond and graphite are 3.5 and 2.3 gm/mL.
C (diamond) ƒ C (graphite) DrH = –1.9 kJ/mole
favourable conditions for formation of diamond are
(A) high pressure and low temperature (B) low pressure and high temperature
(C) high pressure and high temperature (D) low pressure and low temperature
34. The equilibrium SO2Cl2(g) ƒ SO2(g) + Cl2(g) is attained at 25°C in a closed rigid container and an inert
gas, helium is introduced. Which of the following statements is/are correct.
(A) concentrations of SO2, Cl2 and SO2Cl2 do not change
(B) more chlorine is formed
(C) concentration of SO2 is reduced
(D) more SO2Cl2 is formed

35. The yield of product in the reaction

2A(g) + B(g) 2C(g) + Q kJ
would be lower at :
(A) low temperature and low pressure (B) high temperature & high pressure
(C) low temperature and to high pressure (D) high temperature & low pressure
 EXERCISE # O-II
More than one may be correct
1. Following two equilibrium is simultaneously established in a container
PCl5(g) PCl3(g) + Cl2(g)
CO(g) + Cl2(g) COCl2(g)
If some Ni(s) is introduced in the container forming Ni (CO)4 (g) then at new equilibrium
(A) PCl3 concentration will increase (B) PCl3 concentration will decrease
(C) Cl2 concentration will remain same (D) CO concentration will remain same

2. For the reaction PCl5(g) ƒ PCl3(g) + Cl2(g), the forward reaction at constant temperature is favoured
by
(A) introducing an inert gas at constant volume
(B) introducing chlorine gas at constant volume
(C) introducing an inert gas at constant pressure
(D) introducing PCl5 at constant volume.

3. When NaNO3 is heated in a closed vessel, oxygen is liberated and NaNO2 is left. At equilibrium
(A) addition of NaNO2 favours reverse reaction
(B) addition of NaNO3 favours forward reaction
(C) increasing temperature favours forward reaction
(D) increasing pressure favours reverse reaction

4. For the gas phase reaction, C2H4 + H2 ƒ C2H6 (DH = – 32.7 kcal), carried out in a closed vessel,
the equilibrium moles of C2H4 can be increased by
(A) increasing the temperature (B) decreasing the pressure
(C) removing some H2 (D) adding some C2H6
CE0089
5. Phase diagram of CO2 is shown as following

73
Solid Liquid
67
P (atm)
5

1 Gas

195 217 298 304

T(K)
Based on above find the correct statement(s)
(A) 298K is the normal boiling point of liquid CO2
(B) At 1 atm & 190 K CO2 will exist as gas.
(C) CO2(s) will sublime above 195K under normal atmospheric pressure
(D) Melting point & boiling point of CO2 will increase on increasing pressure

6. The equilibrium between, gaseous isomers A, B and C can be represented as

Reaction Equilibrium constant
A (g) l B (g) : K1 = ?
B (g) l C (g) : K2 = 0.4
C (g) l A (g) : K3 = 0.6
If one mole of A is taken in a closed vessel of volume 1 litre, then
(A) [A] + [B] + [C] = 1 M at any time of the reactions
(B) Concentration of C is 4.1 M at the attainment equilibrium in all the reactions

1
(C) The value of K1 is
0.24
(D) Isomer [A] is least stable as per thermodynamics.

7. For the gas phase exothermic reaction, A2 + B2 ƒ C2, carried out in a closed vessel, the equilibrium
moles of A2 can be increased by
(A) increasing the temperature (B) decreasing the pressure
(C) adding inert gas at constant pressure (D) removing some C2

8. Consider the equilibrium HgO(s) + 4I– (aq) + H2O (l) ƒ HgI42– (aq) + 2OH– (aq), which changes
will decrease the equilibrium concentration of HgI42–
(A) Addition of 0.1 M HI (aq) (B) Addition of HgO (s)
(C) Addition of H2O (l) (D) Addition of KOH (aq)
9. Decrease in the pressure for the following equilibria : H2O (s) ƒ H2O(l) result in the :
(A) formation of more H2O (s) (B) formation of more H2O(l)
(C) increase in melting point of H2O(s) (D) decrease in melting point of H2O(s)

Assertion Reason
10. Statement -1 :Total number of moles in a closed system at new equilibrium is less than the old
equilibrium if some amount of a substance is removed from a system
(consider a reaction A(g) B(g) ) at equilibrium.
Statement -2 :The number of moles of the substance which is removed, is partially compensated
as the system reached to new equilibrium.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for
statement-1.
(C) Statement-1 is false, statement-2 is true.
(D) Statement-1 is true, statement-2 is false.

11. Statement-1 : Ammonia at a pressure of 10 atm and CO2 at a pressure of 20 atm are introduced
into an evacuated chamber. If Kp for the reaction
NH2COONH4 (s) ƒ 2NH3 (g) + CO2 (g) is 2020 atm3, the total pressure
after a long time is less than 30 atm.
Statement-2 : Equilibrium can be attained from both directions.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.

12. Statement-1 : Catalyst does not alter the equilibrium constant

Statement-2 : Because for the catalysed reaction and uncatalysed reaction DH remain same an
equilibrium constant depend on DH.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.

13. Statement-1 : Equilibrium constant may show higher or lower values with increase in temperature
Statement-2 : The change depend on heat of reaction.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.
Comprehension :
Paragraph for Question Nos. 12 to 15
In a 7.0 L evacuated chamber, 0.50 mol H2 and 0.50 mol I2 react at 427°C .
H2(g) + I2(g) ƒ 2HI(g). At the given temperature, KC = 49 for the reaction.
14. What is the value of Kp ?
(A) 7 (B) 49 (C) 24.5 (D) None

15. What is the total pressure (atm) in the chamber?

(A) 83.14 (B) 831.4 (C) 8.21 (D) None

16. How many moles of the iodine remain unreacted at equilibrium?

(A) 0.388 (B) 0.112 (C) 0.25 (D) 0.125

17. What is the partial pressure (atm) of HI in the equilibrium mixture?

(A) 6.385 (B) 12.77 (C) 40.768 (D) 646.58

Paragraph for Question Nos. 16 to 18

Influence of pressure, temperature, concentration and addition of inert gas on a reversible chemi-
cal reaction in equilibrium can be explained by formulating the expression for equilibrium constant
Kc or Kp for the equilibrium. On the other hand Le Chatelier principle can be theoretically used
to explain the effect of P, T or concentration on the physical or chemical equilibrium both.
18. ˆˆˆ
†
For the reaction : PCl5 ‡ˆˆˆ PCl3 + Cl2 increase of pressure shows :
(A) An increase in degree of dissociation and a decrease in Kc
(B) A decrease in degree of dissociation and a decrease in Kc
(C) An increase in degree of dissociation but Kc remains constant
(D) A decrease in degree of dissociation but Kc remains constant

19. ˆˆˆ
†
For the reaction : 2SO2 + O2 ‡ˆˆˆ 2SO3; DH = –ve, An increase in temperature shows :
(A) More dissociation of SO3 and a decrease in Kc
(B) Less dissociation of SO3 and an increase in Kc
(C) More dissociation of SO3 and an increase in Kc
(D) Less dissociation of SO3 and an decrease in Kc
20. ˆˆˆ
†
For the reaction : Fe3+ (aq.)+ SCN – (aq.) ‡ˆˆˆ [Fe(NCS)] (aq.) ; in equilibrium if little more aqueous
2+

Yellow Re d

solution of FeCl3 is added, than :

(A) Forward reaction becomes more and red colours is deepened
(B) Backward reaction becomes more and red colour faintens
(C) Solution becomes colourless
(D) None of these

Match the column :

21. Column I Column II
(A) KP < KC (P) N2 + 3H2 ƒ 2NH3
(B) Introduction of inert gas at (Q) PCl5 (g) ƒ PCl3 (g) + Cl2 (g)
constant pressure will decrease
the concentration of reactants

(C) K oP is dimensionless (R) 2NO2 (g) ƒ N2O4 (g)

(D) Temperature increase will shift (S) NH3 (g) + HI (g) ƒ NH4I (s)
the reaction on product side.

22. Column-I Column-II

(Reactions) (Favourable conditions)
(A) Oxidation of nitrogen (p) Addition of inert gas at constant pressure
ˆˆˆ
†
N2(g) + O2(g) + 180.5 kJ ‡ˆˆˆ 2NO(g)
(B) Dissociation of N2O4(g) (q) Decrease in pressure
ˆˆˆ
N2O4(g) + 57.2 kJ ‡ˆˆ †ˆ 2NO2(g)
(C) Oxidation of NH3(g) (r) Decrease in temperature
ˆˆˆ
†
4NH3(g) + 5O2(g) ‡ˆˆˆ 4NO(g)+6H2O(g)
+ 905.6 kJ
(D) Formation of NO2(g) (s) Increase in temperature
ˆˆˆ
NO(g) + O3(g) ‡ˆˆ †
ˆ NO2(g) + O2(g)
+ 200 kJ
Matching list type :
Answer Q.No. 23, 24 and 25 by appropriately matching the information given in the three columns
of the following table.
Column-I Column-II Column-III
(Reaction) (If a is negligiable
w.r.t. 1)
ˆˆˆ
†
(A) 2X(g) ‡ˆˆˆ Y(g) + Z(g), DH = –ve (P) a = 2 × Kp (I) K increase with increase in
temperature
ˆˆˆ
†
(B) X(g) ‡ˆˆˆ Y(g) + Z(g), DH = +ve (Q) a = 3 × K p .P (II) K decrease with increase in
temperature
1/3
ˆˆˆ
†
(C) 3X(g) ‡ˆˆˆ Y(g) + Z(g) , DH = +ve (R) a = æ 2Kp ö (III) Pressure has no effect
ç P ÷
è ø
ˆˆˆ
†
(D) 2X(g) ‡ˆˆˆ Y(g) + 2Z(g), DH = +ve (S) a = Kp / P (IV) Addition of inert gas at
constant pressure shift
equilibrium in forward
direction
23. Which of the following option is correctly matched ?
(A) A-Q-III (B) B-S-II (C) C-Q-II (D) D-R-IV

24. Correct representation of reaction in option (A) is represented by graph

lnKP lnKP

(A) (B)

1/T 1/T

lnKP lnKP

(C) (D)

1/T 1/T

25. For the reaction of option (B) if degree of dissociation varies inversily as square root of pressure
of the system. Suppose at constant temperature volume is increased 16 times of its initial volume
the degree of dissociation (a) for this reaction will become :
(A) 4 times (B) 2 times (C) 1/4 times (D) 1/2 times
 ANSWER KEY
EXERCISE # S-I
1. (a) incomplete (b) almost complete

(PSO3 ) [SO3 ]
2. (a) KP = 1 ; KC = 1
(PSO2 )(PO2 ) 2
[SO2 ][O2 ]2
(b) KC = [H2O] [here H2O(l) is a pure liquid so its concentration is 1.]
KP = PH 2O
= vapour pressure
= aqueous tension
(c) KC = [NH3]2 [CO2] (Q active mass of solid is 1)

KP = ( PNH3 ) PCO2
2

(d) KC =
[CH 3COOC 2 H 5 ] [ H 2O ] [here H2O is not in excess]
[CH 3COOH ][C2 H 5OH ]
KP is not defined for liquid phase.

éë NH +4 ùû [ OH - ]
(e) KC =
[ NH3 ] [here H2O(l) is in excess (solvent) so its concentration is 1]

PH2 ´ [Zn 2+ ]
(f) K PC = [Q active mass of solid is 1]
[ H + ]2

3. (a) Here, Dng = 1+ 1 – 1 = 1

Kp = Kc (RT)1 = KcRT
(b) Here, Dng = 2 – (3+1) = –2
Kp = Kc (RT)–2
(c) Here, Dng = 2 – (1+1) = 0
Kp = Kc (RT)0 = Kc
(d) Here, Dng = 2 + 1 – 2 = 1
Kp = Kc (RT)1 = KcRT
(e) Here, Dng = 2 – (2 + 1) = –1
Kp = Kc (RT)–1 = Kc / RT
4. Q K1 > K2
So the stability of XO < XO2
For reactants, stability increases when value of K decreases.
5. Qc > Kc so the reaction will proceed in the reverse direction.
[CH 3COOC 2 H 5 ][H 2O]
6. (a) QC = [Q Water is not a solvent here]
[CH 3COOH][C 2 H 5OH]
(0.171) ´ (0.171)
(b) Kc = = 3.92
(1 - 0.171) ´ (0.180 - 0.171)

(0.214) ´ (0.214)
(c) Qc = = 0.204 ¹ K c
(0.786) ´ (0.286)
\ Equilibrium has not been reached.
7. 2 × 109
8. 0.9
9. KC = 100
10. Kp = 0.2463
11. 64 × 10–32
12. K c = 0.44
13. KP = 1.2 atm.
1
14. [HI] = M
3
1
[I2] = [H2] = M
30
15. (a) 0.1 (b) 0.4
16. [A] = 5 M, [B] = 5 M, [C] = 1 M, [D] = 25 M
17. new equilibrium PCl5 PCl3 Cl2
Mole 4 4 2
Partial pressure 20 atm 20 atm 10 atm
Kp
18. a=
4P + K p

4
19. (A) a = = 0.8 (B) K C = 16
5
20. KC = 0.001
21. [NO] = 2M, [N2] = [O2] = 0.5M

22. PCIF = PF2 = 0.1 atm, PClF3 = 05 atm 23. KP = 0.4, a ~ 0.1

24. 50% 25. Kp = 0.01 atm

26. Kp= 2.5 atm, P = 15 atm 27. K=4
28. PCS = 1.8 atm, PS = 0.2 atm 29. 22.4 mg
2 2
30. PH 2O = 5 × 10-15 atm 31. 0.821 atm

32. (a) K = [CH3OH]/[H2]2[CO] ,

(b) 1. [H2] increase, [CO] decrease, [CH3OH] increase ; 2. [H2] increase, [CO] decrease, [CH3OH]
decrease ; 3. [H2] increase, [CO] increase, [CH3OH] increase ; 4. [H2] increase, [CO] increase,
[CH3OH] increase ; 5. [H2] increase, [CO] increase, [CH3OH] decrease ; 6. no change
33. 2
34. 250
35. kr increase more than kf, this means that Ea (reverse) is greater than Ea (forward). Hence
exothermic reaction.
EXERCISE # S-II
1. Ans.(2.4 atm) 2. Ans.31/27
3. Ans.(0.11) 4. Ans.( 2 × 10–4)
5. [PCl3] = [Cl2] =0.027 M
6. (a) 6.667 × 10 –3 mol L –1 ; (b) n (N 2 O 4 ) = 0.374 mol; n (NO 2 ) = 0.052 mol ;
(c) 10.49 atm (d) 6.44 %
7. (i) 2; (ii) 1.2 mol/L; (iii) 0.1 moles/hr
8. Ans.Kc=54, nHI=0.9 mol, nI2= 0.05 mol, nH2 = 0.3 mol
9. Ans.3.6 × 10–3 atm
10. Ans.(a) 400mm2, 900mm2 (b) 4: 9, (c) 72.15 mm Hg
11. Ans. (4) 12. Ans. (SrCl2 × 2H2O)
1 3
13. Ans. (10) 14. K p1 = 2 ;
K p2 =
20P0 20P02
15. (a) 84 ; (b) 0.095 ; (c) 17.35 %
EXERCISE # O-I
1. (D) 2. (C) 3. (D)] 4. (B)
5. (C) 6. (C) 7. (A) 8. (C)
9. (A) 10. (A) 11. (A) 12. (C)
13. (C) 14. (A) 15. (B) 16. (B)
17. (A) 18. (D) 19. (B) 20. (D)
21. (C) 22. (B) 23. (B) 24. (A)
25. (C) 26. (C) 27. (C) 28. (B)
29. (C) 30. (D) 31. (A) 32. (A)
33. (C) 34. (A) 35. (D)
 EXERCISE # O-II
1. (B) 2. (C,D) 3. (C,D) 4. (A,B,C,D)
5. (C,D) 6. (A,C,D) 7. (A,B,C) 8. (C,D)
9. (A,C) 10. (A) 11. (D) 12. (A)
13. (A) 14. (B) 15. (C) 16. (B)
17. (A) 18. (D) 19. (A) 20. (A)
Match the column :
21. (A) - P,R,S (B) - P,Q,R,S (C) - P, Q, R, S ; (D) - Q
22 A - (s), B - (p,q,s), C - (p,q,r), D - (r)
23. (D) 24. (C) 25. (A)
 Marked Questions may have for Revision Questions.

PART - I : SUBJECTIVE QUESTIONS

Section (A) : Inductive effect
A-1. Show the direction of inductive effect in following compounds

(1) (2) (3) CH3–CH=CH2

(4) CH3–CH2–CH2–Li (5) CH3–CH2–CH2–MgBr (6) CH3–CH2–OH

CH=CH2

(7) (8) (9)

NO2
NH3

(10)

CH3

Section (B) : Resonance Concepts, Conditions, Resonating Structures & Conjugation

B-1. Which of the following compounds have delocalized electrons ?
O
||
(P) CH2  CHCCH3 (Q) (R) (S) CH3CH2NHCH=CHCH3

B-2. Number of  electrons in resonance in the following structure is.

Section (C) : Stability of Resonating Structures and different species

C-1. In the following sets of resonating structure, label the major and minor contributors towards resonance
hybrid.

(P)  (Q)  

(R)  (S)  

C-2. Write the stability order of following resonating structures :
I II I II

(P) (Q)

 O
O
(R) (S)


Section (D) : Mesomeric Effect

D-1. Arrange the following groups in the increasing order of +M :
(i) –I, –Cl, –F, –Br (ii) –NH2, –OH,
D-2. Arrange the following groups in the increasing order of –M :

(i) –NO2, –COOR, –CHO, –CN, –COR (ii) , ,

D-3. Which of the following groups (attached with benzene ring) show +M effect ?

Section (E) : Steric Inhibition of Resonance (SIR Effect)

E-1. Compare the SIR effect between orthochloro benzoic acid, orthobromobenzoic acid and orthoiodo
benzoic acid.
Section (F) : Hyperconjugation
F-1. Define hyperconjugation by taking an example of propene.
F-2. In which molecules or ions hyperconjugation effect is observed and write the number of
hyperconjugable hydrogen atoms.

(A) C6H5–CH=CH2 (B) CH3–CH2–CH=CH2 (C) CH2=CH2 (D) CH3 – CH2
CH3 C 2H5 CH3
|  | |
(E) (F) CH3 — C — C H2 (G) C 2H5 — C  (H) CH3 — C
| | |
CH3 C 2H5 CH3

(I) (J) (K) (L)

Section (G) : Concept of Aromaticity
G-1. What is aromaticity ?
G-2. Classify the following as aromatic, antiaromatic and nonaromatic compounds.

(a) (b) (c) (d) (e)

(f) (g) (h) (i) (j)

O

(k) (l) (m)

G-3. Why cyclooctatetraene is nonplanar.

Section (H) : Applications of electronic effect

H-1. The correct decreasing order of electron density in aromatic ring of following compounds is :
O O O
|| || ||
C–H O–C–H NH – CH3 C – NH – CH3

(I) (II) (III) (IV)

H-2. Correct dipole moment order is

(p) (q) (r)

PART - II : ONLY ONE OPTION CORRECT TYPE

Section (A) : Inductive effect
A-1. Inductive effect involves :
(A) Delocalisation of -electrons (B) Partial displacement of -electrons
(C) Delocalisation of -electrons (D) Displacement of lone pair electrons.
A-2. Select correct statement about I effect?
(A) I effect transfers electrons from one carbon atom to another.
(B) I effect is the polarisation of  bond electrons.
(C) I effect creates net charge in the molecule.
(D) I effect is distance independent.
A-3. Which of the following group shows +I-effect :
–
(A) –Br (B) –COOH (C) –OR (D) –COO
A-4. Which of the following alkyl group has the maximum +I effect ?
(A) (CH3)2CH– (B) (CH3)3C– (C) CH3CH2– (D) CH3–
A-5. Decreasing –I effect of given groups is :
(i) –CN (ii) – NO2 (iii) –NH2 (iv) –F
(A) iii > ii > i > iv (B) ii > iii > iv > i (C) iii > ii > iv > i (D) ii > i > iv > iii
A-6. Which of the following is the strongest – group :
  
(A) – N (CH3)3 (B) – NH3 (C) – S (CH3)2 (D) – F

Section (B) : Resonance Concepts, Conditions, Resonating Structures & Conjugation

B-1. Resonance is delocalisation of :
(A)  electrons (B)  electrons (C)  electrons (D) None
B-2. Resonance involves :
(A) Delocalization of -electrons along a conjugated system.
(B) Delocalization of lone pair along a conjugated system.
(C) Delocalization of negative charge along a conjugated system.
(D) All are correct.
B-3. During delocalization, which statement is INCORRECT :
(A) Net charge remains same
(B) Number of paired electrons remain same
(C) Number of unpaired electrons remain same
(D) Energy of resonating structures always remains same
B-4. Resonance structure of the molecule does not have
(A) higher energy than their hybrid structure.
(B) identical arrangement of atoms.
(C) the same number of paired electrons.
(D) always equal contribution to the resonance hybrid.
B-5. Which of the following species can not show resonance?

(A) (B) (C) (D)

B-6. Resonance is not possible in :

(A) (B) (C) CH2=CH–Cl (D)

B-7. Which does not have conjugate system ?

(A) CH2=CHCl (B) CH2=CHCHO (C) CH3CH=CH2 (D)

B-8. The compound which is not resonance stabilised

(A) CH2=CH–Cl (B) (C) CH2=CH–CH2Cl (D)

B-9. Which of the following is not acceptable as resonating structure :

(A) (B) (C) (D) None of these

B-10. Which of the following pair is not pair of resonating structures?


(A) & (B) & CH2 – CH  O
   
(C) CH2=CH–O–CH3 & CH2 – CH  O– CH3 (D) CH3 – C  O & CH3 – C  O
B-11. Which of the following structures are resonance structures ?

(A) & CH3–O–N=O (B) &

(C) (CH3)2CO & (D) CH3–CH=CH–CH3 & CH3–CH2–CH=CH2

B-12. Among the given sets, which represents the resonating structure ?

(A) and (B) and

(C) and (D) and

B-13. In which of the following resonance is not possible?
(A) CH2=C=CH2 (B) CH2=C=CH (C) CH2=C=CH (D) CH2=C=CH
Section (C) : Stability of Resonating Structures and different species
C-1. Which one of the following is least stable resonating structure ?

(A) (B) (C) (D)

C-2. Which of the following resonating structure is the least contributing structure ?

(A) (B) (C) (D)

C-3. HNCO (isocyanic acid) has following resonating structures :
H  N  C  O   

I
The order of stablity is :
(A) I > III > II (B) I > II > III (C) II > III > I (D) II > I > III
C-4. The correct stability order of the following resonanating structures is :

(A) (IV) > (I) > (III) > (II) (B) (II) > (IV) > (I) > (III) (C) (III) > (II) > (IV) > (I) (D) (I) > (IV) > (III) > (II)
C-5. Which is the most stable resonating structure ?

(A) (B) (C) (D)

Section (D) : Mesomeric Effect

D-1. Which of the following group show +M effect ?
(A) –CN (B) –O–NO (C) –CCl3 (D) –CHO
D-2. Which of the following group show –M effect?

(A) –CMe3 (B) (C) (D)

D-3. Which of the following group show +M and –I effect ?
(A) (B) (C) –O (D) –OH

D-4. Which of the following group show +M > –I effect?

(A) –F (B) (C) (D) –COOH

D-5. Which of the following group show –M and –I effect ?

(A) –NO2 (B) –NH2 (C) –OH (D) –F
D-6. +M and +I both effects are shown by :
(A) (B) (C) (D) – C (CH3)3
D-7. The weakest +M group of the given species is :
(A) – OCH3 (B) – F (C) – I (D) – N (CH3)2
Section (E) : Steric Inhibition of Resonance (SIR Effect)
E-1. Maximum extent of steric inhibition of resonance can be expected in

(A) (B) (C) (D)

Section (F) : Hyperconjugation

F-1. In hyperconjugation there is overlap between :
(A) p- and -orbitals (B) 2-orbitals (C) d- and -orbtial (D) - and p-orbitals
F-2. Which of the following cannot exhibit hyperconjugation -

(A) CH3 C H2 (B) (C) CH3CH = CH2 (D)

F-3. Which of the following alkenes will show maximum number of hyperconjugation forms ?

(A) CH2 = CH2 (B) CH3–CH=CH2 (C) CH3–CH2–CH=CH2 (D)

F-4. Which one of the following has inductive, mesomeric and hyperconjugation effect ?
(A) CH3Cl (B) CH3–CH=CH2
(C) CH3CH= CH – C – CH3 (D) CH2=CH–CH=CH2
||
O

F-5. Which of the following group has the maximum hyperconjugation effect when attached to bezene ring ?
(A) CH3– (B) CH3CH2– (C) (CH3)2CH– (D) (CH3)3C–
Section (G) : Concept of Aromaticity
G-1. Which out of the following is aromatic hydrocarbon ?

(A) (B) (C) (D)

G-2. Identify the aromatic compound ?

(A) (B) (C) (D)

G-3. Aromatic compounds burn with sooty flame because :
(A) They have a ring structure of carbon atoms.
(B) They have a relatively high percentage of hydrogen.
(C) They resist reaction with oxygen of air.
(D) They have a relatively high percentage of carbon.
Section (H) : Applications of electronic effect
H-1. The decreasing order of electron density on the ring is :

(A) III > II > I (B) II > III > I (C) I > III > II (D) III > I > II
H-2. Correct dipole moment order is

(p) (q) (r)

(A) p > q > r (B) r > q > p (C) q > r > p (D) p > r > q
H-3. Arrange following compounds in decreasing order of their dipole moment.
CH3—CH2—NO2 CH3—CH2—NH2 CH3—CH2—F CH3—CH2—CN
I II III IV
(A) IV > III > I > II (B) IV > I > III > II (C) I > III > IV > II (D) I > IV > III > II
H-4. The stability order of alkene in following compounds is :

(I) (II) (III) (IV)

(A) I < II < III < IV (B) II < I < III < IV (C) II < III < I < IV (D) II < IV < I < III
H-5. Select the correct statement about this compound.
NO2
3

1 5

NO2 NO2
Br
(A) All three C–N bond length are same.
(B) C1–N and C3–N bonds length are same but shorter than C5–N bond length.
(C) C1–N and C5–N bonds length are same but longer than C3–N bond length.
(D) C1–N and C3–N bonds length are different but both are longer than C5–N bond length.
H-6. Arrange the stability of following :

I II III
(A) I < II < III (B) II < I < III (C) I < III < II (D) II < III < I
 PART - III : MATCH THE COLUMN
1. Match the following :
Coulmn – I Coulmn – II
(Compounds) (Characteristics)
(A) O (p) Mesomeric effect / resonance
(B) Ph–CH=CH–CH3 (q) Inductive effect.
(C) (r) Hyperconjugative effect

(D) (s) Nonpolar

(t) Polar

PART - I : ONLY ONE OPTION CORRECT TYPE

1. The most unlikely representation of resonance structures of p-nitrophenoxide ion is:

(A) (B) (C) (D)

2. In which delocalisation of positive charge is possible ?

–
NH OH O
3 H H 2

N 
(A) (B)  (C) (D)

3. Decreasing order of potential energy of the following cations is :

(I) (II) (III)

(A) II > I > III (B) I > II > III (C) III > II > I (D) II > III > I
4. Stability order of the following species ?

(A) > >  (B) > >  (C) > >  (D) > > 
5. In which of the following first resonating structure is more stable than the second ?
(A)  (B)  
(C) CH2=CH–NH2  (D) 

6. Which of the following is incorrect for stability of structures.

O O
| |
(A) CH3  CH  CH  CH2 > CH3  C  CH  CH3 (B) <
 
(C) > (D) CH2  CH  CH  CH  CH2 > CH2  CH2  CH  CH2

7. Least contributing resonating structure of nitroethene is :

(A) (B) (C) (D)

8. Which of the following statement is correct ?

(A) In the dianion , all the C–C bonds are of same length but C–O bonds are of different

length
(B) In the dianion, all C–C bonds are of same length and also all C–O bonds are of same lengths
(C) In the dianion, all C–C bond lengths are not of same length
(D) None of the above
9. The decreasing order of bond length of C = C bond in the following compounds is:

I II III IV
(A) II > I > IV > III (B) III > I > II > IV (C) IV > II > I > III (D) IV > I > II > III
10. Which of the following is correct about the following compound

(Naphthalene)
(A) All the C-C bond length are same
(B) C1–C2 bond length is shorter than C2–C3 bond length
(C) C1–C2 bond length is greater than C2–C3 bond length
(D) All the C-C bond length are equal to C-C bond length of benzene
11. The correct order of +M effect of ‘N’ containing functional group on benzene ring, amongst the given
compounds is

(A) I > II > IV > III (B) II > I > III > IV (C) I > II > III > IV (D) IV > III > II > I
12. In which case the -bond pair and -bond pair of electrons both are attracted in the same direction,
(towards same atom.) :
(A) H2C=CH–Cl (B) CH3–CH2–NH2 (C) H2C=CH–CH=O (D) H2C=CH–OCH3
13. The correct stability order of given resonating structures is :

  

(A) I > II > III > IV (B) IV > III > II > I (C) I = II = III = IV (D) II = III > I = IV
14. The longest C–N bond length in the given compound is :

(A) x (B) y (C) z (D) w

15. Select the correct order of heat of hydrogenation ?

(I) (II)

(III) (IV)

(A) I > II > III > IV (B) IV > III > II > I (C) II > III > IV > I (D) II > III > I > IV

16. does not involve :

(A) –p overlap (B) –* overlap (C) p–p overlap (D) p–d overlap
17. Stability of -bond in following alkenes in the increasing order is :
CH3–CH=CH–CH3

(I) (II) (III) (IV)

(A) I < III < IV < II (B) I < II < III < IV (C) IV < III < II < I (D) II < III < IV < I

18.

In this molecules, -electron density is more on :

(A) C1 and C3 (B) C2 and C4 (C) C2 and C3 (D) C1 and C4
19. If the given compound is planar. Select the correct statement.

(A) The boron is sp2 hybridized and the p-orbital contains an unshared pair of electron
(B) The boron is sp2 hybridized and a hybrid orbital contains an unshared pair of electron.
2
(C) The boron in sp hybridized and hybrid orbital is vacant
2
(D) The boron is sp hybridized and the p-orbital is vacant
20. The correct order of electron density in aromatic ring of following compounds is :

I II III IV
(A) IV > III > II > I (B) I > II > III > IV (C) IV > II > I > III (D) IV > II > III > I

PART - II : SINGLE AND DOUBLE VALUE INTEGER TYPE

1. Among the given sets, how many of the following not represents the resonating structure :
(i) and H–O–CN
(ii) and H–O–CN

(iii) and
(iv) and H–N=C=O
(v) and

(vi) CH2=CH–NH2 and

(vii) and
2. How many of the following species can show resonance.

, , , , , ,

CH2=CH–Cl, , , CH2=CH–CH2–Cl,

3. How many groups (attached with benzene ring) can show +M effect ?

(i) (ii) (iii) (iv)

(v) (vi) (vii) (viii)

(ix) (x) (xi)

4. Identify the number of compounds in which positive charge will be delocalised ?

(i) (ii) (iii) (iv)

(v) (vi) (vii)

5. In how many of the following cases, the negative charge is delocalised?

(i) (ii) (iii) (iv)

(v) (vi) (vii) (viii)

(ix) (x)

6. In how many of the following compounds Hyperconjugation effect is observed -

(A) C6H5–CH=CH2 (B) Ph–CH3 (C)

(D) (E) (F)

(G) (H) (I)

7. How many of the following compounds is/are aromatic ?

(i) (ii) (iii) (iv)

(v) (vi) (vii) (viii)

(ix) (x) (xi)

8. Total number of moelcules which are antiaromatic ?

(a) (b) (c) (d)

(e) (f) (g) (h)

(i) (j) (k)

9. Find the number of carbon atoms including the given structure which can have negative change in
resonating structures. (The structure with charge reperating are not accepted)

10. Observe the following compound and write the number of hydrogen atom involved in hyperconjugation?

11. Find the total number of positions where positive charge can be delocalized by true resonance

. (Excluding the given position)

PART - III : ONE OR MORE THAN ONE OPTIONS CORRECT TYPE

1. Which statement is/are true about resonance ?
(A) It decreases the energy of system.
(B) The hybridisation of atoms do not change due to resonance
(C) Resonance hybrid is more stable than any resonating structure.
(D) Resonanting structures can not be isolated at any temperature
2. Which of the following statement is incorrect about resonance ?
(A) The most stable structure explains all the characteristics of a species.
(B) All resonating structures remain in equilibrium.
(C) Resonance hybrid has maximum similarity with most stable resonating structure.
(D) Resonance hybrid is real.
3. In which of the following pairs of compounds, will second structure have more contribution to resonance
hybrid than first ?

(A) & (B) &

(C) & (D) &

4. In which of the following pairs of resonating structures first resonating structure is more stable than
second ?

(A)  (B) 

(C)  (D) 

5. In which of the following compounds delocalisation of electrons and shifting of electron in the same
direction ?

(A) (B) CH3–NH–NO2

H
(C) CH2=CH–CH=CH–NO2 (D) |
H2N – C  CH2

6. Which of the following groups cannot participate in resonance with benzene :


(A) – COOH (B) COO (C) – NH3 (D) – COCl

7.  Which of the following is/are correct :

(A) is antiaromatic (B) is aromatic

(C) is aromatic (D) is aromatic

8. Which of the following is/are correct statement :

–
(A) > > e density

–
(B) > > e density

(C) , , all are aromatic

(D) > > Dipole moment

9. The correct orders for bond length are :

(A) (a > a) (B) (b = b)

(C) (c > c) (D) (d > d)

PART - IV : COMPREHENSION
Read the following passage carefully and answer the questions.
Comprehension #
Hydrogenation of unsaturated hydrocarbons is an exothermic reaction. Due to hyperconjugation and
resonance the stability of unsaturated hydrocarbons increases and the increase in stability is more due
to resonance. Compound with same number of -bonds and more stability has lower heat of
hydrogenation.
Heat of formation is defined as the energy evolved when a molecule is formed from its atoms. For
isomers the more stable compound has higher heat of formation.
1. The correct heat of hydrogenation order is :
(p) 1,3-Pentadiene (q) 1,3-Butadiene
(r) 2,3-Dimethyl-1,3-butadiene (s) Propadiene
(A) p > q > r > s (B) s > q > p > r (C) q > s > p > r (D) s > p > q > r
2. The order of heat of formation of the following molecules is :

(A) I > II > III > IV (B) II > III > IV > I (C) IV > II > III > I (D) IV > III > II > I
Comprehension # 2
Answer Q.3, Q.4 and Q.5 by appropriately matching the information given in the three columns
of the following table.
Column-I Column-II Column-III
N
(P) (i) lone pair is present in hybrid orbital (I) delocalised lone pair

H
(Q) N (ii) Charge is present in hybrid orbital (II) localised lone pair


(iii) lone pair is present in p-orbital
(R) (III) localised charge


CH2
(S) (iv) charge is present in p-orbital (IV) delocalised charge

3._ The only correct combination for pyridine is –

(A) (Q) (i), (ll) (B) (P) (i) (II) (C) (R) (iv) (III) (D) (Q) (ii) (ll)

4._ The only correct combination for benzyl cation is–

(A) (P) (ii), (II) (B) (R) (iv) (IV) (C) (S) (iv) (IV) (D) Q (i) (II)

5._ The only correct combination for pyrrole is

(A) (P) (ii), (II) (B) (R) (iv) (IV) (C) (S) (iv) (IV) (D) Q (iii) (I)
 EXERCISE - 1
PART – I

A-1. (1) (2) (3)

(4) CH3 CH2 CH2 Li (5) CH3 CH2 CH2 MgBr (6)

(7) (8) CH3 COOH (9) (10)

B-1. (P), (R), (S) B-2. 8

C-1. (P) I – minor II – major (Q) I – minor II – major
(R) I – minor II – major (S) I – minor II – major
C-2. (P) I > II ; (Q) II > I ; (R) I > II ; (S) II > I

D-1. (i) +m : – I < – Br < – Cl < – F (ii) +m : –OH < –NH2 <

D-2. (i) –m : –COOR < –COR < CHO < CN < NO2 (ii) –m : < < 
O
||
O — S — OH

D-3.

have +M group.
E-1. SIR effect increases with the size of ortho group. The order of SIR effect is o-iodo benzoic acid > o-
bromo benzoic acid > o-chloro benzoic acid.
F-1. It is delocalisation of sigma electron with p-orbital. It may take place in alkenes, alkynes, carbocations,
free radicals, alkelyl benzene.
Necessary Condition: Presence of at least one hydrogen at saturated carbon which is  with respect
to alkene, alkynes, carbocation, free radical, benzene nucleus.

Propene 

F-2. (A) 0 (B) 2 (C) 0 (D) No hyperconjugation

(E ) 0 (F) 0 (G) 6 (H) 9
(I) 3 (J) 10 (K) 0 (L) 10
G-1. Those molecules are aromatic which have very high resonance energy. Only those molecules has
sufficiently high amount of resonance energy to become aromatic which
(a) are cyclic (b) are planar
(c) contains (4n +2) number of  -electrons in ring.
(d) must have cyclic resonance between (4n + 2) number of -electrons Where n = 0, 1, 2, 3, 4 ..........
G-2. Aromatic : (a), (b), (c), (d), (e), (f), (h), (l) ; Antiaromatic : (g), (i), (j), (m)
Nonaromatic : (k)
G-3. Cyclooctatetraene is nonplanar to avoid its anti aromaticity and it becomes tub-shaped structure.

H-1. (III) > (II) > (IV) > (I)

+m group increases electron density and –m group decreases electron density in aromatic ring.
H-2. p>q>r

PART – II
A-1. (B) A-2. (B) A-3. (D) A-4. (B) A-5. (D)
A-6. (A) B-1. (A) B-2. (D) B-3. (D) B-4. (D)
B-5. (A) B-6. (A) B-7. (C) B-8. (C) B-9. (B)
B-10. (A) B-11. (B) B-12. (B) B-13. (A) C-1. (C)
C-2. (B) C-3. (A) C-4. (D) C-5. (B) D-1. (B)
D-2. (D) D-3. (D) D-4. (B) D-5. (A) D-6. (C)
D-7. (C) E-1. (C) F-1. (D) F-2. (D) F-3. (B)
F-4. (C) F-5. (A) G-1. (C) G-2. (B) G-3. (D)
H-1. (A) H-2. (B) H-3. (D) H-4. (A) H-5. (C)
H-6. (C)

PART – III
1. (A) - p,q,r,t ; (B) - p,q,r,t ; (C) - p,q,r,t ; (D) - p,q,s

EXERCISE - 2
PART - I
1. (C) 2. (D) 3. (A) 4. (A) 5. (C)
6. (A) 7. (C) 8. (B) 9. (B) 10. (B)
11. (C) 12. (C) 13. (D) 14. (D) 15. (B)
16. (D) 17. (A) 18. (B) 19. (D) 20. (D)

PART - II
1. 5 (i, iii, iv, v, vii) 2. 8 (ii, iii, iv, vi, vii, viii, ix, xi) 3. 5 (i, ii, v, vi, ix)
4. 5 (i, iii, v, vi, vii) 5. 5 (i, ii, iv, vi, ix) 6. 3 (B, C & G).
7. 6 (i, iv, v, vi, vii, x)
8. 3
Aromatic – a, c, g, h, i, j, k. ; Antiaromatic – b, d, e ; Nonaromatic – f
9. 6 10. 9 11. 2
 PART – III
1. (ABCD) 2. (AB) 3. (ABC) 4. (BC) 5. (BC)
6. (C) 7. (BD) 8. (AD) 9. (ABD)

PART - IV
1. (B) 2. (C) 3. (B) 4. (C) 5. (D)

 Marked Questions may have for Revision Questions.

PART - I : SUBJECTIVE QUESTIONS

Section (A) : Carbanions
A-1. Arrange the following in decreasing order of stability.
(a) ,

(b)

A-2. Arrange the following in decreasing order of stability

..
.. CH3
–
(a) ..
..

–
CH3
1 2 3 4

(b)

.. ..
(c) C Cl3 CF3
1 2

Section (B) : Carbon free radicals

B-1. Rank the following free radicals in increasing order of their stability and give appropriate reasons.

B-2. Arrange the following free radicals in decreasing order of stability :

 
CH3 – CH2 CH3
I IV

Section (C) : Carbocations

C-1. Arrange the following carbocations in decreasing order of their stability :

(I) (II) (III) (IV)

  
 CH3 — CH — C H2 CH3 — CH — C H2 CH3 — CH — C H2
(P) CH3—CH2— C H2 | | |
F Br Cl

(Q)

(R)
C-2. Which of the following carbocation is more stable and why ?

(I) (II)

C-3. Draw the structures of P and Q.

Section (D) : Basic strength

D-1. Compare the basic strength of the following compounds:
– – – – –
C2H5O C2H5 C2H5NH NH2 F
(I) (II) (III) (IV) (V)
D-2. Compare the basic strength of the following compounds :
(a) PhNH2 Ph2NH Ph3N
(b)

N
 N
–

:NH2 H
(c) Ph–CH2–CH2–NH2

D-3. Which of the following group is most basic in the given compounds :

D-4. Which of the following is a stronger base ? Give reason to justify your answer.

Section (E) : Acidic strength

E-1. Which ‘H’ atom is most acidic in the following compounds.

(I) (II) (III)

E-2. Arrange the following in decreasing order of acidity

E-3. The given compound X = is a strong acid. Justify this statement.

Section (F) : Feasible reactions of acids and bases
F-1. Which of the follwing reactions is/are feasible ?
(a) CH3COOH + HCOONa  (b) HCC–Na + H2O 

(c) +  (d) + 

F-2. Which of the following reaction is feasible?


H  
(a)  
 (b) + NH3 +

(c) +  +


N H2 CH2 NH CH 2
|| || || || 
(d) NH2  C  NH2 + CH3  C  NH2  NH2  C  NH2 + CH3  C  NH3
F-3. Which of the following acids (given below) react with NaHCO3 and liberate CO2(g) ?

CCl3–COOH CH3–CH2–OH HCl

Section (G) : Tautomerism

G-1. Which of the following compounds can exhibit tautomerism ?
CH3
– –

(A) CH3 – C – C – H (B) Ph – C – CH3 (C) (D)

CH3 O O

O O
O
(E) (F) (G) (H)
O

G-2. Write the tautomers of the following compounds :

(P) (Q) CH3–CH=NH (R) (S)

G-3. Monocarbonyl compounds have very small percentage enol form at equilibrium. Explain.
 PART - II : ONLY ONE OPTION CORRECT TYPE
Section (A) : Carbanions
A-1. Which of the following is the least stable carbanion?
(A) (B) (C) (D)

A-2. The most stable anion is :

(A) (B) (C) (D)

A-3. In which of the following pairs of carbanion the first one is more stable than second.
(A) , (B) ,

(C) , (D) ,

A-4. Arrange the following carbanions in decreasing order of stability :

I II III IV
(A) III > I > IV > I (B) III > II > I > IV (C) I > III > II > IV (D) III > I > II > IV
A-5. The most stable anion is :

(A) (B) (C) (D)

A-6. Arrange the following carbanions in increasing order of stability :

(A) III > IV > I > II (B) I > III > IV > II (C) I > II > III > IV (D) I > IV > III > II

Section (B) : Carbon free radicals

B-1. Among the following, the paramagnetic species is :
(A) Free radical (B) Carbocation (C) Carbanion (D) All the three
B-2. The stability of given free radicals in decreasing order is :
  
(i) CH3– CH2 (ii) CH3– CH –CH3 (iii) (iv) CH3

(A) iii > iv > i > ii (B) i > ii > iii > iv (C) iii > ii > iv > i (D) iii > ii > i > iv
B-3. Which of the following is the correct order of stability of free radicals ?
(A) benzyl > allyl > 2º > 1º (B) allyl > benzyl > 2º > 1º
(C) allyl > 2º > 1º >benzyl (D) benzyl > 2º > 1º > allyl
B-4. Most stable radical among the following is :

(A) (B) (C) (D)

B-5. Arrange the following radicals in decreasing order of their stability.

(I) (II) (III) (IV)

(A) IV > I > III > II (B) IV > III > II > I (C) I > II > III > IV (D) IV > III > I > II
B-6. Least stable radical among the following is :

(A) (B) (C) (D)

Section (C) : Carbocations

C-1. The most unstable carbocation is :
   
(A) CH3 CH2 (B) Cl – CH2 – CH2 (C) CH2 – CHO (D) CH2 – O – CH3

C-2. The most stable carbocation is :

(A) (B) (C) (D)

C-3. Which of the following shows the correct order of decreasing stability ?

(A) > > > CH3 – C H2


(B) > > > CH3 – C H2


(C) > > > CH3 – C H2


(D) > > CH3 – CH2 >

C-4. Which of the following is the rearranged more stable carbocation of the given species ?
CH3
| 
CH3 – C – C H  CH3 
|
CH3
CH3 CH3
| | 
(A) CH3 – C – C H – CH3     (B) CH3 – C – C H2 – C H2
|  |
CH3 CH3
CH3
CH3 CH3 |
| | 
(C) CH3 – C — CH – CH3 (D) CH3 – CH – CH  C H2
 |
CH3
C-5. Most stable rearranged form of given carbocations is :

(A) (B) (C) (D)

C-6. Which of the following in the rearranged more stable carbocation of the given species?

(A) (B)

(C) (D)

Section (D) : Basic strength

D-1. The correct basic strength order of following anions is :
(A) > > > > >

(B) > > > > >

(C) > > > > >

(D) > > > > >

D-2. Which of the following shows the correct order of decreasing basicity in gas phase ?
(A) (CH3)3N > (CH3)2NH > CH3NH2 > NH3 (B) (CH3)2NH > (CH3)3N > CH3NH2 > NH3
(C) (CH3)2NH > CH3NH2 > (CH3)3N > NH3 (D) (CH3)2NH > CH3NH2 > NH3 > (CH3)3N
D-3. Find the order of basic strength. (If R = Me) ?
(I) R4 N+OH¯ (II) R3N (III) R2NH (IV) RNH2
(A) I > III > IV > II (B) IV > III > I > II (C) II > IV > III > I (D) II > IV > I > III
D-4. Which of the following cannot be a base?

(A) (B) CH3  C  NH2 (C) (D)

||
O
D-5. Select the basic strength order of following molecules ?

(I) Piperidine (II) Pyridine (III) Morpholine (IV) Pyrrole

(A) (IV) > (I) > (III) > (IV) (B) (III) > (I) > (IV) > (II)
(C) (II) > (I) > (III) > (IV) (D) (I) > (III) > (II) > (IV)
D-6. Arrange the following in increasing order of pKa value ?

(I) (II) (III)

(A) II < I < III (B) III < I < II (C) III < II < I (D) II < III < I
D-7. Select the decreasing order of relative basic strengths of following species :

(I) (II) (III) (IV)

(A) II > IV > I > III (B) III > I > IV > II (C) III > IV > I > II (D) II > I > IV > III
D-8. Select the basic strength order of following molecule :

(A) II > III > IV > I (B) II > IV > III > I (C) IV > II > III > I (D) IV > III > I > II

Section (E) : Acidic strength

E-1. Among the following compounds, the strongest acid is :
(A) HC  CH (B) C6H6 (C) C2H6 (D) CH3OH
E-2. Which of the following is not correct decreasing Ka order.
(A) CH4 > NH3 > H2O > HF (B) CH3–OH > CH3–NH2 > CH3–F > CH3–CH3
(C) HI > HBr > HCl > HF (D) PhOH > H2O > C2H5OH > CH3–CCH
E-3. Which of the following acid has the smallest dissociation constant ?
(A) (B) O2N–CH2–CH2–COOH

(C) Cl–CH2–CH2–COOH (D) NC–CH2–CH2–COOH

E-4. Find the strongest acid among the following compounds is :
(A) HOOC–(CH2)2–COOH (B) H3N–(CH2)2–COOH
(C) F–(CH2)2–COOH (D) CH3–(CH2)2–COOH
E-5. Which of the following option shows the correct order of decreasing acidity :
(A) PhCO2H > PhSO3H > PhCH2OH > PhOH (B) PhSO3H > PhOH > PhCH2OH > PhCO2H
(C) PhCO2H > PhOH > PhCH2OH > PhSO3H (D) PhSO3H > PhCO2H > PhOH > PhCH2OH
E-6. Arrange increasing order of acidic strength of following dibasic acids :
(I) oxalic acid, (II) succinic acid, (III) malonic acid, (IV) adipic acid
(A) III < II < I < IV (B) II < III > I > IV (C) I > III > II > IV (D) II > I > III < IV

E-7.

I II III
Arrange above phenol in increasing order of pKa value :
(A) I < II < III (B) III < I < II (C) III < II < I (D) I < III < II
E-8. Order of Ka of following acids is :
O O O
C C – OH
OH C – OH

O2N CH3O
I II III
(A) I > II > III (B) II > I > III (C) I > III > II (D) III > I > II
E-9. Arrange the following compounds in increasing order of their acidic strength.

(A) IV < II < I < III (B) I < II < III < IV (C) IV < II < III < I (D) I < III < II < IV
E-10. Find the order of Ka of following compounds :
COOH COOH
COOH COOH

(I) (II) (III) (IV) (V) NO2

NO2
NO2
(A) I < II < III < IV < V (B) IV < I < III < II < V (C) III < II < I < IV < V (D) II < I < III < IV < V
Section (F) : Feasible reactions of acids and bases

1 Mole of CH COONa
3
F-1. 
 ; The products will be :

(A) + CH3COOH (B) + CH3COOH

(C) + CH3COOH (D) Reaction is not feasible

F-2. Which of the following reactions is not feasible ?
COONa

(A) + NaHCO3  + H2O + CO2

(B) + NaHCO3  + H2O + CO2

(C) + NaHCO3  + H2O + CO2

(D) +  +

F-3. Which of the following will accept H+ from NH4+ ion.

(A) (B) (C) (D) CH3–CH2–NH2

F-4. 2 Mole Product

NaHCO3

(A) (B) (C) (D)

Section (G) : Tautomerism

G-1. Keto-enol tautomerism does not observe in :

(A) (B)

(C) (D)
G-2. The enolic form of acetone contains :
(A) 9  bonds, 1  bond and 2 lone pairs (B) 8  bond, 2  bond and 2 lone pairs
(C) 10  bond, 1  bond and 1 lone pair (D) 9  bond, 2  bond and 1 lone pair

G-3. Molecule can be enolised by which hydrogen ?

(A) y–H (B) z–H (C) both (D) None of these

G-4. Which among the following compound will give maximum enol content in solution :
O O
(A) (B) CH3 – C – CH2 – C – CH3
O O
(C) CH 3 – C – CH 2 – CH 2 – CH 3 (D) CH 3 – C – CH 2 – COOC 2H 5
G-5. Arrange the following in decreasing order of percentage enol content.

(i) (ii) (iii) (iv)

(A) I > II > III > IV (B) II > I > III > IV (C) II > III > I > IV (D) III > II > IV > I

PART - III : MATCH THE COLUMN

1. Match the column %
Column-I (Keto) Column-II (% enol)
(A) CH3 – CH = O (x) 95 %
(B) (y) 76 %

(C) (z) 0.0001 %

(D) (w) 7.2 %

2. Match the column :

Column-I Column-II

(A) NaHCO3 will react with (p)

(B) Na will react with (q)

(C) NaOH will react with (r)

(D) NaNH2 will react with (s)

 Marked Questions may have for Revision Questions.

PART - I : ONLY ONE OPTION CORRECT TYPE

1. Arrange the following carbanions in decreasing order of stability :

(A) III > II > IV > I (B) III > II > I > IV (C) III > I > II > IV (D) II > III > I > IV
2. Correct decreasing stability order of following carbanions :

I II III IV
(A) III > IV > II > I (B) IV > II > III > I (C) IV > III > II > I (D) III > II > I > IV
3. Select the most stable intermediates :

(A) (B) (C) (D)

4. Which of the following is most stable carbocation?

(A) CH3 (B) CH3 (C) CH3 – (D)

5. The most stable carbocation is :
(A) (B)
+ +
(C) +
(D)
+

6. The following carbocation rearranges to

CH3 CH3
|  |
CH2  C  C  C H  CH  CH3
| |
CH3 CH3

(A) (B)

CH3 CH3
 | |
CH2  C  C  CH  CH  CH3
(C) (D)
| |
CH3 CH3

7. Correct basic strength order is :

NH2 NH2 NH – Et NH2
Et NO2

p q r s
(A) r > q > p > s (B) r > p > q > s (C) q > r > p > s (D) r > q > s > p
8. The order of basic strength of the given basic nitrogen atoms is :

(A) III > II > I > IV (B) III > I > II > IV (C) I > III > II > IV (D) II > III > I > IV
9. In the labelled N-atoms which is correct basic strength order :

(A) 2 > 1 > 3 (B) 3 > 1 > 2 (C) 2 > 3 > 1 (D) All are equally basic
10. Choose the strongest base among the following :

(A) (B) (C) (D)

11. Select the basic strength order of following molecules ?

(A) III > II > I (B) II > III > I (C) I > III > II (D) III > I > II
12. Which is the weakest base among the followings ?

(A) (B) (C) (D)

13. Write the order of K a1 values of following acids :

(I) (II) (III)

(A) II > III > I (B) I > III > II (C) III > II > I (D) II > I > III
14. The acid strength order is :

(A) I > IV > II > III (B) III > I > II > IV (C) II > III > I > IV (D) I > III > II > IV
15. (X) (C6H3ClBrCOOH) are a dihalosubstituted benzoic acids. The strongest acid among all isomers is -

(A) (B) (C) (D)

16. The order of acidity of the H-atoms underlined in the following compounds is in the order :
(I) (II) (III) (IV)

(A) IV>II>I>III (B) II>IV>III>I (C) III>IV>I>II (D) I>III>II>IV

17. Most acidic hydrogen is present in :

(A) (B) (C) (CH3CO)3CH (D) (CH3)3COH

18. The correct orders are :

(A) > Acid strength

(B) > Acid strength

(C) > Basic strength

(D) > Boiling point

19. Observe the following sequence of reactions :

+ CH3NH2 
(1) + + CH3NH2 +

Select the correct option regarding the relative basic strength (Kb) :

(A) > CH3  C  NH2 (B) > CH3  C  NH2

|| ||
NH NH
(C) CH3  C  NH2 > CH3NH2 (D) CH3NH2 >
||
NH

20. Order of Ka which can be predicted by following reaction is :

(A) NH3 > Ph3CH > C2H2 > H2O (B) H2O > HCCH > Ph3CH > NH3
(C) HCCH > H2O > Ph3CH > NH3 (D) Ph3CH > HCCH > H2O > NH3
21. The gases produced in the following reactions are respectively
I : CH3NH2 + NH4Br 
II : CH3SO3H + NaHCO3 
III : CH3  C  NH2 + NaH 
||
O
(A) NH3, NH3, CO2 (B) NH3, SO2, H2 (C) NH3, SO2, NH3 (D) NH3, CO2, H2
22. Decreasing order of enol content of the following compounds in liquid phase

(A) 2 > 1 > 3 > 4 (B) 1 > 2 > 3 > 4 (C) 4 > 3 > 2 > 1 (D) 3 > 1 > 2 > 4
 PART - II : SINGLE AND DOUBLE VALUE INTEGER TYPE
1. How many of the following carbocation can undergo rearrangement :

(a) (b) (c) (d)

(e) (f) (g) (h)

(i) (j) (k)

2. Consider following compound, which H-atom deprotonated first ?

3. How many of the following are correct orders for Basic Strength :
S1 : > CH3–NH2 >

S2 : > > C2H5–NH2

S3 : > >

S4 : > >

S5 : > > C2H5–NH2

4. How many following compounds are more basic than aniline.

CH3–CH2= NH
5. How many of the following compounds give CO2 on reaction with NaHCO3.

, HCl , , , ,

, HCOOH, C2H5–OH , CH3COOH ,

6. How many of the following are more acidic than HCOOH.

–
(i) CH2 – COOH (ii) CH3–COOH (iii) O OC – CH2 – COOH (iv) NC–CH2–COOH
|
Cl
(v) CH2 – COOH (vi) CH2 – COOH (vii) CH2 – COOH (viii) CH2 – COOH
| | | |
F NO2 NH– NH3
7. How many of the following compound have less pKa than benzoic acid :

(i) HCOOH (ii) CH3COOH (iii) (iv)

COOH COOH

(v) (vi) (vii) (viii)

NO2
OCH3

8. 90 g of acetic acid react with excess of NaHCO3 then what volume of CO2 will produce at S.T.P. Write
your answer in terms of nearest integer.
9. In how many of the following pairs first will have higher enol content than second.

(i) &

(ii) &

(iii) &

(iv) &

(v) &
10. Consider the following compound and write number of enolizable H-atom

PART - III : ONE OR MORE THAN ONE OPTIONS CORRECT TYPE

1. Which of the following stability order of anions is/are correct :

(A) II > III > I

  
(B) CH2 – C – H CH2 – C – OCH3 CH2 – CH3 I > II > III
|| || ( III)
O O
(I) ( II)

(C) I > II > III

 
(D) CH3 > CD3 I > II
I II

2. Which of the following is/are correct for basic strength :

(A) (CH3)2NH > (CH3)3N > CH3NH2 > NH3 (B) (C2H5)2NH > (C2H5)3N > C2H5NH2 > NH3

(C) PhNH2 > Ph2NH > Ph3N (D) > >

3.

Among the following which statement(s) is/are correct :

(A) Both N of pyrimidine are same basic strength
(B) In imidazole protonation take places on N-3.
(C) In purine only one lone pair of N is delocalised.
(D) Pyrimidine, imidazole and purine all are aromatic.
4. Consider the following compounds
O O O O
|| || || ||
O2N – CH2 – C – OH F – CH2 – C – OH Ph – CH2 – C – OH CH3 – CH2 – C – OH
(I) ( II) ( III) (IV )
Which statement is/are correct :
(A) I > II > III > IV (Acidic strength order)
(B) I is most acidic because of –M effect of –NO2 group
(C) I is most acidic because of –I effect of –NO2 group
(D) IV is least acidic because of +I Effect.
5. Carbolic acid is less acidic than :

(A) CH3COOH (B)

(C) (D)

6.

OHb
Observe the compound and choose correct statement :
(A) It has carboxylic acid group (B) It is Ascorbic acid
(C) Hb is most acidic Hydrogen atom (D) Ha is least acidic Hydrogen atom

7. Which of the following reactions favour backward direction?

(A) + +

(B) + +

(C) + +

(D)

8. The correct statement(s) concerning the structures P, Q, R & S is/are

(P) (Q) (R) (S)

(A) Q & S are not resonating structures (B) R & S are resonating structures
(C) P & R are tautomers (D) P & Q are resonating structures
9. Among the given pairs, in which pair second compound has less enol content :
O
||
(A) and CH3 – C – CH3 (B) and

(C) and (D) and

PART - IV : COMPREHENSION
Read the following passage carefully and answer the questions.
Comprehension # 1
Reaction intermediates : Reaction intermediates are short lived species and are highly reactive. They
are formed by heterolytic and homolytic bond fission. There are various types of reaction intermediates
in which the most important are carbocation, carbanion and free radical.
Carbocation is an organic species in which carbon have positive charge and six electrons in its
outermost shell. The stability of carbocation can be increased by positive inductive effect,
hyperconjugation and delocalisation. If -atom with respect to carbocation has one or more lone pair of
electrons then lone pair of electron strongly stabilises the carbocation due to octet completion.
Species in which carbon have negative charge is called carbanion. Carbanion carries three bond pairs
and one lone pair. The stability of carbanion can be increased by negative inductive effect, negative
mesomeric effect and delocalisation.
Free radical is a species which have seven electrons in its outermost shell. The stability of free radical
can be increased by hyperconjugation and delocalisation.
1. Which of the following is the most stable carbanion intermediate ?

(A) (B)

(C) (D)

2. The stability order of following free radicals is :

(A) I > II > III > IV (B) II > III > I > IV (C) I > III > II > IV (D) III > II > I > IV
3. The stability order of following carbocations is

(A) I > II > III (B) II > I > III (C) III > I > II (D) II > III > I
Comprehension # 2
Ortho effect is a special type of effect that is shown by o-substituents. This ortho-effect operates at the
benzoic acids irrespective of the polar type. Nearly all o-substituted benzoic acid are stronger than
benzoic acid. Benzoic acid is a resonance stabilised and so the carboxyl group is coplanar with the ring.
An o-substituent tends to prevent this coplanarity.
4. What is the order of Ka of following compounds ?
COOH COOH COOH COOH COOH
NO2 Br Cl F OCH3

  IV V
(A) I > II > III > IV > V (B) II > I > III > IV > V (C) V > IV > III > I > II (D) III > II > I > V > IV
5. Which among the following will be the strongest acid ?

(I) (II) (III) (IV)

(A) I (B) II (C) III (D) IV

6. Which of the following is/are correct pKa order ?

(A) > > >

(B) CH3–COOH > > >

(C) > > >

(D) > > >

Comprehension # 3
The lone pair of amines makes them basic. They react with acids to form acid-base salts. Amines are
more basic than alcohols, ethers and water. When an amine is dissolved in water, an equilibrium is
established, where water acts as an acid and transfer a proton to the amine. The basic strength of an
amine can be measured by basicity constant Kb.
Arylamines are less basic than alkylamines because the lone pair of nitrogen is delocalised with the
aromatic ring and are less available for donation.
Substituted arylamines can be either more basic or less basic than aniline, depending on the
substitutent. ERG substituents, such as –CH3, –NH2 and –OCH3 increases the basicity and EWG
substituents, such as –Cl, –NO2 and –CN decreases basicity. While sp2-hybridized nitrogen atom in
3
pyridine is less basic than the sp -hybridized nitrogen in an alkylamine.
7. Select the correct order of Kb.
(A) CH3NH2 > NaOH
(B) Pyridine >
(C) p-Methyl aniline > p-Chloroaniline > p-Amino acetophenone
(D) p-Bromoaniline > p-Nitroaniline > p-Amino benzaldehyde
8. pKb order of the following compound is :
(I) NH2OH (II) NH2NH2 (III) NH3 (IV) H2O
(A) IV > I > II > III (B) III > II > I > IV (C) I > IV > II > III (D) III > I > II > IV
9. The correct basicity order of various atoms is :

(A) 1 < 2 < 3 < 4 (B) 2 < 4 < 3 < 1 (C) 3 < 2 < 1 < 4 (D) 3 < 4 < 1 < 2
Comprehension # 4
Observe the following reaction and answer the following questions :

10. The product ‘R’ is :

(A) (B)

(C) (D)

11. The structure of Q1 is :

(A) (B)

(C) (D)

Comprehension # 5
Answer 12, 13 and 14 by appropriately matching the information given in the three columns of the
following table.
Column-1, 2 & 3 containing starting material, reaction condition & electronic effect / intermediate respectively.
Column-1 Column-2 Column-3
Cl

(I) (i) SbCl5 or AlCl3(Anhy.) (P) Rearrangement

Cl

(II) (ii) Na (Q) Resonance

 +
(III) N (iii) H (R) Hyperconjugation
|
H H
Cl

(IV) (iv) NaOH (S) Carbocation intermediate

12._ Which combination will give hydrogen gas ?
(A) (IIl) (iii) (P) (B) (ll) (ii) (R) (C) (lV) (ii) (Q) (D) (l) (iii) (P)

13._ In which product formation is not possible ?

(A) (l) (ii) (Q) (B) (ll) (i) (R) (C) (lll) (ii) (Q) (D) (lV) (i) (S)

14._ In which amongs the following aromatic product will not form ?
(A) (l) (i) (P) (B) (ll) (i) (Q) (C) (lll) (iv) (Q) (D) (lV) (ii) (Q)
 EXERCISE - 1
PART - I
A-1. (a) 1 > 2 > 3 ; (b) 1 > 2 > 3 A-2. (a) 2 > 1 > 3 > 4 ; (b) 1 > 2 > 3 ; (c) 1 > 2
B-1. Stability order : I < II < III < IV
IV is most stable being 3º and delocalised but III is 2º and delocalised.
B-2. III > II > I > IV C-1. (P) I > III > IV > II ; (Q) IV > III > II > I ; (R) III > II > IV > I
C-2. (II) is more stable carbocation due to extented conjugation

C-3. (P) = ; (Q) =

D-1. II > III > IV > I > V

D-2. (a) PhNH2 > Ph2NH > Ph3N

(b) > >


N
 N
–

:NH2 H
(c) Ph–CH2–CH2–NH2 > >

D-3. 2

D-4. I is less basic than II because, in compound (I) the lone pair of electrons is involved in resonance but
not in II.

E-1. I - a, II - b, III - c, (acidic strength  stability of conjugate base)

E-2. III > I > II (acidic strength  stability of conjugate base) In III conjugate base is highly stabilised by intra
molecular H-bonding.


H
E-3.     etc.

Its conjugate base (anion) is resonance stabilised like RCOO anion of carboxylic acid.
F-1. (a) Not feasible (b) Feasible (c) Not feasible (d) Not feasible
+
F-2. (c) Strong base accept H ions so this reaction is feasible.
F-3. (i, iii, iv, v, vi, vii)
G-1. B, C, E, G, H can show tautomerism.
OH
|
G-2. (P) CH3  C  CH2 (Q) CH2=CH–NH2 (R) (S)

G-3. In Monocarbonyl Keto form is more stable due to greater strength of the carbon-oxygen double bond as
compared to the carbon carbon double bond.
 PART - II
A-1. (C) A-2. (A) A-3. (B) A-4. (D) A-5. (B)
A-6. (D) B-1. (A) B-2. (D) B-3. (A) B-4. (C)
B-5. (B) B-6. (C) C-1. (C) C-2. (B) C-3. (B)
C-4. (C) C-5. (D) C-6. (B) D-1. (C) D-2. (A)
D-3. (A) D-4. (D) D-5. (D) D-6. (A) D-7. (D)
D-8. (D) E-1. (D) E-2. (A) E-3. (C) E-4. (B)
E-5. (D) E-6. (C) E-7. (C) E-8. (C) E-9. (A)
E-10. (D) F-1. (B) F-2. (C) F-3. (D) F-4. (C)
G-1. (A) G-2. (A) G-3. (B) G-4. (A) G-5. (A)

PART - III
1. (A - z) ; (B - x) ; (C - w) ; (D - y) 2. (A - p,q,s) ; (B - p,q,r,s) ; (C - p,q,r,s) ; (D - p,q,r,s)

EXERCISE - 2
PART - I
1. (B) 2. (C) 3. (A) 4. (C) 5. (A)
6. (D) 7. (B) 8. (D) 9. (A) 10. (D)
11. (A) 12. (D) 13. (A) 14. (D) 15. (B)
16. (A) 17. (C) 18. (A) 19. (C) 20. (B)
21. (D) 22. (B)

PART - II
1. 7 2. 2 3. 4 (S1, S2, S4, S5) 4. 5 (ii, iii, iv, vi, vii)
5. 6 (i, ii, iii, vi, vii, ix) 6. 5 (i, iv, v, vi, viii) 7. 5 (i, iv, v, vi, viii)
8. 34 9. 3 10. 10

PART - III
1. (ABCD) 2. (BCD) 3. (ABCD) 4. (ACD) 5. (ACD)
6. (BC) 7. (BD) 8. (ABCD) 9. (ACD)

PART - IV
1. (D) 2. (D) 3. (A) 4. (A) 5. (C)
6. (B) 7. (C) 8. (A) 9. (D) 10. (D)
11. (C)