Some Basic Concept of Chemistry

Structure of Atom

Chemical Bonding

Redox Reaction

Modern Periodic Table

Elements of Group 13,14,15 ( p block elements)

Chemical Equilibrium

Basic Principle of Organic chemistry

Hydrocarbon
 SOME BASIC CONCEPT OF CHEMISTRY

1. Which of the following statements is correct 4. A metal oxide has the formula Z2O3. It can be
about the reaction given below ? reduced by hydrogen to give free metal and water.
4Fe(s) + 3O 2 (g) ¾¾ ® 2Fe 2 O 3 (g) 0.1596 g of the metal oxide requires 6 mg of
hydrogen for complete reduction. The atomic
(a) Total mass of iron and oxygen in reactants =
weight of the metal is
total mass of iron and oxygen in product
(a) 27.9 (b) 159.6 (c) 79.8 (d) 55.8
therefore, it follows law of conservation of mass.
5. 4 g of a hydrated crystal of formula A.xH2O has
(b) Total mass of reactants = total mass of 0.8 g of water. If the molar mass of the anhydrous
product; therefore, law of multiple crystal (A) is 144 g mol–1, The value of x is
proportions is followed. (a) 4 (b) 1 (c) 2 (d) 3
(c) Amount of Fe2O3 can be increased by 6. A solution of 20.2 g of 1,2-dibromopropane in
reducing the amount of any one of the MeOH upon heating with excess Zn produces
reactants (iron or oxygen). 3.58 g of an unsaturated compound X. The yield
(d) Amount of Fe2O3 produced will decrease if (%) of X is closest to [Atomic weight of Br is 80]
the amount of any one of the reactants (iron (a) 18 (b) 85 (c) 89 (d) 30
or oxygen) is taken in excess.
7. 5.0 g of a certain element X forms 10.0 g of its
2. Which of the following statements indicates that
oxide having the formula X4O6. The atomic mass
law of multiple proportion is being followed.
of X is
(a) Sample of carbon dioxide taken from any
(a) 12.0 amu (b) 24.0 amu
source will always have carbon and oxygen
(c) 30.0 amu (d) 32.0 amu
in the ratio 1 : 2.
8. The maximum number of molecules are present
(b) Carbon forms two oxides namely CO2 and
in
CO, where masses of oxygen which
(a) 15 L of H2 gas at STP
combine with fixed mass of carbon are in
(b) 5 L of N2 gas at STP
the simple ratio 2 : 1.
(c) 0.5 g of H2 gas
(c) When magnesium burns in oxygen, the (d) 10 g of O2 gas
amount of magnesium taken for the reaction 9. Number of moles of MnO4- required to oxidize
is equal to the amount of magnesium in one mole of ferrous oxalate completely in acidic
magnesium oxide formed. medium will be
(d) At constant temperature and pressure, 200
(a) 0.6 moles (b) 0.4 moles
mL of hydrogen will combine with 100 mL
(c) 7.5 moles (d) 0.2 moles
oxygen to produce 200 mL of water vapour. 10. A metallic chloride contain 47.22% metal.
3. The number of water molecules in 250 mL of Calculate the equivalent weight of metal.
water is closest to [Given, density of water is 1.0 (a) 39.68 (b) 31.76 (c) 36.35 (d) 33.46
g mL–1; Avogadro’s number = 6.023 × 1023]
(a) 83.6 × 1023 (b) 13.9 × 1023
23 23

(c) 1.5 × 10 (d) 33.6 × 10

1
11. The number of moles of water present in a 18. 5 g sample contain only Na2CO3 and Na2SO4.
spherical water droplet of radius 1.0 cm is This sample is dissolved and the volume made
[Given: density of water in the droplet = 1.0 g up to 250 mL. 25 mL of this solution neutralizes
cm–3] 20 mL of 0.1 M H2SO4. Calculate the % of Na2SO4
in the sample.
p 2p 2p
(a) (b) (c) 24p (d) (a) 42.4 (b) 57.6 (c) 36.2 (d) 0.576
18 27 9 19. 1 mole of equimolar mixture of ferric oxalate and
12. If potassium chlorate is 80% pure, then 48 g of ferrous oxalate requires x mole of KMnO4 in
oxygen would be produced from (atomic mass acidic medium for complete oxidation. x is:
of K =39) (a) 0.5 mole (b) 0.9 mole
(a) 153.12 g of KClO3 (b) 122.5 g of KClO3 (c) 1.2 mole (d) 4.5 mole
(c) 245 g of KClO3 (d) 98 g of KClO3 20. Two solutions of a substance (non electrolyte)
13. 10 g CaCO3 were dissolved in 250 mL of 100 M are mixed in the following manner. 480 mL of 1.5
HCl or the solution was boiled. What volume of M first solution + 520 mL of 1.2 M second
2M KOH would be required to equivalence point solution. What is the molarity of the final mixture?
after boiling? Assume no change in volume (a) 2.70 M (b) 1.344 M
during boiling. (c) 1.50 M (d) 1.20 M
(a) 50 mL (b) 25 mL (c) 75 mL (d) 60 mL
14. The density of 3M solution of sodium chloride Numeric Value Answer
is 1.252 g mL–1. The molality of the solution will 21. A mixture of HCOOH and H2C2O4 is heated
be : with concentrated H2SO4. The gas produced is
(molar mass, NaCl = 58.5 g mol–1) collected and on treating with KOH solution,
(a) 260 m (b) 2.18 m (c) 2.79 m (d) 3.00m the volume of gas decreases by one-sixth.
15. 2 g of a mixture of CO and CO2 on reaction with Calculate the molar ratio of the two acids
excess I2O5 produced 2.54 g of I2. What would (HCOOH : H2C2O4) in the original mixture.
be the mass % of CO2 in the original mixture? 22. One gram of a metallic chloride was found to
(a) 60 (b) 30 (c) 70 (d) 35 contain 0.835 g of chlorine. Its vapour density is
85.5. If its molecular formula is MxCly, then what
16. 3.0 g of oxalic acid [(CO2H)2.2H2O] is dissolved is value of (x + y)?
in a solvent to prepare a 250 mL solution. The
23. 0.7875 g of crystalline barium hydroxide is
density of the solution is 1.9 g/mL. The molality
dissolved in water. For the neutralization of this
and normality of the solution, respectively, are
solution 20 mL of N/4 HNO3 is required. How
closest to
many moles of water of crystallization are present
(a) 0.10 and 0.38
in one mole of this base? (Given : Atomic mass
(b) 0.10 and 0.19
Ba = 137, O = 16, N = 14, H = 1)
(c) 0.05 and 0.19
24. A mixture contains 1.0 mole each of NaOH, Na2CO3
(d) 0.05 and 0.09
and NaHCO3. When half of mixture is titrated with
17. How many moles of P4O6 and P4O10 will be
HCl, it required x mole of HCl in presence of
produced by the combustion of 12.4 g of
phenolphthalein. In another experiment, half of
phosphorous (atomic mass 31) in 12.8 g of
mixture required y mole of same HCl in presence of
oxygen, leaving no P4 or O2?
methyl orange. Find the value of (x + y).
(a) 0.1 and 0.3 mol
25. A 0.276 g impure sample of copper ore is dissolved
(b) 0.15 mol and 0.25 mol
and Cu2+ is titrated with KI solution. I2 liberated
(c) 0.05 mol each
required 40 mL of 0.1M Na2S2O3 solution for
(d) 0.1 mol each titration. What is the % of impurities in the ore?

2
 26. Density of a sulphuric acid solution is 1.225g/
mL. and it is 40% H2SO4 by weight. Determine
molarity of this solution.
27. A 16.24 mL sample of vinegar of density 1.06 g/
mL required 48.24 mL of 0.36 N solution of a
standard alkali. Determine percentage weight of
acetic acid in vinegar.
28. How much volume of sulphur dioxide at STP will
be obtained by completely burning 10 g of pure
sulphur?
29. How much volume of 4.0 M HNO3 is required to
prepare 60 mL of 0.2 M HNO3 from a stock
solution of 4.0 M HNO3?
30. The minimum number of moles of O2 required
for complete combustion of 1 mole of propane
and 2 moles of butane is ______.

ANSWER KEY
1 (a) 4 (d) 7 (b) 10 (b) 13 (b) 16 (c) 19 (b) 22 (5) 25 (8) 28 (7)
2 (b) 5 (c) 8 (a) 11 (b) 14 (c) 17 (c) 20 (b) 23 (8) 26 (5) 29 (3)
3 (a) 6 (b) 9 (b) 12 (a) 15 (b) 18 (b) 21 (4) 24 (3) 27 (6) 30 (18)

3
 Hints & Solutions
1. (a) Law of mass conservation states that matter Eq. wt. of Z + Eq. wt. of O = E + 8 = 26.6
can neither be created nor destroyed, or in a Þ Eq. wt. of Z = 26.6 – 8 = 18.6
chemical reaction, the total mass of the reactants Valency of metal in Z2O3 = 3
is equal to the total mass of the products.
Atomic wt.
4 Fe (s) + 3 O2 (g) ® 2FeO3 (g) Eq. wt.of metal =
valency
56 ´ 4 32 ´ 3 2 ´ 160
= 224g = 96 g = 320 g \ At. wt. of Z = 18.6 × 3 = 55.8
2. (b) Statement (b) is correct according to the 5. (c) Q Given of weight of hydrated crystal = 4 g
law of multiple proportions. Weight of water = 0.8
3. (a) Given: Density of water = 1.0 g mL–1 \ Weight of anhydrous salt = 4 – 0.8 = 3.2
Volume of water = 250 mL Q 3.2 g anhydrous salt = 0.8 g of water
\ Mass of water = Density × Volume \ 144 g anhydrous salt
= 1.0 × 250 = 250 g 0.8
= ´ 144 = 36 g of water
18 g of water contains 3.2
= 6.023 × 1023 molecules
\ 250 g of water contains 36
\ x= =2
18
6.023 ´ 1023
= ´ 250 = 83.65 × 1023 molecules 6. (b)
18
4. (d) The reaction may given as
Z2O3 + 3H2 ¾ ¾® 2Z + 3H2O
0.1596 g of Z2O3 react with H2 = 6 mg = 0.006 g
\ 1 g of H2 react with
Moles of 1, 2-dibromo propane
0.1596
= = 26.6g of Z2O3 20.2
0.006 = = 0.01 mole
\ Eq. wt. of Z2O3 = 26.6 (from the definition of 202
eq. wt.)
358
Moles of prop-1-ene = = 0.085 mole
42

0.085
% yield = ´ 100 = 85%
0.1

4
7. (b) Using the relationship \ Equivalent weight of metal
Mol. mass of oxide mass of oxide æ Mass of Metal ö
= =ç ÷ ´ 35.5
Mass of metal in molar mass mass of metal è Mass of chloride ø

4 x + 96 10 47.22
= Þ x = 24 = ´ 35.5 = 31.76
4x 5 52.78
8. (a) No. of molecules in different cases 11. (b) Volume of a spherical water droplet
(a) Q 22.4 litre at STP contains 4 3 4
= 6.023 × 1023 molecules of H2 = pr = p (1)3
3 3
15
\ 15 litre at STP contains = ´ 6.023 ´ 10 23 4
22.4 V= p cm3
3
= 4.03 × 1023 molecules of H2
Mass of spherical water droplet
(b) Q 22.4 litre at STP contains
= 6.023×1023 molecules of N2 4 4
= P × V = 1´ p = p g
5 3 3
Q 5 litre at STP contains = ´ 6.023 ´ 10 23 18 g of water = 1 mol
22.4
= 1.344 × 1023 molecules of N2 no. of moles of water in a spherical water droplet
(c) Q 2 g of H2= 6.023×1023 molecules of H2 4p 2p
= =
0.5 3 ´ 18 27
Q 0.5 g of H2= ´ 6.023 ´ 10 23
2
12. (a) heat
= 1.505 × 1023 molecules of H2 2KClO3 ¾¾¾
® 2KCl + 3O 2
(d) Similarly 10 g of O2 gas 2 ´ 122.5 g 3´32 g
245 96
10
= ´ 6.023 ´ 10 23 molecules of O2 48 g of oxygen will be produced from 122.5 g of
32
KClO3
= 1.88 × 1023 molecules of O2 \ Amount of 80% KClO3 needed
Thus (a) will have maximum number of molecules
100
COO– = ´ 122.5 = 153.12 g
5 MnO–4 H+ ¾® 80
9. (b) – +2 + 16
16 H
COO
oxalate ion 10
13. (b) Meq. of CaCO 3 = × 1000 = 200
2+ 50
2 Mn +10CO2+8H2O Meq. of HCl = 250 × 1 = 250
From above equation 2 moles MnO4 required to Meq. of HCl left in the solution = 250 – 200 = 50
oxide 5 moles of oxalate. \ Meq. of KOH requred V × 2 = 50
Thus number of moles of MnO4 required to \ V = 25 mL
oxidise one mole of oxalate = 2/5 = 0.4 14. (c) The relation between molarity (M) and
10. (b) Suppose weight of metallic chloride = 100 g molality (m) is
Then weight of metal = 47.22 g
d = M æç
1 M ö
Weight of chlorine = 100 – 47.22 = 52.78 g + 2 ÷ , M2 = Mol. mass of solute
è m 1000 ø
On putting value

1.252 = 3 æç
1 58.5 ö
+ ÷
è m 1000 ø
on solving m = 2.79

5
15. (b) 5CO + I2 O5 ® 5CO2 + I2 18. (b) Only Na2CO3 reacts with H2SO4;
Na2CO3 + H2SO4 ¾¾ ® Na2SO4 + H2CO3
1 mol of I 2 º 1 mol of I 2O 5 º 5 mol of CO
m-moles of Na2CO3 = m-moles of H2SO4
= 20 × 0.1 = 2
Hence, mol of CO = 5 ´ 2.54 = 0.05
254 m-moles of Na2CO3 in 250 mL solution
Mass of CO = 0.05 ´ 28 = 1.4 g 250
= × 2 = 20
Mass of CO2 = 2 - 1.4 = 0.6 g 25
wt. of Na2CO3 = 20 × 106 × 10– 3 = 2.12 g
0.6
Mass % of CO2 = ´ 100 = 30% 2.12
2 % of Na2CO3 = × 100 = 42.4
16. (c) Given mass of oxalic acid = 3 g 5
Molar mass of oxalic acid, \ % Na2SO4 = 100 – 42.4 = 57.6
(COOH)2.2H2O = 126 19. (b) Fe2 (C2 O 4 )3 + MnO 4– + H + ¾¾
® 2Fe3+
Mass ( n = 6) ( n = 5)
We know that, density = + 6CO2+ H2O
Volume
V = 250 mL Fe C2O 4 + MnO 4– + H + ¾¾
® Fe3+ + 2 CO 2 + H 2O
(n = 3) ( n = 5)
M
r= ÞM=r×V Total equivalents of (Fe2(C2O4)3 + FeC2O4)
V
= equivalents of KMnO4
\ Mass of solvent = Density × Volume
\ 0.5 × 6 + 0.5 × 3 = x × 5
nsolute m/M moles of KMnO4 = x = 0.9
Molality (m) = m = rV 20. (b) From the molarity equation.
solvent
M1V1 + M2V2 = MV
3 /126
= Let M be the molarity of final mixture,
1.9 ´ 250 ´ 10-3
103 M1V1 +M V2
2
= M= where V = V1 + V2
42 ´ 19 ´ 25 V
m = 0.05
nf of oxalic acid = 2 480 ´ 1.5 + 520 ´ 1.2
M= = 1.344 M
Normality (N) = Molality × nf 480 + 520
n H2SO 4
N= ´ nf 21. (4) HCOOH ¾¾¾¾ ® H2O + CO
V(in L) a moles a moles
3 /126
= ´2 H 2C2O4 ¾¾¾¾
H SO
2 4 ® H O + CO + CO
250 ´10–3 2 2
40 b moles b moles b moles
= ´ 2 = 0.19 Total number of moles of gases formed
42
12.4 = a + 2b
17. (c) Moles of P4 = = 0.1 Moles of gas (CO2) absorbed by KOH = b
4 ´ 31
12.8
Moles of O 2 =
32
= 0.4 Hence, b = 1 (a + 2b ) [Volume µ No. of moles)
6
Let x moles of P4 form P4O 6 . a/b = 4
Then, moles of O 2 required = x × 3 + (0.1 – x) × 22. (5) MxCly = MCly (Q valency of Cl = 1)
5 = 0.4 (given) Þ x = 0.05 Molar mass of Mx Cly = 85.5 × 2 = 171 g/mol
(M)(x) + (35.5)(y) = 171 ... (i)

6
 Þ Mass of acetic acid
Mass of chlorine 0.835
= = 17.366 × 10–3 × 60 = 1.042 g
Mass of metalic chloride 1
Þ Mass of solution = 17.21 g
35.5 y Þ Mass percentage of acid
= 1.042
M( x) + (35.5)(y) = × 100 = 6
17.21
On solving y = 4 and x = 1 28. (7) The reaction involved is: S + O2 —® SO2
x+y=5 i.e., one mole of S combines with one mole of O2
23. (8) Ba(OH)2×xH2O(aq)×+HNO3(aq) ¾¾ ® to produce one mole of SO2.
Ba(NO3)2 + H2O(l)
10
Eq. of Ba(OH)2 × x H2O = eq. of HNO3 Moles of S = = 0.3125
32
0.7875 1 20
´2 = × Þ Moles of SO2 = 0.3125
(171 + 18x ) 4 1000 Þ Vol of SO2 = 0.3125 × 22.4 = 7.0L
x=8 29. (3) Molarity × Volume (in mL) = milimoles of
24. (3) In HPh Eq. of NaOH + Eq. of Na2CO3 = Eq. solute (mmoles)
of HCl Therefore, mmoles of HNO3 required
(0.5) (1) + (0.5) (1) = (x) (1) x = 1 = 60 × 0.2 = 12
In MeOH, Eq. of NaOH + Eq. of Na2CO3 + Eq.
of NaHCO3 = Eq. of HCl m mole 12
Þ V(mL) = = = 3 mL
(0.5) (1) + (0.5) (2) + (0.5) (1) = (y)(1) molarity 4
y=2 30. (18) Complete combustion of hydrocarbons
x+y=3 can be represented by the following reaction.
25. (8) Cu 2+ + KI ¾¾
® I 2 + Cu + æ yö y
n-factor =1 n -factor = 2 C x H y + ç x + ÷ O2 ¾¾
® xCO 2 + H 2O
è 4ø 2
I2 + Na 2 S2 O3 ¾¾
® NaI + Na 2S4 O 6 For propane combustion reaction is
n - factor = 2 n–factor=1
Eq. of Cu2+ = Eq. of I2 produced = Eq. of æ 8ö 8
C3H8 + ç 3 + ÷ O2 ¾¾
® 3CO2 + H 2 O
I2 reacted = Eq. of Na2S2O3. è 4ø 2
æ 40 ö
(x) (1) = çè 1000 ÷ø (0.1) (1) \ C3 H8 + 5O 2 ¾¾
® 3CO 2 + 4H 2 O
x = 4 × 10– 3 mol Similarly, for butane is
Mass of pure Cu = 4 × 10– 3 × 63.5 = 0.254 g
æ 10 ö 10
C4 H10 + ç 4 + ÷ O2 ¾¾
® 4CO2 + H 2O
0.254 è 4ø 2
% Purity = × 100 = 92%
0.276
% Impurity = 8% 13
\ C4 H10 + , O2 ¾¾
® 4CO2 + 5H 2O
26. (5) Consider one litre of solution. Weight of 2
solution = 1225 g;
13
Weight of solute = 1225 × 0.4 = 490 g Q For 1 mol of C4H10 required O2 = mol
2
490
Moles of solute = = 5.0 \ For 2 mol of C4H10 required O2
98
Hence, molarity (M) = 5.0 13
= × 2 = 13 mol
27. (6) m.eq of acid in 16.24 mL of its solution 2
= 48.24 × 0.36 = 17.366 \ Number of moles of O2 required = 5 + 13 = 18

7
 STRUCTURE OF ATOM

1. The potential energy of electron present in 5.

ground state of Li2+ ion is represented by :
monochromatic
An electron in radiations
the groundof wave
statelength (l
of hydrogen
+3e 2 - 3e
(a) (b) was excited to a higher energy level using
4 pe 0 r 4 pe 0 r resulting spectrum is due to transition from:
) 975
Å. The
(a) longest
n 4 ¾¾ ® n1wave length
(b) that appears
n 4 ¾¾ ® n 3 the
in
-3e 2 -3e 2
(c) (d) (c) n 5 ¾¾
® n4 (d) n 5 ¾¾
® n1
4pe0 r 2 4 pe 0 r
2. Let mp be the mass of a proton, mn that of a
20
6.
neutron, M1 that of a 10 Ne nucleus and M2
If m and e are the mass and charge of the
that of a 40 nucleus. Then
20 Ca revolving electron
electron will be: in the orbit of radius r for
(a) M2 = 2M1 hydrogen atom, the total energy of the revolving
(b) M1<10(mp + mn) 1 e2 e2
(a) (b) -
(c) M2 > 2M1 2 r r
(d) M1 = M2
3. Which of the following pairs of nucleides are me2 1 e2
(c) (d) -
isodiaphers ? r 2 r
(a) 13 and 16 (b) 1 and 12 H 7.
6 C 8 O 1H
The correct representation of wavelength
3 55 65 radiation
intensityatrelationship
two differentof
temperatures T1 andbody
T2
(c) 1H and 42 He (d) 25 Mn and 30 Zn an ideal black
is
æ Z2 ö
4. Based on equation E = – 2.178 × 10-18 J ç ÷
ç n2 ÷ , T2 T2 >T1
è ø
Intensity

certain conclusions are written. Which of them (a)

is not correct ? T1
(a) Larger the value of n, the larger is the orbit
radius. Wavelength
(b) Equation can be used to calculate the change
in energy when the electron changes orbit.
(c) For n = 1, the electron has a more negative
T2 T2 >T1
energy than it does for n = 6 which mean
Intensity

that the electron is more loosely bound in

the smallest allowed orbit. (b) T1
(d) The negative sign in equation simply means
that the energy or electron bound to the
Wavelength
nucleus is lower than it would be if the electrons
were at the infinite distance from the nucleus.
8
 12. A electron in a hydrogen atom in its ground
T1 T 2 >T 1 state absorbs 1.5 times as much energy as the
minimum required for it to escape from the atom.

Intensity
(c) What is the velocity of the emitted electron?
T2
(a) 1.54 ´ 106 m/s
(b) 1.54 ´ 108 m/s
Wavelength (c) 1.54 ´ 103 m/s
(d) 1.54 ´ 104 m/s
13. For a multi-electron atom, the highest energy
T1 T2 > T1 level among the following is
(a) n = 5, l = 0, m = 0, s = +½
Intensity

(d) (b) n = 4, l = 2, m = 0, s = +½
T2 (c) n = 4, l = 1, m = 0, s = +½
(d) n = 5, l = 1, m = 0, s = +½
Wavelength

14. For Balmer series in the spectrum of atomic

hydrogen, the wave number of each line is given
8. Among the following, the incorrect statement is
(a) No two electrons in an atom can have the æ 1 1 ö
same set of four quantum numbers by v = R H ç – ÷ where RH is a constant
2
è n1 n 22 ø
(b) The maximum number of electrons in the
shell with principal quantum number, n is and n 1 and n 2 are integers. Which of the
equal to n2 + 2 following statement(s) is (are) correct?
(c) Electrons in an orbital must, have opposite I. As wavelength decreases, the lines in the
spin series converge.
(d) In the ground state, atomic orbitals are filled II. The integer n 1 is equal to 2.
in the order of their increasing energies III. The ionization energy of hydrogen can be
9. What transition in He+ ion shall have the same calculated from the wave number of these
wave number as the first line in Balmer series of lines.
H atom? IV. The line of longest wavelength corresponds
(a) 7 ® 5 (b) 6 ® 4 to n2 = 3.
(c) 5 ® 3 (d) 4 ® 2 (a) I, II and III
10. The velocity of an electron in excited state of H- (b) II, III and IV only
atom is 1.093 ´ 106 m/s. What is the circumference (c) I, II and IV
of this orbit? (d) II and IV only
(a) 3.32 ´ 10–10 m (b) 6.64 ´ 10–10 m 15. Calculate the minimum and maximum number of
(c) 13.30 ´ 10 m (d) 13.28 ´ 10–8 m
–10 electrons which may have magnetic quantum
11. The angular momentum of an electron in a number, m = +1 and spin quantum number,
Bohr’s orbit of He+ is 3.1652 × 10–34 kg-m2/sec. 1
s= - in chromium (Cr):
What is the wave number in terms of Rydberg 2
constant (R) of the spectral line emitted when (a) 0, 1 (b) 1, 2
an electron falls from this level to the first excited (c) 4, 6 (d) 2, 3
state. [Use h = 6.626 ´ 10–34 J × s]
16. The correct order of energy of 2s-orbitals in H,
5R
(a) 3R (b) Li, Na and K, is
9
(a) K < Na < Li < H
3R 8R (b) Na < Li < K < H
(c) (d)
4 9 (c) Na < K < H < Li
(d) H < Na < Li < K

9
17. Which of the following radial distribution graphs (c) the characteristics of cathode rays depend
correspond to l = 2 for the H atom ? upon the material of electrodes.
(d) the characteristics of cathode rays depend
upon the gas present in the cathode ray
(a) tube.

20. A 600 W mercury lamp emits monochromatic

radiation of wavelength 331.3 nm. How many
(b) photons are emitted from the lamp per second?
h = 6.62 × 10–34 Js velocity of light = 3 × 108 ms–1
(a) 1.0 × 1019 (b) 1.0 × 1023
(c) 1.0 × 10 21 (d) 2.0 × 1023

(c)

(d)

18. The electrons, identified by quantum numbers n

and l,
(I) n = 3, l = 2 (II) n = 5, l = 0
(III) n = 4, l = 1 (IV) n = 4, l = 2
(V) n = 4, l = 0 can be placed in order of
increasing energy, as
(a) I < V < III < IV < II (b) I < V < III, II, IV
(c) V < I < III < II < IV (d) V < I < II < III < IV
18. The energies E1 and E2 of two radiations are 25
eV and 50 eV, respectively. The relation between
their wavelengths i.e., l1 and l2 will be :
(a) l1 = l2 (b) l1 = 2l2
1
(c) l1 = 4l2 (d) l1 = l2
2
19. Among the following, the correct statement
about cathode ray discharge tube is
(a) the electrical discharge can only be
observed at high pressure and at low
voltages.
(b) in the absence of external electrical or magnetic
field, cathode rays travel in straight lines.

10
 Numeric Value Answer 27. Calculate the ratio of wavelength of first line of
Balmer series of H-atom to the wavelength of first
21. An electron has a speed of 30,000 cm sec–1
line of Lyman series of 10 times ionized sodium atom.
accurate upto 0.001%. What is the uncertainty
28. To stop the flow of photoelectrons produced by
in locating it’s position.
electromagnetic radiation incident on a certain
22. If the energies of two radiations of wavelength 800
metal, a negative potential of 300 V is required. If
nm and 400 nm are E1 and E2 respectively. Then
the photoelectric threshold of metal is 1500 Å,
calculate the value of E2/E1.
what is the frequency of the incident radiation (in
23. Determine the Bohr orbit of Li2+ ion in which
terms of 1016 Hz)?
electron is moving at speed equal to the speed
29. The energy of the electron in the second and
of electron in the first Bohr orbit of H-atom.
the third Bohr’s orbits of the hydrogen atom is –
24. A hydrogen atom with an electron in the first shell
5.42 × 10–12 erg and –2.41 × 10–12 erg respectively.
absorbs ultraviolet light with a wavelength of 1.03
Calculate the wavelength of the emitted radiation
× 10–7 m. To what shell does the electron jump?
when the electron drops from the third to the
25. What is the sum of radial node(s) and nodal
second orbit.
plane(s) for 4dz2–orbital?
30. Naturally occurring boron consists of two isotopes
26. An electron with de Broglie wavelength 4 × 10–6 m
whose atomic weights are 10.01 and 11.01. The
makes transition to a state with de Broglie
atomic weight of natural boron is 10.81. Calculate
wavelength 6 × 10–6 m. The wavelength of photon
the percentage of isotope with atomic weight 11.01
mc
generated is ´ x ´ 10-11 m . What is thevalue ofx? in natural boron.
h

ANSWER KEY
1 (d) 4 (c) 7 (a) 10 (c) 13 (d) 16 (a) 19 (b) 22 (2) 25 (1) 28 (7.45)
2 (a) 5 (b) 8 (b) 11 (b) 14 (c) 17 (c) 20 (c) 23 (3) 26 (576) 29 (6.604)
3 (d) 6 (d) 9 (b) 12 (a) 15 (d) 18 (b) 21 (2) 24 (3) 27 (653.4) 30 (80)

11
 Hints & Solutions
- Ze 2 é1 1 ù
1. (d) In S.I. units the P.E. = . For Li2+, Z = 3. or E = 13.6 ê - ú eV [Q n1 = 1]
4peo r 2
êë1 n 2 úû

-3e 2
\ P.E. = . é 1ù
4pe 0r or 12.72 = 13.6 ê1 - 2 ú [Q E = 12.72 eV]
ë n2 û
20
2. (a) 10
Ne contains 10 protons and 10 neutrons
1 12.72
or 1- =
\ M1 = 10 mp + 10mn n 22 13.6
40
20
Ca contains 20 protons and 20 neutrons 1 13.6 - 12.72 0.88 1
or = = ;
\ M2 = 20 mp + 20 mn n 22 13.6 13.6 16
\ M2 =2M1
or n 22 ; 16
3. (d) Isodiaphers have same difference of
number of neutrons and protons or (A – 2Z) or n22 ; 4
must be same. The transition n4 ¾¾® n3 will give the longest
4. (c) Energy of an electron at infinite distance from wave length.
the nucleus is zero. As an electron approaches 6. (d) Total energy of a revolving electron is the
the nucleus, the electron attraction increases and sum of its kinetic and potential energy.
hence the energy of electron decreases and thus Total energy = K.E. + P. E.
becomes negative. Thus as the value of n
e 2 æ e 2 ö e 2 - 2e 2
decreases, i.e. lower the orbit is, more negative is = + ç- ÷ =
2r è r ø 2r
the energy of the electron in it.
5. (b) The energy associated with radiation of e2
wave length 975 Å is given by =-
2r
12400
E= eV = 12.72 eV 7. (a) The frequency distribution of the emitted
975
[For a radiation of wavelength x Å, we radiation from black body depends only on its
temperature. The maximum value of intensity of
12400
know E = eV] radiation emitted will be more for higher
x
temperature. Thus, correct representation is
é1 1ù shown in option (a).
E = 13.6 ê 2 - 2 ú eV 8. (b) The maximum number of electrons in the
ë n1 n 2 û
shell with principle quantum number (n) is 2n2.

12
9. (b) For H atom, first Balmer line in series is 13. (d) According to (n + l) rule, maximum is the
(n + l) value higher is the energy level. If two
- E1 (H) E1 (H) 5 E1 (H)
E3 – E2 = + = level has same (n + l) value then the level which
(3) 2 (2)2 36
has higher value of n will have higher energy.
For He+ ion (Z = 2) 14. (c) (I) Beyond a certain wavelength the line
E1 (H) ´ (2)2 E1 (H) ´ (2)2 spectrum becomes band spectrum.
E6 – E4 = - -
(II) For Balmer series n1 = 2
62 42
(IV) For calculation of longest wavelength use
16 - 36 nearest value of n 2. Hence for longest
= –E1(H) ´ 22
16 ´ 36 wavelength in Balmer series of hydrogen
spectrum, n1 = 2 & n2 = 3.
4 ´ 20 5E1 (H)
= E (H) = 15. (d)
36 ´ 16 1 36
10. (c) vn = 2.186 ´ 106 1s 2s 2p 3s 3p 4s

1
Þ 1.093 ´ 106 = 2.186 ´ 106 ´ ;n=2 3d
n Out of 6 electrons in 2p and 3p must have
from Bohr theory we know 2pr = nl 1
h one electron with m = + 1 and s = - but in
2
= 2l, where l =
mv 3d-subshell an orbital having m = + 1 may have
n2 spin quantum no.
or r = 0.529 Þ 0.529 ´ 4 Å Therefore, minimum an maximum possible val-
Z
\ Circumference of the orbit ues are 2 and 3 respectively.
Þ 2 ´ ´ 0.529 ´ 4 ´ 10–10 16. (a) As we know that,
Þ 13.30 ´ 10–10 m -Z 2
En µ
11. (b) Angular momentum =
nh n2
2p
-Z
n ´ 6.626 ´ 10 -34
or E2 s µ
3.1652 × 10–34 = ; (2)2
2p
Therefore, as the atomic number increases, the
n=3 energy of orbital decreases. The atomic number
- æ 1 1 ö of H, Li, Na and K respectively, are 1, 3, 11 and 19.
\ n = R × Z2 × ç 2 - 2 ÷ ;
Thus, the correct order of energy of 2s-orbitals
è n1 n 2 ø
5R
is K < Na < Li < H.
æ 1 1ö
17. (c) l = 2 represent d orbital for which
–
ν = R × 22 × ç 2 - 2 ÷ Þ
è2 3 ø 9

12. (a) Energy absorbed = 13.6 ´ 1.5 = 20.4 eV out r2y 2

®

of this 6.8 eV is converted to K.E.

6.8 eV Þ 6.8 ´ 1.6 ´ 10–19 J; ®r
æ 1ö 18. (b) Given E1 = 25eV E2 = 50 eV
6.8 ´ 1.6 ´ 10–19 = K.E. Þ ç ÷ mv2
è 2ø hc hc E1 l 2
E1 = E = \ =
2KE 2 ´ 1.088 ´ 10
-18 l1 2 l 2 E 2 l1
v= = -31
m 9.1 ´ 10
l 2 25 1
\ = = \ l1 = 2l 2
= 1.54 ´ 106 m/s l1 50 2

13
19. (b) Cathode rays are independent of the nature E1 : E2 = 1 : 2 or E2 = 2E1
of the gas and electrodes placed in discharge Thus, energy of the radiation with wavelength
tube. They travel in a straight line in the absence 400 nm is twice that of the radiation of wavelength
of external electrical or magnetic field. 800 nm.
20. (c) Energy emitted by the bulb = 600 W = 600 23. (3) In the 1st Bohr orbit of H :
Js–1 (1W = 1 Js–1) n = 2.18 ´ 106 ms–1.
l = 331.3 × 10–9 m Now, let us consider that in Li2+ the electron is
in nth orbit. Speed of electron in n th Bohr orbit
hc
Energy of one photon = hv = of Li2+ is
l
3
n = (Li2+) = 2.18 ´ 106 ´
6.62 ´ 10 -34 ´ 3 ´ 108 n
=
331.3 ´ 10-9 Now, applying the condition of equal speed :
= 0.059 ´ 10–17 » 0.06 ´ 10 -17
J 3
2.18 ´ 106 ´ = 2.18 ´ 106 Þ n = 3
No. of photon emitted from the lamp per second n

600 hc 6.63 ´ 10 -34 ´ 3 ´ 108

= = 1.0 ´ 1021 24. (3) DE = =
0.06 ´ 10-17 l 1.03 ´ 10 -7

0.001 = 1.93 ´ 10–18 J

21. (2) Dv = × 30,000 = 0.3 cm sec–1
100 1 1
According to uncertainty principle, Also: DE = kZ 2 - = 2.18 ´ 10 –18
n12 n 22
h h
Dx . Dp » ; Dx.Dv » æ 1 1ö
4p 4pm
çè n 2 - n 2 ÷ø
1 2
6.625 ´10 27 ´ 7
Dx × 9.1 × 10–28 × 0.3 »
4 ´ 22 æ 1ö
Þ 1.93 ´ 10–18 = 2.18 ´ 10–18 çè 1 - ÷
Dx » 1.93 cm. » 2 n2 ø
hc Þ n = 3.
22. (2) Energy of photon, E = hn =
l 25. (1) For 4dz2–orbital, n = 4 and l = 2.
Here, c = 3.0 × 108 ms–1 Number of radial nodes = n – l – 1 = 4 – 2 – 1 = 1
In first case, l = 800 nm = 800 × 10–9 m
z
(6.626 ´ 10 -34 Js) ´ (3 ´ 108 ms-1 )
\ E1 =
800 ´ 10 -9 m
= 2.48 × 10–19 J
In second case, l = 400 nm = 400 × 10–9 m x y
-34 8 -1
(6.626 ´10 Js) ´ (3 ´ 10 ms )
\ E2 =
400 ´10-9 m
= 4.91 × 10–19 J Nodal planes are planes having zero probability
Ratio of energy of first and second radiations, of finding electron. Due to unusual shape of dz2–
E1 2.48 ´ 10 -19 J 1 orbital, it does not have a nodal plane but it
= = does possess 2 nodal cones or 2 angular nodes.
E2 4.97 ´ 10-19 J 2

14
 h h h K.E. of photoelectron = h( n – n0 ) = h æ n – c ö
26. (576) l= Þ v1 = and v2 =
mv ml1 ml 2 çè λ0 ÷ø

1 1 ( n 0 = Threshold frequency)
E = mv 2 Þ E1 - E2 = m(v12 - v22 )
2 2
æ 3 ´ 108 ö
hc h æ 1 1 ö
2 4.806 × 10–17 = 6.626 × 10 34 çç n – ÷
–10 ÷
Þ = ç - ÷ è 1500 ´10 ø
l 2m çè l12 l 22 ÷ø
= 6.626 × 10–34 ( n – 2 × 1015)
1 h æ 1 1 ö 1 4.806 ´10 –17
Þ = ç - ÷ n – 2 × 1015 = = 72.53 ´ 1015
l 2mc è 42 6 2 ø (10 -6 )2 6.626 ´10 – 34

1 h æ 20 ö 1 Þ n = 7.45 × 1016 Hz
Þ = ç ÷
l 2mc è 36 ´16 ø 10-12 hc
29. (6.604) DE = E3 – E2 = hn = or
l
mc æ 36 ´16 ö -12 mc
l= ç ÷10 m = ´ 576 ´10-11 m
h è 10 ø h hc
l=
E3 - E2
Þ x = 576
Given E2 = – 5.42 × 10–12 erg
1 æ 1 1ö E3 = – 2.41 × 10–12 erg
27. (653.4) v = = RZ 2 ç 2 – 2 ÷
l è n1 n2 ø
6.626 ´ 10 -27 ´ 3 ´ 1010
\ l=
1 æ 1 1 ö 5 -2.41 ´ 10 -12 - (–5.42 ´ 10 -12 )
2
= R ´1 ç 2 – 2 ÷ = 36 R
lH è2 3 ø
19.878 ´ 10 -17
= = 6.604 × 10–5 cm = 6.604Å
1 æ 1 1 ö 363
2 3.01 ´ 10 -12
= R ´ 11 ç 2 – 2 ÷ = R
l Na+ è1 2 ø 4 30. (80) Let the % of isotope with At. wt. 10.01 = x
\ % of isotope with At. wt. 11.01 = (100 – x)
363R
x ´ 10.01 + (100 - x) ´ 11.01
lH At. wt. of boron =
Hence = 4 = 653.4 100
l + 5R
Na
36 x ´ 10.01 + (100 - x) ´ 11.01
Þ 10.81 =
28. (7.45) 100
K.E. of photoelectron = e– × stopping potential \ x = 20
= 1.602 × 10–19 × 300 Hence % of isotope with At. wt. 10.01 = 20%
= 4.806 × 10–17 J \ % of isotope with At. wt. 11.01 = 100 – 20 = 80%

15
 CHEMICAL BONDING

1. For AB bond if percent ionic character is plotted 4. Which of the following statements is/are true
against electronegativity difference (XA – XB), 1. PH 5 and BiCl5 do not exist
the shape of the curve would look like
2. p p – d p bond is present in SO2
C
100 3. I3+ has bent geometry
Percent ionic character

B
A D 4. SeF4 and CH4 have same shape
50 (a) 1, 2, 3 (b) 1, 3
(c) 1, 3, 4 (d) 1, 2, 4

0 5. The number of sigma (s) and pi (p) bonds present

1 2 3 in 1,3,5,7 octatetraene respectively are
(XA – XB)
The correct curve is (a) 14 and 3 (b) 17 and 4
(a) (A) (b) (B) (c) 16 and 5 (d) 15 and 4
(c) (C) (d) (D) 6. The hybridizations of N, C and O shown in the
2. The electronegativity difference between N and following compound
F is greater than that between N and H yet the R
dipole moment of NH3 (1.5 D) is larger than that N==C==O
of NF3 (0.2D). This is because respectively, are
(a) in NH3 the atomic dipole and bond dipole
(a) sp2, sp, sp2 (b) sp2, sp2, sp2
are in the same direction whereas in NF3
these are in opposite directions (c) sp2, sp, sp (d) sp, sp, sp2
7. The bond dissociation energy of B – F in BF3 is
(b) in NH3 as well as NF3 the atomic dipole and 646 kJ mol–1 whereas that of C – F in CF4 is 515
bond dipole are in opposite directions kJ mol–1. The correct reason for higher B – F
(c) in NH3 the atomic dipole and bond dipole bond dissociation energy as compared to that
are in the opposite directions whereas in of C – F is
NF3 these are in the same direction
(a) stronger s bond between B and F in BF3 as
(d) in NH3 as well as in NF 3 the atomic
compared to that between C and F in CF4.
dipole and bond dipole are in the same
(b) significant pp – pp interaction between B
direction
and F in BF3 whereas there is no possibility
3. Among the following, the species with identical
of such interaction between C and F in CF4.
bond order are
(c) lower degree of pp – pp interaction between B
(a) CO and O2– 2
and F in BF3 than that between C and F in CF4.
(b) O2– and CO
(d) smaller size of B– atom as compared to that
(c) O2–
2 and B2 of C– atom.
(d) CO and N+2

16
8. The most polarizable ion among the following is (b) NO > NO - > NO +
(a) F– (b) I–
+
(c) NO + > NO > NO -
(c) Na (d) Cl–
9. Minimum F - S - F bond angle present in : (d) NO + > NO - > NO
(a) SSF2 (b) SF6 15. Which of the following represents the correct
(c) SF2 (d) F3SSF order of Cl–O bond lengths in
10. Which of the following statement is correct ClO – , ClO 2– , ClO3– , ClO 4– ?

about I3+ and I3- molecular ions? (a) ClO 4–= ClO 3–= ClO 2–= ClO –

(a) Number of lone pairs at central atoms are (b) ClO – < ClO 2– < ClO3– < ClO 4–
same in both molecular ions
(c) ClO4– < ClO3– < ClO2– < ClO –
(b) Hybridization of central atoms in both ions
are same (d) ClO3– < ClO4– < ClO2– < ClO –
(c) Both are polar species
(d) Both are planar species 16. Which one of the following molecule will have
all equal X—F bond length? (where X = Central
11. In which of the following species, d-orbitals atom)
having xz and yz two nodal planes involved in (a) SOCl2F2 (b) SeF4
hybridization of central atom? (c) PBr2F3 (d) IF7
(a) IO2F–2 17. Select the incorrect statement about N2F4 and
(b) ClF–4 N2H4 :
(c) IF7 (I) In N 2F4, d-orbitals are contracted by
(d) None of these electronegative fluorine atoms, but d-
+
12. The type of bonds present in sulphuric orbital contraction is not possible by H-
anhydride is, atom in N2H4
(a) 3s and three pp – dp (II) The N-N bond energy in N2F4 is more than
(b) 3s, one pp – pp and two pp – dp N-N bond energy in N2H4
(c) 2s and three pp – dp (III) The N-N bond length in N2F4 is more than
(d) 2s and two pp – dp that of in N2H4
13. The correct statement with regard to H+2 and (IV) The N-N bond length in N2F4 is less than
that of in N2H4
H-2 is (a) I, II and III
(b) I and III
(a) Both H+2 and H-2 do not exist
(c) II and IV
(b) H-2 is more stable than H+2 (d) II and III
18. The correct order of ‘S—O’ bond length is
(c) H+2 is more stable than H-2
(a) SO 32 - > SO24 - > SO3 > SO2
(d) Both H+2 and H-2 are equally stable
(b) SO 32 - > SO24 - > SO2 > SO3
14. The correct order of bond energies in NO, NO
and NO– is: (c) SO 24 - > SO24 - > SO2 > SO3
(a) NO - > NO > NO + (d) SO 24 - > SO24 - > SO3 > SO2

17
19. Among the following transformations, the Numeric Value Answer
hybridization of the central atom remains
21. Consider the following molecule
unchanged in
(a) CO2 ® HCOOH
O O O
(b) BF3 ® BF4- S S
+
(c) NH3 ® NH4 O O
O O
(d) PCl3 ® PCl5 S
20. In which species, X—O bond order is 1.5 and O O
contains pp – dp bond(s).
Calculate the value of p ÷ q, here p and q are
(a) IO2F–2 (b) HCOO–
total number of dp–pp bonds and total number
(c) SO2– 3 (d) XeO2F2 of sp3 hybridised atoms respectively in given
molecule.
22. Calculate the value of “x + y – z” here x, y and z
are total number of non-bonded electron pair(s),
pie(p) bond(s) and sigma (s) bonds in hydrogen
phosphite ion respectively.
23. Total number of species which used all three p-
orbitals in hybridisation of central atoms and
should be non-polar also are

XeO2F2, SnCl2, IF5, I3+ , XeO4, SO2, XeF7+ , SeF4

24. Consider the following orbitals 3s, 2px, 4dxy, 4dz2 ,

3d , 3py, 4s, 4pz and find total number of
x2 - y2

orbital(s) having even number of nodal plane.

25. For the following molecules :

PCl5, BrF3, ICl-2 , XeF5- , NO3- , XeO2F2, PCl+4 , CH3+

a+b
Calculate the value of
c
a = Number of species having sp 3
d-hybridisation
b = Number of species which are planar
c = Number of species which are non-planar
26. Find total number of orbital which can overlap
colaterally, (if inter nuclear axis is z) s, px, py, pz,
dxy, dyz, dxz, d z 2, dx 2 - y 2

18
 30. Consider the following values for an ionic
27. In O-2 , O2 and O 22- molecular species, the sum
compound NaCl.
of the total number of antibonding electrons is D Hf (NaCl) = –200 KJ/mol
________
D Hsub(Na(s)) = 650 KJ/mol
D Hdiss(Cl2(g)) = 400 KJ/mol
28. Dipole moment of X is 1.6 D. What
I.E.1(Na(g)) = 500 KJ/mol
is the dipole moment of following compound: Electron gain enthalpy (Cl(g)) = –350 KJ/mol
29. What is the % of p-character with central atom Using Born Haber Cycle, find the value of lattic
in SF6 molecule? energy (U) in KJ/mol.

ANSWER KEY
1 (c) 4 (a) 7 (b) 10 (d) 13 (c) 16 (a) 19 (c) 22 (3) 25 (3) 28 (1.6)
2 (a) 5 (b) 8 (b) 11 (c) 14 (c) 17 (b) 20 (a) 23 (2) 26 (6) 29 (50)
3 (c) 6 (a) 9 (d) 12 (b) 15 (c) 18 (b) 21 (1) 24 (5) 27 (21) 30 (1200)

19
 Hints & Solutions
1. (c) Percent ionic character is given by 1
following equation. B.O = (10 - 8) = 1
% of ionic character = 16(XA – XB) + 3.5(XA – XB)2 2
From the above relation, it is clear that as soon as The electronic configuration of O -2 (17) is
(XA – XB) increases, % ionic character will also
increase. Therefore, curve C show a correct path. s1s 2s *1s 2 s 2s 2s *2s 2 s2pz2 p 2px2 = p 2 py2
2. (a) In NH3 the atomic dipole (orbital dipole due
to lone pair) and bond dipole are in the same p*2p2x = p *2 p1y
direction whereas in NF3 these are in opposite
direction so in the former case they are added 1 3
up whereas in the latter case net result is B.O = (10 - 7) = = 1.5
2 2
reduction of dipole moment. It has been shown The electronic configuration of B2 (10) is
in the following figure :
s1s 2s *1s 2 s 2s 2s *2s 2 p 2 px1 = p 2 py1

1 2
B.O = [6 - 4] = = 1
N N 2 2
N N
H F Electronic configuration of N +2 (13) is
H F
H F
s1s 2s *1s 2 s2 s 2s *2s 2 p2 p2x = p2 py2 s2p1z
NH3 NF3
1 1 5
3. (c) B.O. = ( Nb - Na ) B.O = [9 - 4] = = 2.5
2 2 2
where, Nb = electrons in bonding orbitals Na = Thus, option (c) is correct.
electrons in antibonding orbitals. 4. (a) 1. PH5 doesn’t exist because d–orbital of
The electronic configuration of CO (14) is P interact with s–orbital of H. Bond formed is
not stable and not energetically favorable and
s1s s*1s 2 s 2s 2 s *2 s 2 2 pz2 p 2 px2 = p 2p2y in case of BiCl5 + 5 oxidation state is not stable
due to inert pair effect.
1 6 2.
\ B.O = (10 - 4) = = 3
2 2 3s 3p 3d
The electronic configuration of O 22 - (18) is S–atom
144
424443 dp – pp
s1s 2s *1s 2 s 2s 2s *2s 2 s2pz2 p 2px2 = p 2 py2
2
sp

p*2p2x = p *2 py2
O atom O atom

20
 + 8. (b) As the size of anion increases polarizibility
··
3. I3+ I- I -I sp3 hybridisation of anion increase. Among given anions I– has
·· maximum size.
F
F F
S S
S F
I 9. (d) F F F
F
I ÐFSF < 109°28' ÐFSF = 90°
I
144 42444 3 F
Bent geometry F
S S
4. SeF4 sp3d see–saw F
F S F
CH4 sp3 tetrahedral F
Thus, option (a) is correct ÐFSF < 109°28' ÐFSF < 90°
5. (b) I
H—C—
ss s s s s s s s 10. (d)
p C— C —p C— C —p C— C —p C—H + –
s s s s s s s s I I
H H H H H H H H I
1, 3, 5, 7 - octatetraene I I
17 s and 4 p 3 3
6. (a) R—N==C==O Hyb. : sp Hyb. : sp d
Nitrogen has 2 sigma bond and a lone pair of m¹0 m= 0
electron Planar Planar
\ hybridisation is sp2. Carbon has 2 sigma bond
\ hybridisation is sp. Oxygen has 1 sigma bond 11. (c) IO 2 F2- : Hyb. sp3 d , [ º sp x p y p z d 2 ]
z
and two lone pair of electron \ hybridisation is sp2.
ClF4- 3 2
: Hyb. sp d [ º sp x p y p z d d ]
NOTE: p-bonding electron does not take part x2 - y 2 z 2
in hybridisation.
7. (b) The delocalised pp - pp bonding between IF7 : Hyb. sp3 d 3.[ sp x p y p z d d d ]
x 2 - y 2 xy z 2
filled p-orbital of F and vacant p-orbital of B leads dxy : orbital has two nodal planes xz and yz.
to shortening of B–F bond length which results 12. (b) SO3
in higher bond dissociation energy of the B–F
bond.
s bond = 3 ü
ý number of covalent bond = 6
p bond = 3 þ
F 1
Lone pair = = ( 6 - 6) = 0
B F 2
F Hybridization = 3 + 0 = 3 (sp2)
Unhybridized p–orbitals left = 1 so pp–pp = 1
Vacant Filled
p bond = 3
2p-orbital 2p-orbital pp – dp = 3 – 1 = 2
Thus, SO3 has 3s, one pp–pp and two pp – dp
F F bonds.
+
B=F B–F 13. (c) H +2 : (s1s1)
+
F F
1 1
+ +1/3 \ B.O. = (1 - 0) =
F F 2 2
+1/3
B–F
+1/3
B F H -2 : (s1s 2 )(s *1s1 )
F F 1 1
\ B.O. = (2 - 1) =
2 2

21
 Even though the bond order of H +2 and H-2 are F
Br
equal but H +2
is more stable than as in the H-2 Þ F P Þ Equatorial P—F bond is
latter, an electron is present in the antibonding Br
(s*1s) orbital of higher energy, which results in F
repulsion and decrease the stability. shorter than axial P—F bond.
14. (c) Bond energy µ Bond order F
Bond order can be determined by MO F F
configuration. Þ I F Þ Equatorial I—F bond is
NO : No. of electrons = 7 + 8 = 15 F F
F
s1s2, s*1s2, s2s2, s*2s2, s 2Pz2 , p2p 2x = p2p 2y , p * 2p1x longer than axial I—F bond.
10 - 5
\ Bond order = = 2.5
2 F H
NO+ : No. of electrons = 15 – 1 = 14 N F N H
17. (b) F N H N
Delete p* 2p1x from NO configuration F H
10 - 4
\ Bond order = =3
2 It can be explained on the basis of Bent's rule. In
NO– : No. of electrons = 15 + 1 = 16 N2F4, N—N bond has more s-character hence
bond length decreases.
s1s 2 , s *1s 2 , s2s 2 , s * 2s 2 , s2p 2z , p2p 2x = p2p 2y ,
While in N2H4, N—N bond has less s-character
1
p *2p1x = p * 2p y (i.e., more p-character), hence bond lengths
increases.
10 - 6
\ Bond order = =2 O O
2
\ Bond order; hence bond strength S S
18. (b) O O O O
NO+ > NO > NO–
O
15. (c) The B.O in Cl – O– is 1
The B.O in O = Cl – O– is 1.5 4 6
B.O. = = 1.33 B.O. = = 1.5
3 4
5
The B.O. in O = Cl = O is = 1.66
3 é 1 ù
ê B.L. µ B.O. ú
O – ë û
O
7 \SO32- > SO 42- > SO 2 > SO3
The B.O. in O = Cl – O – is = 1.75 Bent 's Rule
4
O 19. (c)
The bond length increases as B.O. decreases. Compounds Hybridization of
F central atom
Cl CO2 sp
16. (a) Þ O S Þ both S—F bonds are of HCOOH sp2
Cl BF3 sp2
F –
BF4 sp3
equal length.
NH3 sp3
F NH4+ sp3
F
Þ Se Þ Equatorial Se—F bond is PCl3 sp3
PCl5 sp3d
F
F Hybridization of NH3 and NH4+ remains
shorter than axial Se—F bond. unchanged after transformation i.e. sp3.

22
20. (a) F – pp-pp bond(s) = 0
O F +
I pp-dp bond(s) = 1 F F
O Bond order of (I—O) = 1.5 F Xe
Sn
F F F
pp-pp bond(s) = 1 O O F
O
H— C pp-dp bond(s) = 0 sp 2 sp3d 3
–
O Bond order of (C—O) = 1.5 polar non-polar
F
O pp-pp bond(s) = 0 F
Xe F
pp-dp bond(s) = 1
O Se
Bond order of (S–O) = 1.33 F
F
F
pp-pp bond(s) = 0 sp3d
– S – pp-dp bond(s) = 2 polar
O O Bond order of (Xe—O) = 2.0
O 24. (5) Species Nodal Plane
sp 2 O sp 2 3s 0
O
4d 0
pp- dp

z2
p

sp 3 s
-d
pp

s 4s 0
O
21. (1) Ssp 3 sp 3
S s 2px 1
s pp-dp O sp 2
3d 2
sp 2 O O sp 3 O sp 3 x2 - y2
sp 3 4pz 1
S
- dp
pp
-d 4dxy 2
pp s s
p
O sp 2 O sp 2 3 py 1
\ Total no. of orbitals
p = 3s, 4dxy 4d z2 , 3d x 2 - y 2 , 4s (Five)
p = 6, q = 6; =1
q
22. (3) – 25. (3) ® sp 3d , non-planar
PCl5 ¾¾
O

P ® sp 3d , bent, T-shape, planar

BrF3 ¾¾
H–O O
H ICl-2 ¾¾
® sp3d , linear, planar
x = 7, y = 1, z = 5
7 + 1 – 5 = 3. XeF5- ¾¾
® sp 3d 3 , pentagonal planar

23. (2) XeO4 , XeF7+ NO3- ¾¾

® sp 2 , planar
F F
O F F ® sp 3d , see-saw, non-planar
XeO2 F2 ¾¾
Xe I
Sn
O F F PCl+4 ¾¾
® sp 3 , tetrahedral, non-planar
F3 Cl Cl
2 3 2
sp d sp sp d CH3+ ¾¾
® sp 2 , Trigonal planar
polar polar polar a = 4, b = 5, c = 3
O
a+b
+ so, =3
Xe c
I 26. (6) (p x , p y , d xy , d yz , d xz , d )
O x 2 –y 2
I I O O
3 3 27. (21) Molecular orbital electronic configuration
sp sp
of these species are :
polar non-polar
O -2 (17e- ) = s1s 2 , s *1s 2 , s2s 2 , s * 2s 2 , s2 p2z ,
23
 p2 p 2x = p 2 p 2y , p * 2 px2 = p * 2 p1y m= m12 + m 22 + 2m1m 2 cos q
O 2 (16e- ) = s1s 2 , s *1s 2 , s2s 2 , s * 2s 2 , s2 pz2 , = 1.62 + 1.62 + 2 ´ 1.6 ´ 1.6 ´ cos(120) = 1.6 D
p2 px2 = p2 p 2y , p * 2 p1x = p * 2 p1y 29. (50) The hybridization of S in SF6 is sp3d2.
O 22- (18e- ) = s1s 2 , s *1s 2 , s2s 2 , s * 2 s 2 , s2 pz2 , 3
% p character = ×100 = 50
6
p2 px2 = p2 p 2y , p * 2 px2 = p * 2 p 2y 30. (1200) 1
Therefore number of antibonding electrons are Na(s) + Cl (g)
2 2
7, 6 and 8 respectively and the sum is 21. 1 DHf
DHsub DH diss
28. (1.6) The substituent in o– and p– position, 2
will cancel each others dipole moment.
Na(g) Cl(g)
X Na+Cl–(s)
1 I.E.1 –e– –D Heg +e–
X X
6 2
Na+(g) Cl–(g) –U
5 3
4
X 1
DHf = DHsub + DHdiss + I.E.1 – DHeg – U
The angle between 2 and 6 positions is 120°. 2
The resultant dipole moment generated by these
1
two is: Þ –200 = 650 + × 400 + 500 – 350 – U
2
Þ U = 1200 kJ/mol

24
 REDOX REACTION

1. Which reaction involves neither oxidation nor 6. The oxidation state of the most electronegative
reduction? element in the products of the reaction between
BaO2 and H2SO4 are
(a) CrO 24 - ¾¾
® Cr2O 72 -
(a) 0 and –1 (b) –1 and – 2
(c) – 2 and 0 (d) – 2 and +1
(b) Cr ¾¾
® CrCl3
7. Which of the following substances acts as an
(c) Na ¾¾
® Na + oxidising as well as a reducing agent?
(a) Na 2O (b) SnCl2
(d) 2S2 O32 - ¾¾
® S4 O 62 -
(c) Na 2O 2 (d) NaNO 2
2. In the reaction
Cr2 O 72 - + 14 H + + 6 I - ¾
¾® 2Cr 3+ + 7 H 2 O + 3I 2
8. Which of the following reactions depicts the
Which element is reduced oxidising property of SO2 ?
(a) I (b) O (a) SO 2 + H 2 O ® H 2 SO 3
(c) H (d) Cr
(b) 2H 2S + SO 2 ® 3S + 2H 2O
3. Which one of the following reaction involves
(c) Cl 2 + SO 2 ® SO 2 Cl 2
oxidation-reduction ?
(d) 2MnO 4– + 5SO 2 + 2H 2 O ®
(a) H 2 + Br2 ® 2HBr
5SO 24– + 2Mn 2+ + 4H +
(b) NaBr + HCl ® NaCl + HBr 9. The most powerful oxidizing agent from the
(c) HBr + AgNO3 ® AgBr + HNO3 following is
(d) 2NaOH + H 2SO4 ® Na 2SO4 + 2H 2O (a) H3BO3 (b) HPO3
(c) H3PO4 (d) H2SO4
4. Oxidation numbers of chlorine atoms in CaOCl2 10. Which one of the following reactions involves
are disproportionation?
(a) 0, 0 (a) 2H2SO4 + Cu ® CuSO4 + 2H2O + SO2
(b) –1, –1 (b) As2O3 + 3H2S ® As2S3 + 3H2O
(c) –1, +1 (c) 2KOH + Cl2 ® KCl + KOCl + H2O
(d) None of these (d) Ca3P2 + 6H2O ® 3Ca(OH)2 + 2PH3
5. In the reaction 11. In the standardization of Na2S2O3 using K2Cr2O7
by iodometry, the equivalent weight of K2 Cr2 O7 is
3Br2 + 6CO 32 - + 3H 2 O ® 5Br - + BrO3– + 6HCO 3-
(a) Molecular weight/2
(a) bromine is oxidised and carbonate is (b) Molecular weight/6
reduced. (c) Molecular weight/3
(b) bromine is reduced and water is oxidised (d) Same as molecular weight
(c) bromine is neither reduced nor oxidised
(d) bromine is both reduced and oxidised

25
12. Which of the following statements are correct
Numeric Value Answer
concerning redox properties?
(i) A metal M for which E° for the half life 16. In the chemical reaction,
ˆˆ† M is very
reaction M n+ + ne – ‡ˆˆ K 2 Cr2 O7 + X H 2SO 4 + YSO2 ®
negative will be a good reducing agent. K 2SO4 + Cr2 (SO4 )3 + Z H 2O
(ii) The oxidizing power of the halogens
X, Y and Z is
decreases from chlorine to iodine.
17. Atomic number of an element is 22. The highest
(iii) The reducing power of hydrogen halides
O.S. exhibited by it in its compounds is
increases from hydrogen chloride to
18. The number of electrons required to balance the
hydrogen iodide
following equation
(a) (i), (ii) and (iii) (b) (i) and (ii)
NO3– + 4H + + e – ¾¾
® 2H 2 O + NO is -
(c) (i) only (d) (ii) and (iii)
13.
–
E Values of some redox couples are given 19. The O.N. of nitrogen in NO3- is
below. On the basis of these values choose the
-
correct option. 20. The oxidation state of iodine in H4 IO6 is
–
E values : Br2/Br – = + 1.90; Ag+ /Ag(s) = + 0.80
Cu2+ /Cu(s) = + 0.34; I2(s) /I– = 0.54
(a) Cu will reduce Br – (b) Cu will reduce Ag
(c) Cu will reduce I – (d) Cu will reduce Br2
14. Standard reduction electrode potentials of three
metals A, B & C are respectively + 0.5 V, – 3.0 V &
–1.2 V. The reducing powers of these metals are
(a) A > B > C (b) C > B > A
(c) A > C > B (d) B > C > A
15. The formal oxidation numbers of Cr and Cl in the
ions Cr2O72– and ClO3–, respectively are
(a) + 6 and +7 (b) +7 and +5
(c) +6 and +5 (d) +8 and +7

ANSWER KEY
1 (a) 3 (a) 5 (d) 7 (d) 9 (d) 11 ( b) 13 (d) 15 (c) 17 (4) 19 (5)
2 (d) 4 (c) 6 (b) 8 (b) 10 (c) 12 (a) 14 (d) 16 (5) 18 (3) 20 (7)

26
 Hints & Solutions
1. (a) Ox. no. of Cr on both side is + 6. 8. (b) SO2 oxidises H2S to S, since the O.N. of S
2. (d) 2I - ® I2 is oxidation (loss of electrons) ; change from –2 to 0.
Cr (+6) changes to Cr (+3) by gain of electrons. 9. (d) In H 2SO4 , sulphur is in highest oxidation
Hence Cr is reduced.
state (+6), hence H2SO4 will be strongest
3. (a) In a redox reaction, one molecule is oxidised
oxidising agent.
and other molecule is reduced i.e. oxidation
10. (c) A reaction in which a substance undergoes
number of reactants are changed.
simultaneous oxidation and reduction is called
0 0 +1 -1 disproportionation reaction. In these reactions
H2 + Br2 ¾¾
® 2 HBr
the same substance simultaneously acts as an
Here H2 is oxidised and Br 2 is reduced, thus it is oxidising agent and as a reducing agent. Here Cl
oxidation-reduction reaction. undergoes simultaneous oxidation and
4. (c) CaOCl2 or Ca (OCl) Cl is the mixed salt of reduction.
Ca(OH)2 with HCl and HOCl. 0 -1 +1
2KOH + Cl2 ® KCl+ KOCl + H 2O.
0
5. (d) 3Br + 6CO2– + 3H O ®
2 3 2 11. ( b) The reaction involve 6 electrons, i.e.
Cr2O72– accepts 6 electrons for its reduction to Cr3+
-1 +5
5 B r – + Br O3– + 6HCO3– 2Cr2 O 72- + 14H + + 6I - ® 2Cr 3+ + 7H 2O + 3I2
O.N. of Br2 changes from 0 to –1and +5 hence it ˆˆ† M, for this reaction,
12. (a) (i) Mnn+ + ne– ‡ˆˆ
is reduced as well as oxidised.
high negative value of E° indicates lower
6. (b) BaO2 + H2SO4 ® BaSO4 + H2O2
reduction potential, that means M will be a good
The most electronegative element O is present
reducing agent.
in BaSO4 and H2O2, where its O.N. are – 2 and
– 1 respectively. Stronger reducing agent Þ Easy to oxidise
7. (d) In Na2O, SnCl2 and Na2O2 central atom is ß
either in lowest or highest oxidation state, so it Lower reduction potential Ü higher oxidation potential
can function either as an oxidising or a reducing (ii) Element F Cl Br I
agent but not both. However, the oxidation state Reduction +2.87 +1.36 +1.06 +0.54
of N in NaNO2 is +3 which lies between its potential
highest (+5) and lowest (–3) values. (E° volt)

27
 As reduction potential decreases from fluorine
16. (5) K 2 Cr2O7 + H 2SO4 + 3SO 2 ®
to iodine, oxidising nature also decreases from X =1 Y =3
fluorine to iodine.
(iii) The size of halide ions increases from F – to K 2SO 4 + Cr2 (SO4 )3 + H 2O
Z =1
I –. The bigger ion can loose electron easily.
Hence the reducing nature increases from HF to HI. The sum of x, y and z = 1 + 3 + 1 = 5
13. (d) 17. (4) The element is Ti (At. no. 22). Electronic
14. (d) A B C configuration is 1s2, 2s2p6, 3s2p6d2, 4s2. the
+0.5C –3.0V –1.2V
energy level of 3d and 4s is very close. It can
The higher the negative value of reduction have Ti4+ O.S.
potential, the more is the reducing power. 18. (3) In the equation all the atoms are balanced,
Hence the correct order is B > C > A. to balance charge add 3e– to L.H.S.

15. (c) In Cr2 O37- , let the oxidation state of Cr be x. NO3– + 4H + + 3e – ¾¾

® 2H 2 O + NO
\ 2(x) + 7 (–2) = – 2 19. (5) NO3–
2x – 14 = –2 Let x be the oxidation number of nitrogen
2x = 12 [x + 3 × (–2)] = –1 Þ x = –1 + 6 = + 5
x = +6 20. (7) H 4 IO6- : 4 + x - 12 = -1
In ClO3- , let the oxidation state of Cl be x. Þ x=7
\ 1(x) + 3 (–2) = –1 Oxidation state of I = +7
x–6 = –1
x = +5

28
 MODERN PERIODIC TABLE

1. Which form coloured salts? (a) 23 and 5 (b) 23 and 15

(a) Non-metals (c) 33 and 15 (d) 33 and 5
(b) Metals 8. Which one of the following ions has the highest
(c) p-block elements value of ionic radius ?
(d) Transitional elements (a) O2– (b) B3+
+ (d) F–
2. The ionic radii of Na+, F–, O2–, N3– follow the (c) Li
order 9. The first ionisation potential in electron volts
(a) O2– > F– > Na+ > N3– of nitrogen and oxygen atoms are respectively
(b) N3– > Na+ > F– > O2–
given by
(c) N3– > O2– > F– > Na+ (a) 14.6, 13.6 (b) 13.6, 14.6
(d) Na+ > F– > O2– > N3– (c) 13.6, 13.6 (d) 14.6, 14.6
3. The electronic configuration of four elements 10. In which of the following process highest
are given below. Which elements does not be- energy is absorbed?
long to the same family as others? Br ® Br -
(a) Cu ® Cu + (b)
10 2
(a) [Xe]4 f 14 5d 10 ls 2 (b) [Kr]4d 5s
(c) I ® I- (d) Li ® Li +
(c) [Ne]3s23p5 (d) [Ar] 3d10 4s2
11. Which ionisation potential (IP) in the following
4. The elements with atomic numbers 9, 17, 35, 53
equations involves the greatest amount of
and 85 belong to
energy?
(a) alkali metals
(a) Na ® Na + + e -
(b) alkaline earth metals
(c) halogens (b) K + ® K 2+ + e -
(d) noble gases (c) C 2 + ® C 3+ + e-
5. Eka-aluminium and Eka-silicon are known as (d) Ca + ® Ca 2 + + e -
(a) gallium and germanium
12. Which of the following order is wrong?
(b) aluminium and silicon
(a) NH3 < PH3 < AsH3 – Acidic
(c) iron and sulphur
(b) Li < Be < B < C – First IP
(d) manganese and magnesium
(c) Al2O3 < MgO < Na2O < K2O – Basic
6. What is the atomic number of the next halogen
(d) Li+ < Na+ < K+ < Cs+ – Ionic radius
if discovered?
(a) 85 (b) 117
13. The incorrect statement among the following
(c) 167 (d) 104
is
7. The electronic configuration of an element is
(a) The first ionization potential of Al is less
1s 2 2s 2 2 p 6 3s 2 3 p 3 . The atomic number and than the first ionization potential of Mg
the group number of the element ‘X’ which is (b) The second ionization potential of Mg is
just below the above element in the periodic greater th an the second ionization
table are respectively potential of Na

29
 (c) The first ionization potential of Na is less 19.
than the first ionization potential of Mg C and D are given below :
Electronic configurations of four elements A, B,
(d) The third ionization potential of Mg is (i) 1s2 2s2 2p6
greater than the third ionization potential (ii) 1s2 2s2 2p4
of Al. (iii) 1s2 2s2 2p6 3s1
14. The ease of loss of electron from Ne and Na+ (iv) 1s2 2s2 2p5
ion (both isoelectronic) are
(a) 4562 kJ mol–1, 2081 kJ mol–1 increasing
Which tendency
of the followingto gain electron
is the correct? order of
(b) 2081 kJ mol–1, 4562 kJ mol–1 (a) (i) < (iii) < (ii) < (iv)
(c) 2081 kJ mol–1 each (b) (i) < (ii) < (iii) < (iv)
(d) 4562 kJ mol–1 each (c) (iv) < (ii) < (iii) < (i)
15. The electron affinity for the inert gases is (d) (iv) < (i) < (ii) < (iii)
(a) zero (b) high
20. The basic character of MgO, BaO, Na2
(c) negative (d) positive O and
FeO follow the order
16. The correct order of acidic strength :
(a) Cl 2 O 7 > SO 2 > P4O10 (a) MgO < FeO < BaO < Na 2O

(b) K 2O > CaO > MgO (b) FeO < MgO < Na 2O < BaO

(c) CO 2 > N 2 O 5 > SO 3 (c) FeO < MgO < BaO < Na 2O
(d) Na 2 O > MgO > Al 2O 3
(d) Na 2 O < MgO < FeO < BaO
17. The formation of the oxide ion O2–(g) requires
first an exothermic and then an endothermic step
as shown below :
O( g ) + e - = O - ( g ) DHº = -142 kJmol -1

O - ( g ) + e - = O 2 - ( g ) DHº = 844 kJmol -1

This is because
(a) O– ion will tend to resist the addition of
another electron
(b) Oxygen has high electron affinity
(c) Oxygen is more electronegative

(d) O– ion has comparatively larger size than

oxygen atom
18. Amphoteric-oxide combinations are in
(a) ZnO, K2O, SO3
(b) ZnO, P2O5, Cl2O7
(c) SnO2, Al2O3, ZnO
(d) PbO2, SnO2, SO3

30
 Numeric Value Answer
21. In the IUPAC nomenclature of elements, what
is atomic number for the element ‘Unh’?
22. The first ionisation potential of Cu, Ag and Au
are 731, 745 and 890 KJ/mol (not in the same
order). What is the numerical value of I.E. for Ag?
23. How many completely filled periods are there in
the long form of the periodic table ?
24. What is the number of elements in the third period
of the periodic table except metalloids?
25. How many pairs are, in which first species has
lower ionisation energy than second species:
(i) N and O (ii) Br and K
(iii) Be and B (iv) I and I–
(iv) Li and Li+ (v) O and S
(vii) Ba and Sr

ANSWER KEY
1 (d) 4 (c) 7 (c) 10 (a) 13 (b) 16 (a) 19 (a) 22 (731) 25 (2)
2 (c) 5 (a) 8 (a) 11 (b) 14 (b) 17 (a) 20 (c) 23 (7)
3 (c) 6 (b) 9 (a) 12 (b) 15 (a) 18 (c) 21 (106) 24 (7)

31
 Hints & Solutions
1. (d) Most of the transition metal compounds 7. (c) Atomic number of the given element = 15;
(ionic as well as covalent) are coloured both group no. = 10 + 5 (valence electrons) = 15,
in the solid state and in aqueous solution in period = 4th Therefore atomic number of the
contrast to the compounds of s and p-block element below the above element = 15 + 18 = 33.
elements due to the presence of incomplete 8. (a) O– – and F– are isoelectronic. Hence have
d-subshell. same number of shells, therefore greater the
2. (c) In iso-electronic species, cation with nuclear charge smaller will be the size i.e.,
greater positive charge will have a smaller radius O– – > F–
and anion with greater negative charge will have further Li+ and B3+ are isoelectronic, therefore
the largest radius. Li+ > B3+
Thus, the order of ionic radii will be, Hence the correct order of atomic size is.
N3– > O2– > F– > Na+ O-- > F– > Li+ > B3+
3. (c) Elements (a), (b) and (d) belong to the same 9. (a) Ionisation potential of nitrogen is more than
group since each one of them has two electrons that of oxygen. This is because nitrogen has
in the s sub shell. In contrast, element (c) has more stable half-filled p-orbitals. (N = 1s2, 2s2,
seven electrons in the valence shell and hence 2p3, O = 1s2, 2s2, 2p4)
does not lie in the same group in which elements 10. (a) In Cu it has completely filled d-orbital so
(a), (b) and (d) lie. highest energy is absorbed when it convert in
4. (c) atomic number 9 is for F so its halogen Cu+ ion.
series. 11. (b) K+ ® K2+ + e–. Since e– is to be removed
5. (a) There are four elements which is lighter from stable configuration.
than the rare–earth elements that are: 12. (b) Along the period, I.P. generally increases
(i) eka – boron (Eb) – scandium but not regularly. Be and B are exceptions. First
(ii) eka – aluminium (Ea) – Gallium I.P. increases in moving from left to right in a
(iii) eka – manganese (Em) – Technetium period, but I.P. of B is lower than Be.
(iv) eka – Silicon (Es) – Germanium 13. (b) IE2 of Mg is lower than that of Na because
6. (b) The atomic number 85 lies in the sixth period in case of Mg+, 3s-electron has to be removed
and since the next halogen, if discovered, will lie whereas in case of Na+, an electron is removed
in the 7th period. Hence, its atomic number must from the stable inert gas configuration which is
be 85+32=117. difficult.

32
14. (b) In case of Ne, the electron is being removed 19. (a) (i) < (iii) < (ii) < (iv). In case of half filled or
from a species with a charge of +1 whereas in case completely filled subshell, not easy to add elec-
of Na+, the electron is being removed from a species tron so (i) & (iii) has less tendency to accept
with charge of + 2. Hence IE1 of Na+ > IE1 of Ne. electron. Thus option (a) is correct.
15. (a) Zero, because of the stable electronic 20. (c) The basic character of metal oxides
configuration the noble gases do not show any decreases from left to right in a period and
force of attraction towards the incoming electron. increases down the group.
16. (a) Acidic character of oxide µ Non-metallic 21. (106) Unh = Un – nil – hexium = 106
nature of element. 22. (731) The I.E. of Ag will be less than Cu, due
Non-metallic character increases along the to bigger size of Ag. From Ag to Au, 14f
period. Hence order of acidic character is electrons are added, which provides very poor
Cl2O7 > SO2 > P4O10. shielding effect. Therefore, due to high nuclear
–
17. (a) O ion exerts a force of repulsion on the charge, the I.E. of Au > Ag. Correct order: Au
incoming electron. The energy is required to (890) > Cu (745) > Ag (731).
overcome it. 23. (7) Long form of periodic table contains 18
18. (c) Basicity of oxides decreases in a period and groups and 7 periods (completely filled)
increases in a group. 24. (7) Third period contains total 8 elements but
\ SnO2, Al2O3 and ZnO are amphoteric oxides. ‘Si’ is metalloid.
25. (2) (iv) Li < Li+ (vii) Ba < Sr

33
 ELEMENTS OF GROUP
13,14 ,15 ( P BLOCK ELEMENTS)

R.T.
1. H3BO3 on heating up to 373 K yields 6. BX3 + NH3 ¾¾¾
® BX3.NH3 + Heat of
(a) boric anhydride adduct formation (DH)
(b) orthoboric acid The numerical value of DH is found to be
(c) metaboric acid maximum for :
(d) tetraboric acid (a) BF3
2. Aluminium chloride exists as dimer, (Al2Cl6) in (b) BCl3
solid state as well as in solution of non-polar (c) BBr3
solvents such as benzene. When dissolved in (d) BI3
water, it gives
(a) [Al(OH) 6 ]3- + 3HCl
7. When aluminium is heated in atomoshere of
(b) [ Al( H 2 O ) 6 ]3+ + 3Cl - nitrogen it forms :
(c) Al3+ + 3Cl - (a) AlN (b) Al2N
(d) Al2 O3 + 6HCl (c) Al3N (d) Al2N3
3. In reaction 8. Diborane is prepared on large scale by
BF3 + 3LiBH4 ® 3LiF + X ; X is (a)
450 K
2BF3 (g) + 6LiH(s) ¾¾¾®
(a) B4H10 (b) B2H6
(c) BH3 (d) B3H8 B2 H6 (g) + 6LiF(s)
4. The role of fluorspar ( CaF2) which is added in
450 K
small quantities in the electrolytic reduction of (b) 2BCI3 (g) + 6LiH(s) ¾¾¾®
alumina dissolved in fused cryolite (Na3AlF6) is B2 H 6 (g) + 6LiCl(s)
(a) as a catalyst
450 K
(b) to make the fused mixture very conducting (c) 2BF3 (g) + 6NaH ¾¾¾® B2 H 6 + 6NaF
(c) to increase the temperature of the melt.
450 K
(d) to decrease the rate of oxidation of carbon (d) 2BCl3 + 6NaH ¾¾¾® B2 H 6 + 6NaCl
at the anode.
5. The dissolution of Al(OH)3 by a solution of 9. Silicon dioxide is formed by the reaction of
NaOH results in the formation of (a) SiCl4 + H2O
(b) SiO2 + HF
(a) [Al(H 2 O) 4 (OH )]2 + (c) SiO2 + NaOH
(d) SiCl4 + NaOH
(b) [Al(H 2 O) 2 (OH) 4 ]-
10. SiF4 gets hydrolysed giving........
(c) [Al(H 2O)3 (OH )3 ] (a) SiO2 (b) Si(OH)2F2
(c) H2SiF6 (d) Si(OH)4
(d) [Al(H 2 O) 6 (OH) 3 ]

34
11. Soldiers of Napolean army while at alps during 17. The gas evolved on heating CaF2 and SiO2
freezing winter suffered a serious problem as with concentrated H2SO4, on hydrolysis gives
regards to the tin buttons of their uniforms. a white gelatinous precipitate. The precipitate
White metallic tin buttons got converted to grey is
powder. This transformation is related to (a) hydrofluorosilicic acid
(a) a change in the partial pressure of oxygen (b) silica gel
in the air (c) silicic acid
(b) a change in the crystalline structure of tin (d) calciumfluorosilicate
(c) an interaction with nitrogen of the air at 18. On heating Pb(NO3)2, the products formed are:
very low temperatures (a) PbO, N2, O2 (b) Pb (NO2)2, O2
(d) an interaction with water vapours contained (c) PbO, NO2, O2 (d) Pb, N2, O2
in the humid air 19. The product of the following reaction are:
12. The tendency of X in BX3 (X = F, Cl, OMe, NMe) D
SiO2 + C ¾¾® Pr oducts
to form a p - bond with boron follows the order
(a) SiC and CO2 (b) SiO and CO
(a) BCl3 < BF3 < B(OMe)3 < B(NMe2)3
(c) SiC and CO (d) Si and CO
(b) BF3 < BCl3 < B(OMe)3 < B(NMe2)3
(c) BCl3 < B(NMe2)3 < B(OMe)3 < BF3 20. What is not correct about carbon monoxide ?
(d) BCl3 < BF3 < B(NMe2)3 < B(OMe)3 (a) Carbon in CO is sp hybridised and is linear
13. PbO2 is obtained from molecule
(a) the reaction of PbO with HCl (b) CO is a ligand because it has a lone pair of
(b) thermal decomposition of Pb(NO3 )2 at electrons on the carbon atom
200 °C (c) CO is the reducing agent in metallurgy of
(c) the reaction of Pb3O4 with HNO3 iron
(d) the reaction of Pb with air at room (d) CO has the structure C = O
temperature
14. An allotrope of carbon which exhibits only two
types of C - C bond distance of 143.5 pm and
138.3 pm, is
(a) charcoal (b) graphite
(c) diamond (d) fullerene
15. A solid element (symbol Y) conducts electricity
and forms two chlorides YCln (colourless

volatile liquid) and YCl n - 2 (a colourless solid).

To which one of the following groups of the
periodic table does Y belong?
(a) 13 (b) 14
(c) 15 (d) 16
16. The reducing power of divalent species
decreases in the order
(a) Ge > Sn > Pb
(b) Sn > Ge > Pb
(c) Pb > Sn > Ge
(d) None of these

35
 Numeric Value Answer
21. In aluminates, the coordination number of Al is
22. How many oxides of the following are non-
amphoteric in nature?
CO2, SiO2, SnO2 and CaO
23. How many orbitals of boron are involved in
hybridisation in B2H6?
24. In a molecule of C60 Buckminsterfullerene, what
is the sum of six-membered and five-membered
rings?
25. What is the sum for the molecular masses of
constituents of producer gas?

ANSWER KEY
1 (c) 4 (b) 7 (a) 10 (d) 13 (c) 16 (a) 19 (c) 22 (3) 25 (56)
2 (b) 5 (b) 8 (a) 11 (b) 14 (d) 17 (d) 20 (d) 23 (4)
3 (b) 6 (d) 9 (a) 12 (a) 15 (b) 18 (c) 21 (6) 24 (32)

36
 Hints & Solutions

1. (c) H3BO3 on heating at 373K yields metaboric Although transitions of white to grey tin occurs
acid (HBO2) at any temperature below 15.2°C, it becomes rapid
only at –50°C, unless a catalyst is present. During
373K
H3BO3 ¾¾¾® HBO2 + H2O the conversion of white tin to grey tin (in cold
D
metaboric acid countries) volume increases. Grey Sn is very
(orthorombic form)
brittle easily crumbles down to powder. This
2. (b) Al2Cl6 + 12H2O 2[Al(H2O)6]3+ + 6Cl– phenomenon is called tin diseases, tin past or
tin plague.
3. (b)
12. (a) Lesser electronegativity of X and similar
4. (b) CaF2 when added to fused cryolite, lowers size of valence shell of X and B favours back
the m.p. and increases the conductivity. bonding.
5. (b) Al(OH)3 + OH - ® [Al(OH) 4 ]- Cl and F are more electronegative than
OMe and NMe group and Cl have large size of
3p-orbital.
[Al(OH) 4 (H 2 O) 2 ]-
2H O
¾¾¾®
2
Among B(OMe)3 and B(NMe2)3, N in NMe is
6. (d) Lewis acidic strength : BF3 < BCl3 < BBr3 < BI3 less electronegative than O in OMe group. Thus,
As BI3 is strongest lewis acid among all boron the tendency to form p-bond with boron follows
halides therefore, heat of adduct formation will the order.
the maximum numerically, for BI3. BCl3 < BF3 < B(OMe)3 < B(NMe2)3.
13. (c) Pb3O4 + 4HNO3 ®
7. (a) 2Al + N 2 ¾¾ D
® 2AlN 2Pb(NO3)2 + PbO2 + 2H2O
8. (a) 14. (d) Fullerene contains both single and double
9. (a) bond with C-C at a distance of 143.5 pm and
D 138.3 pm.
SiCl 4 ( s) + 2H 2O(l) ¾¾¾¾ ® Si(OH) 4 ( aq)
-4HCl
Silicic acid 15. (b) SnCl4 is colourless volatile liquid and SnCl2
D
¾¾® SiO 2 .xH2O( s) is colourless solid Sn conducts electricity and it
Silica gel belongs to 14 group.
10. (d) It is hydrolysed with water to form a Si(OH)4. 16. (a) The stability of +2O.S. follows the order
15.2°C 164°C Pb 2 + > Sn 2 + > Ge2 +
ˆˆˆˆˆ†
11. (b) a-tin ‡ˆˆˆˆ ˆˆˆˆˆ
†
ˆ b-Sn ‡ˆˆˆˆ
ˆ
(Grey) Hence reducing power Ge > Sn > Pb
(White)
(most common and stable) 17. (d) 2CaF2 + SiO 2 + H 2SO 4 ¾¾
®
232°C
ˆˆˆˆˆ†
g -Sn ‡ˆˆˆˆˆ Liquid tin hydrolysis
(Brittle)
SiF4 + H 2O + CaSO4 ¾¾¾¾¾ ® CaSiF6
(Rhombic)

37
 D 1 22. (3) CO2, SiO2 acidic CaO basic and SnO2
18. (c) Pb(NO3 )2 ¾¾ ® PbO + 2NO2 + O 2
2 amphoteric.
19. (c) SiO2 + 3C ¾¾
® SiC + 2CO
¬
23. (4) Boron in B2H6 is sp3 hybridised and hence
20. (d) CO molecule is linear (C = O) and it is four orbitals are involved.
supposed that carbon atom in it is sp-hybridised. 24. (32) It contains 20 six-membered rings and 12
CO is electron deficient molecule and has p five-membered rings.
acceptor properties. Due to presence of pair of
Total no. of rings = 20 + 12 = 32
electrons, it acts as ligand or Lewis base. In
metallurgy it is used as reducing agent. 25. (56) Producer gas is CO + N2.
21. (6) In aqueous solution the probable aluminate Sum of molecular mass = (16 + 12) + (14 + 14)
species is [Al(H2O)2(OH)4], hence, co-ordination = 56
number of Al is 6.

38
 CHEMICAL EQUILIBRIUM

1. For the synthesis of ammonia by the reaction 3. K1 and K2 are equilibrium constant for reactions
ˆˆ† 2NH in the Haber process, the
N2 + 3H2 ‡ˆˆ (i) and (ii)
3
ˆˆ† 2 NO (g)
N2(g) + O2 (g) ‡ˆˆ ...(i)
attainment of equilibrium is correctly predicted
by the curve 1 1
ˆˆ†
NO(g) ‡ˆˆ N 2 (g) + O 2 (g) ...(ii)
2 2
Then,
concentration
Molar

H2 2
æ ö
(a) N2 (a) K1 = ç 1 ÷ (b) K1 = K22
çK ÷
NH3 è 2ø

time 1
(c) K1 = (d) K1 = (K2)0
K2
concentration
Molar

H2 4. PCl5 is dissociating 50% at 250°C at a total

(b) N2 pressure of P atm. If equilibrium constant is Kp,
NH3 then which of the following relation is numerically
correct –
time
(a) Kp = 3P (b) P = 3Kp
concentration

NH3 2 KP 2P
Molar

(c) P = (d) Kp =
N2 3 3
(c)
5. 1.0 mole of AB5 (g) is placed in a closed
H2
container under one atmosphere and at 300K. It
time
is heated to 600K, when 20% by mass of it
dissociates as
AB5 (g) ¾
¾® AB(g) + 2 B2 (g).
concentration

NH3
Molar

H2 The resultant pressure is

(d) (a) 1.2 atm (b) 2.4 atm
N2 (c) 1.4 atm (d) 2.8 atm
time 6. For the reaction C(s) + CO 2(g) ® 2CO(g),
2. Two moles of PCl5 were heated in a closed vessel Kp = 63 atm at 1000 K. If at equilibrium : PCO = 10
of 2L. At equilibrium 40% of PCl5 is dissociated PCO2, then the total pressure of the gases at
into PCl3 and Cl2. The value of equilibrium equilibrium is
constant is (a) 6.3 atm (b) 6.93 atm
(a) 0.53 (b) 0.267 (c) 0.63 atm (d) 0.693 atm
(c) 2.63 (d) 5.3

39
7. The value of Kp for the equilibrium reaction the favourable conditions are
N 2 O4 (g) ƒ 2NO2 (g) is 2. (a) low temperature, low pressure and catalyst
(b) low temperature, high pressure and catalyst
The percentage dissociation of N2O4(g) at a
(c) high temperature, low pressure and catalyst
pressure of 0.5 atm is
(d) high temperature, high pressure and catalyst
(a) 25 (b) 88
13. For the reaction
(c) 50 (d) 71
8. For the decomposition of the compound, ˆˆ† XO (s ) + CO 2 ( g ) ,
XCO3 ( s ) ‡ˆˆ
represented as
Kp = 1.642 atm at 727°C. If 4 moles of XCO3(s)
NH2COONH4(s) ƒ2NH3(g) + CO2(g)
was put into a 50 litre container and heated to
the Kp = 2.9 × 10–5 atm3. If the reaction is started
727°C. What mole percent of the XCO3 remains
with 1 mol of the compound, the total pressure at
unreacted at equilibrium?
equilibrium would be :
(a) 20
(a) 1.94 × 10–2 atm (b) 5.82 × 10–2 atm
(b) 25
(c) 7.66 × 10–2 atm (d) 38.8 × 10–2 atm
(c) 50
9. Air containing 79% of nitrogen and 21% of oxy-
(d) None of these
gen by volume is heated at 2200 K and 1 atm
until equilibrium is established according to the
14. The figure shows the change in concentration
reaction
of species A and B as a function of time.
ˆˆ† 2NO(g)
N2(g) + O2(g) ‡ˆˆ
The equilibrium constant Kc for the reaction
If the KP of the reaction is 1.1 × 10–3, calculate
the amount of nitric oxide produced in terms of
volume percent.
(a) 1.67 % (b) 1.23 % 0.4 M B
(c) 1.33 % (d) 1.54%
0.3 M
10. At a certain temperature and 2 atm pressure
Concentration

equilibrium constant (KP) is 25 for the reaction

0.2 M
ˆˆ† SO3 ( g ) + NO ( g )
SO2 ( g ) + NO 2 ( g ) ‡ˆˆ
0.1 M A
Initially if we take 2 moles of each of the four
gases and 2 moles of inert gas, what would be
Time
the equilibrium partial pressure of NO2?
(a) 1.33 atm
(b) 0.1665 atm
(c) 0.133 atm ˆˆ† 2B ( g ) is :
A ( g ) ‡ˆˆ
(d) None of these (a) Kc > 1 (b) K<1
11. The equilibrium constant for a reaction, (c) K = 1 (d) data insufficient
ˆˆ† 2NO(g) is 4 × 10–4 at 2000
N2(g) + O2(g) ‡ˆˆ 15. The degree of dissociation of acetic acid in a 0.1
K. In the presence of catalyst, the equilibrium is M solution is 1.32 × 10 –2 . Find out the
attained 10 times faster. The equilibrium constant dissociation constant of the acid.
in presence of catalyst at 2000 K is : (a) 1.50 × 10–4 (b) 1.80 × 10–16
(a) 10 × 10–4 (b) 4 × 10–2 (c) 1.76 × 10 –5 (d) 1.2 × 10–3
(c) 4 × 10 –4 (d) 40 × 10–4
12. For the manufacture of ammonia by the reaction
ˆˆ† 2NH 3 + 2 kcal
N 2 + 3H 2 ‡ˆˆ
40
16. At 25° C, the solubility product of Hg2Cl2 in Numeric Value Answer
water is 3.2 × 10–17 mol3 dm–9. What is the
21. In the reaction PCl5 ƒ PCl3 + Cl2, the amount of
solubility of Hg2Cl2 in water at 25° C?
each PCl5, PCl3 and Cl2 is 2 mole at equilibrium and
(a) 1.2 × 10–12 M (b) 3.0 × 10–6 M
total pressure is 3 atm. What will be the value of Kp?
(c) 2 × 10–6 M (d) 1.2 × 10–16 M
22. For the reaction : SnO2(s)+2H2(g) ƒ
17. Solid AgNO3 is slowly added to a solution
2H2O(g) + Sn(s)
containing each of 0.01 M NaCl and 0.001 M NaBr.
The value of 2 × KP at 900 K where the equilibrium
What will be the concentration of Cl– ions in
steam hydrogen mixture was 45% H2 by volume is
solution when AgBr will just start to precipitate?
23. For a reaction X + Y ƒ 2Z, 1.0 mol of X, 1.5 mol
Ksp (AgBr) = 3.6 × 10–13, Ksp (AgCl) = 1.8 × 10–10.
(a) 1.8 × 10–7 (b) 3.6 × 10–10 of Y and 0.5 mol of Z were taken in a 1 L vessel and
(c) 0.01 (d) 2 × 10–4 allowed to react. At equilibrium, the concentration
18. A buffered solution is prepared by mixing equal of Z was 1.0 mol L–1. The equilibrium constant of
volumes of x
the reaction is . The value of x is _________.
(a) 0.2 M NH4OH and 0.1 M HCl 15
24. A soft drink was bottled with a partial prssure
(b) 0.2 M NH4OH and 0.2 M HCl
of CO 2 of 3 bar over the liquid at room
(c) 0.2 M NaOH and 0.1 M CH3COOH
(d) 0.1 M NH4OH and 0.2 M HCl temperature. The partial pressure of CO2 over
the solution approaches a value of 30 bar when
19. Among the following, the correct statement is: 44g of CO2 is dissolved in 1 kg of water at room
(a) pH decreases when solid ammonium temperature. The approximate pH of the soft
chloride is added to a dilute aqueous drink is ______ × 10–1.
solution of NH3 (First dissociation constant of
(b) pH decreases when solid sodium acetate is H2CO3 = 4.0 × 10–7; log 2 = 0.3; density of the
added to a dilute aqueous solution of acetic soft drink = 1g mL–1)
acid
(c) pH decreases when solid NaCl is added to
a dilute aqueous solution of NaOH
(d) pH decreases when solid sodium oxalate is
added to a dilute aqueous solution of oxalic
acid
20. Solubility products of CuI and Ag2CrO4 have
almost the same value (~ 4 ´ 10-12). The ratio of
solubilities of the two salts (CuI:Ag2CrO4) is
closest to
(a) 0.01 (b) 0.02
(c) 0.03 (d) 0.10

41
25. If the solubility product of 28. Calculate the pOH of a solution at 25°C that
–11 3
AB2 is 3.20 × 10 M , then the solubility of AB2 contains 1× 10– 10 M of hydronium ions, i.e.
in pure water is ______ × 10–4 mol L–1. H3O+.
[Assuming that neither kind of ion reacts with 29. Calculate pH of a resultant solution of 25 mL of
water] 0.1 M HCl, 50 mL of 0.02 M HNO3 and 25 mL of
26. Calculate the pH at the equivalence point when a 0.1 M NaOH.
solution of 0.01 M CH3COOH is titrated with a 30. 0.1 M NaOH is titrated with 0.1 M HA till the end
solution of 0.01 M NaOH. pKa of CH3COOH is 4.74. point; Ka for HA is 5.6 × 10–6 and degree of
27. A buffer solution is prepared by mixing 0.1 M hydrolysis is less compared to 1. Calculate pH
ammonia and 1.0 M ammonium chloride. At 298 K, of the resulting solution at the end point.
the pKb of NH4OH is 5.0. The pH of the buffer is

ANSWER KEY
1 (a) 4 (b) 7 (d) 10 (c) 13 (d) 16 (c) 19 (a) 22 (3) 25 (2.0) 28 (4)
2 (b) 5 (d) 8 (b) 11 (c) 14 (a) 17 (c) 20 (b) 23 (16) 26 (8.22) 29 (2)
3 (a) 6 (b) 9 (c) 12 (b) 15 (c) 18 (a) 21 (1) 24 (3) 27 (8) 30 (8.98)

42
 Hints & Solutions

1. (a) 5. (d) AB5 (g) AB(g) + 2 B2 (g)

2. ˆˆ† PCl3 + Cl2
(b) PCl5 ‡ˆˆ 1–a a 2a
a (1- x ) ax ax Total moles at equilibrium = 1 + 2 a
a = 2, x = 0.4, V = 2 L
20 ´ 2
2 (1 - 0.4 ) = 1+ = 1.4
\ [ PCl5 ] = = 0.6 mol L-1 100
2
2 ´ 0.4 1´ 300
[ PCl3 ] = [Cl2 ] = 2 = 0.4 mol L-1 P1 n1T1
= ;
1
=
P2 n 2T2 P2 1.4 ´ 600
0.4 ´ 0.4
\ Kc = = 0.267
0.6 \ P2 = 2.8 atm
3. (a) For reation (i) 6. (b) C(s) + CO2(g) ¾® 2CO(g)
Apply law of mass action,
[NO]2
K1 = 2
[N 2 ][O2 ] (PCO ) 2 (10PCO2 )
KP = or 63 =
PCO2 PCO2
and for reaction (ii)

[N 2 ]½ [O 2 ]½ 1 (Given KP = 63 and PCO = 10PCO 2 )

K2 = ; \ K1 = 2
[NO] K2
100(PCO2 )2
4. (b) PCl5 ƒ PCl3 + Cl2 or 63 = or 63 = 100 PCO2
PCO2
Moles at equilibrium
1 1 1
2 2 2 63
PCO2 = = 0.63 atm
Mole fraction at equilibrium 100
1 1 1
3 3 3 PCO = 10PCO 2 = 10 × 0.63 = 6.3 atm
Partial pressure at equilibrium
Ptotal = PCO + PCO = 0.63 + 6.3 = 6.93 atm
P P P 2
3 3 3
7. (d) ˆˆ† 2NO 2 (g)
N 2 O 4 (g) ‡ˆˆ
P P
´ Initial moles 1 0
\ Kp = 3 3=P
P/3 3 Moles at eqm. (1 – a) 2a
(a = degree of dissociation)

43
 Total number of moles at equil.
= (1 – a) + 2a -5 4 P3
\ 2.9 ´ 10 =
= (1 + a) 27

(1 – a ) 2.9 ´ 10 -5 ´ 27
PN 2O 4 = ´P P3 =
(1 + a ) 4

2a 1
PNO 2 = ×P æ 2.9 ´ 10 -5 ´ 27 ö 3
(1 + a ) P=ç ÷
ç ÷ = 5.82 × 10–2 atm
è 4 ø
2
æ 2a ö 9. (c) N2(g) + O2(g) ‡ˆˆ ˆˆ† 2NO(g)
ç ×P÷
2 2
(PNO2 ) (1+ a) ø = 4a P
KP = =è At equilibrium, we have [N2] = 0.79 (1 – a)
PN 2O4 æ 1– a ö 1 – a2 [O2] = 0.21 (1 – a), [NO] = 2a
ç ÷´ P
è 1+ a ø Total no. of moles
= 0.79 (1 – a) + 0.21 (1 – a) + 2a = 1 + a
Given, KP = 2, P = 0.5 atm
0.79 (1 - a) 0.21(1- a)
2 PN 2 = × 1; PO 2 = ×1
4a P 1+ a 1+ a
\ KP =
1 – a2
2a
PNO = .1
1+ a
4a 2 ´ 0.5
2=
1– a 2 2
PNO 4a 2
Kp = P .P = = 1.1 × 10–3
a = 0.707 » 0.71 N 2 O2 0.79 ´ 0.21(1 - a) 2
\ Percentage dissociation
a = 0.0067 vol % of NO = 1.33
= 0.71 × 100 = 71
10. (c)
8. (b) ˆˆ†
NH 2 COONH 4 (s) ‡ˆˆ
ˆˆ† SO3 ( g ) + NO ( g )
SO2 ( g ) + NO2 ( g ) ‡ˆˆ
2NH3 (g) + CO 2 (g)
Initial moles 2 2 2 2
at eqm. 2– x 2– x 2+x 2+x
( PNH ) × ( PCO )
2

( ) ×(PCO ) (Q Qp < K p )
3 2 2
KP = = PNH3
PNH 2COONH 4 (s) 2

Total no. of moles of gases at equilibrium

As evident by the reaction, NH3 and CO2 are = 8 + 2 = 10
formed in molar ratio of 2 : 1. Thus if P is the
total pressure of the system at equilibrium, then PSO3 × PNO
Kp =
2×P 1× P PSO 2 × PNO 2
PNH3 = ; PCO 2 =
3 3
2
æ2+x ö
2 ç ´P÷
æ 2P ö P 4 P3 Þ è 10 ø
KP = ç ÷ × = 25 = 2
è 3 ø 3 27 æ2-x ö
ç ´P÷
Given KP = 2.9 × 10–5 è 10 ø

44
 5=
2+x 16. (c) ® Hg 2 2 + + 2Cl -
Here Hg 2Cl 2 ¾¾
Þ
2-x
2
Þ x = 1.33 Ksp = éHg 22 + ù éCl - ù = s ´ (2s) 2 = 4s3
ë ûë û
2–x
Partial Pressure of NO2 = ´ Ptotal 4s3 = 3.2 × 10–17
10
32
Þ s3 = ´ 10 -18 Þ s3 = 8 × 10–18
0.666 4
= ´ 2 = 0.133 atm
10
\ s = 2 × 10–6 M
11. (c) Catalyst only changes time to achieve 17. (c) Ksp (AgBr) < Ksp (AgCl)
equilibrium, it does not affect the value of Therefore, AgBr will precipitate first and at that
equilibrium constant. time all Cl– will be present.
12. (b) The most favourable conditions are : 18. (a) Buffer solution can be prepared by mixing
(i) high pressure (Dn < 0) equal volumes of 0.2 M NH4OH (weak base)
(ii) low temperature (Exothermic reaction) and 0.1 M HCl (strong acid). It results in the
(iii) catalyst Fe in presence of Mo. formation of NH4OH (weak base) + NH4Cl (salt
13. (d) Moles of CO2 present at equilibrium of weak base NH4OH), which is basic buffer
1.642 ´ 50 mixture.
= =1 19. (a) Dil.aqueous solutions of NH3 is NH4OH.
0.0821 ´ 1000
Mole % of XCO3 decomposed ˆˆ† NH4+ + OH -
NH4OH ‡ˆˆ
1 On adding solid ammonium chloride, the
= ´ 100 = 25%
4 reaction moves backward due to common ion
Hence, 75% remains undecomposed. effect. The concentration of OH– decreases and,
14. (a) From graph, [A]eq = 0.1 M, [B]eq = 0.4 M hence, the pH decreases.
20. (b) Ksp(CuI) = 4 × 10–12

Kc =
[ B]2 = 1.6 Ksp (Ag2CrO4) = 4 × 10–12

[ A ]1 CuI(s) ® Cu + (aq.) + I + (aq.)

s1 s2
15. (c) ˆˆ† CH COO– + H+
CH3COOH ‡ˆˆ 3
0.1 0 0
K sp = s1 ´ s1
1
Initial concentration
Þ 4 × 10–12 = s12
0.1(1 – 0.0132) 0.1 × 0.0132 0.1 × 0.0132 s1 = 2 × 10–6 mol/L
at eqb. Ksp(Ag2CrO4) = 4 × 10–12
[CH 3COO - ] [H + ] Ag2CrO4 ® 2Ag + + CrO24 +
Ka =
[CH3COOH] 2's 2 ' s2

0.1 ´ 0.0132 ´ 0.1 ´ 0.0132 K sp = (2s )2(s )

= = 1.76 × 10–5 2 2 2
0.1(1 – 0.0132)
4 × 10–12 = 4s23
s23 = 10–12

45
 Þ s2 = 10–4 mol/L
X + Y ˆˆ†
‡ˆˆ 2Z
Solubility of CuI s1
0.75 1.25 1
Solubility of Ag 2CrO 4
= s2
2 ´ 10-6 [Z]2 1 x
K eq = = =
= = 2 × 10–2 = 0.02 [X][Y] 0.75 ´ [1.25] 15
10-4
21. (1) PCl5 ƒ PCl3 + Cl2
15
Initial mole 4 0 0 Þx= = 16
Mole at 4 – 2 = 2 2 2
(0.75 ´1.25)
equilibrium
Total mole of equilibrium = 2 + 2 + 2 = 6 mole 24. (3) CO 2 + H 2 O ¾¾ ® H 2 CO3
and total Pressure (P) = 3 atm 30 bar . . . . . . . . . . 1 mol/L
3 bar . . . . . . . . . 0.1 mol/L
PPCl3 PCl2
KP =
PPCl5 ˆˆ† H + + HCO3–
H 2 CO3 ‡ˆˆ
t=0 0.1 0 0
Partial pressure = mole fraction × total pressure at Equb. 0.1(1– α) 0.1α 0.1α
mole of element present at equilibrium
= ´ total pressure 0.1a 2
total mole at equilibrium 4.0 ´10-7 =
1- a
2 2
(PPCl3 ) = ´ 3 = 1 ; (PCl2 ) = ´ 3 = 1 Þ (1 - a ) = 1
6 6
a 2 = 4 ´ 10-6 Þ a = 2 ´ 10-3
2 1´ 1
(PPCl5 ) = ´ 3 = 1 ; K p = = 1atm
6 1 [H + ] = 2 ´ 10-4 M

(PH2O ) 2 pH = 4 ´ log 2 = 3.7 ; 37 ´10-1

22. (3) KP = 25. (2.0)
(PH2 )2
ˆˆ† A 2+ (aq) + 2B- (aq)
AB2 ‡ˆˆ
Given H2 is 45% by volume at constant s 2s
temperature in closed vessel (P µ V).
Ksp = 4s3 = 3.2 ´10-11
So PH2O = 0.55 and PH2 = 0.45

æ 0.55 ö
2 Þ s3 = 8 ´ 10 -12
KP = ç ÷ = 1.5
è 0.45 ø Þ s = 2 ´ 10 -4
Þ 2Kp = 1.5 × 2 = 3 26. (8.22)
23. (16)
ˆˆ† CH COONa + H O
CH3COOH + NaOH ‡ˆˆ 3 2

X + Y ˆˆ† 2 Z
‡ˆˆ Let acid be = V mL
t =0 1 mol 1.5 mol 0.5 mol V mL of 0.01 M CH3COOH will require V mL of
0.01 M NaOH. But CH3COONa formed will make
t = teq 1– x 1.5 – x 0.5 + 2x
solution alkaline due to hydrolysis.
0.5 + 2x = 1; x = 0.25
46
 28. (4) Given [H3O+] = 1 × 10–10 M
ˆˆ† CH COOH + NaOH
CH3COONa + H2O ‡ˆˆ 3 at 25º C [H3O+] [OH–] = 10–14
0.01
[CH3COONa] = = 0.005 M 10-14
2 \ [OH–] = -10
= 10-4
Using equation for pH of salt of weak acid and 10
strong base.
pK logC 4.74 log 0.005 Now, [OH - ] = 10- pOH = 10-4 = 10-pOH
pH = 7 + a + =7+ +
2 2 2 2 \ pOH = 4
= 8.22 29. (2)
27. (8) The chemical reaction of NH4OH (NH3) and H+ + OH - ¾¾
® H 2O
HCl follows the eqn: NH4OH + HCl ® NH4cl + H2O ( 2.5 + 1) m mole ( 2.5) m mole
Henderson Hasselbalch equation can be used
( 3.5 - 2.5)
to calculate the pOH of resulted basic buffer [ H+ ]Final = = 10-2 M
solutions. 25 + 50 + 25
pH = – log [H+] = – log (10–2) = 2
[salt ]
pOH = pKb + log base 30. (8.98) HA + NaOH ¾® NaA + H2O
[ ]
At the end point, the solution contains only NaA
[ NH4Cl] whose concentration is 0.1/2 = 0.05 M
= pKb + log NH OH Since the salt NaA is formed by strong alkali
[ 4 ]
(NaOH) and weak acid HA (indicated by its low
Ka value), its pH can be evaluated by the
[1.0]
= 5 + log 0.1 following relation.
[ ] 1
pH = (pK w + pK a + log C)
pOH = 6 2
pH + pOH = 14 1
= (14 + 5.2518 + ( -1.3010)] = 8.98
pH = 14 – 6 = 8.0 2

47
 BASIC PRINCIPLES OF ORGANIC CHEMISTRY
O
1. The IUPAC name of
NH2 COOH
(c)

O
COOH NH2
(a) o, o¢ – diamino – o, o¢ – dicarboxy biphenyl O
(b) 6, 6¢ – diamino diphenyl – 2, 2¢ –
dicarboxylic acid
(c) diamino dicarboxy biphenyl (d)
(d) none of these
2. The order of stability of the following tautomeric O
compounds is : 4. In the given conformation, if C2 is rotated about
OH O C2 – C3 bond anticlockwise by an angle of 120º
| ||
CH 2 = C - CH 2 - C - CH 3 then the conformation obtained is
4
I CH3
O O H H
|| ||
CH3 - C- CH 2 - C- CH 3
3
II 2
OH O H H
| ||
CH 3 - C = CH - C - CH 3 CH3
1
III (a) fully eclipsed conformation
(a) III > II > I (b) II > I > III (b) partially eclipsed conformation
(c) II > III > I (d) I > II > III (c) gauche conformation
3. Which of the following will show tautomerism ? (d) staggered conformation
5. Indicate whether each of the following pairs are
O identical or not?

(a) F

Br H F
O CH2Br
(I) H3C
H CH3
(b) O = =O F
H

H Cl
CH2CH3 H
Cl
(II) Cl
Cl
CH3 H CH3 CH CH
Cl 2 3

48
 CH3 CH3 (c) nitro groups donate electrons at meta
position
H Br Br H
(d) nitro groups withdraw electrons from ortho/
(III) CH H H CH3 para positions of the aromatic ring
3
11. CH 3 Br + Nu - ¾¾® CH 3 - Nu + Br -
Br Br
The decreasing order of the rate of the above
(a) I-enantiomers; II-diastereomers; III- reaction with nucleophiles (Nu–) A to D is
enantiomers [Nu– = (A) PhO–, (B) AcO–, (C) HO–, (D) CH3O–]
(b) I-identical; II-enantiomers; III-enantiomers (a) A > B > C > D
(c) I-enantiomers; II-diastereomers;III-identical (b) B > D > C > A
(d) I-enantiomers; II-identical; III-identical (c) D > C > A > B
6. Base strength of : (d) D > C > B > A
(A) H3CCH -2 , (B) H 2C = CH - and
12. In the below mentioned compounds the
(C) H - C º C - decreasing order of reactivity towards
electrophilic substitution is
is in the order of :
(a) (B) > (A) > (C) (b) (C) > (B) > (A)
(c) (A) > (C) > (B) (d) (A) > (B) > (C) (i) (ii)
7. Chlorine in vinyl chloride is less reactive because
OCH3 CH3
(a) sp2 - hybridised carbon has more acidic
character than sp3 - hybridised carbon
(b) C - Cl bond develops partial double bond
(iii) (iv)
character
(c) of resonance CF3
(d) All are correct (a) (iv) > (i) > (ii) > (iii)
8. Most stable carbocation is (b) (ii) > (iii) > (i) > (iv)
(a) p—NO2—C6H4—CH2+ (c) (iii) > (i) > (iv) > (ii)
(b) C6H5CH2+ (d) (i) > (ii) > (iii) > (iv)
(c) p—Cl—C6H4—CH2+ 13. The correct order of stability of the following
(d) p–CH3O—C6H4—CH2+ carbanions is
9. Rate of the reaction - –
(i) RCH 2 (ii)
O O –
R – C + Nu R – C + Z is fastest
Z Nu – –
(iii) (iv)
when Z is
(a) OC2H5 (b) NH2 (a) III > IV > I > II (b) I > II > III > IV
(c) Cl (d) OCOCH3 (c) I > III > II > IV (d) IV > III > II > I
10. The replacement of chlorine of chlorobenzene 14. Which of the following is not a resonance form
to give phenol requires drastic conditions, but of the enolate ion formed in the following acid
the chlorine of 2,4-dinitrochlorobenzene is base equilibrium?
O
readily replaced since,
(a) nitro groups make the aromatic ring electron CH 3
+ NaOH
rich at ortho/para positions
(b) nitro groups withdraw electrons from the O
meta position of the aromatic ring

49
 17.
O O– CH3 CH3 CH3
CH 3 CH 2 CH3O NO2

:
(a) (b)
O O H Cl CH3
on hydrolysis, in aqueous acetone will give
O– O–
(i)
CH 3 CH 3
(c) (d) CH3 CH3 CH 3
O O– NO2
CH3O
15. The structure drawn below has four nucleophilic
H OH CH3
sites, arrange them in order of decreasing
nucleophilicity. (ii)

2 CH3 CH3 CH 3
O O CH3O NO2
..
.. OH H CH3
– 1
OOC
3 (iii)
SO3– CH3 CH3 CH 3
4
CH3O NO2
(a) 3 > 4 > 1 > 2 (b) 4 > 3 > 2 > 1 H CH3 OH
(c) 4 > 3 > 1 > 2 (d) 3 > 4 > 2 > 1 (a) Mixture of (i) and (ii)
16. The major product of the following reaction is – (b) Mixture of (i) and (iii)
Me Br (c) Only (iii)
F (d) Only (i)
– +
¾¾¾¾¾¾¾¾
®
Ph S Na 18. H H H
dimethylformamide x z
NO2
y
Me SPh
Me SPh
H H
F
F Arrange the (C – H) bonds x, y and z in
(a) (b) decreasing order of their bond dissociation
energies in homolysis.
NO2
NO2 (a) y > x > z (b) z > x > y
Me Br (c) z > y > x (d) y > z > x
Me Br 19.
SPh
SPh
(c) (d) NH; N
,
NO2
NO2 O
(x) (y) (z)
The correct order of decreasing basic strengths
of x, y and z is:
(a) x > y > z (b) x > z > y
>x>z >z>x

50
 (c) y (d) y 23. X and Y
20. Arrange the following (w, x, y, z) in decreasing H Cl
H H3C H
Cl
order of their boiling points: Cl
H3C H CH3
CH3 Cl
N N X Y
OH O CH3 are
H
(a) enantiomers
(w) (x) (y) (z)
(b) diastereomers
(a) w > x > z > y (b) w > x > y > z
(c) constitutional isomers
(c) w > z > y > x (d) w > z > x > y
(d) conformers
21. Which of the following compounds has most
24. The higher stabilities of tert-butyl cation over
acidic hydrogen?
iso-propyl cation and trans-2- butene over propene,
respectively, are due to orbital interactions involving.
(a) O (a) s ® p and s ® p*
CH
O (b) s ® vacant p and s ® p
(c) s ® s* and s ® p
(d) s ® vacant p and s ® p*
(b) S
CH
S
H 25. The most acidic proton and the strongest, nu-
cleophilic nitrogen in the following compound
(c) N O
CH
N
b c
H N N CH3
a H H
(d) O N
CH H
N
respectively, are
H (a) Na – H; Nb (b) Nb – H; Nc
22. (c) Na – H; Nc (d) Nc – H; Na
+
O –H OH
26. The chlorine atom of the following compound
|| CH3 CH3 c
CH3— C — N CH3— C — N Cl
CH3 + CH3 d b
(I) (II) Cl Cl

OH O a
Cl
+ CH3 that reacts most readily with AgNO3 to give a
CH3— C N
CH3 precipitate is
(III)
(a) Cla (b) Clb
The correct stability order of the given canonical c
(c) Cl (d) Cld
structure is :
27. The lower stability of ethyl anion compared to
(a) I > II > III (b) III > I > II
methyl anion and the higher stability of ethyl
(c) I > III > II (d) II > III > I
radical compared to methyl radical, respectively,
are due to
(a) + I- effect of the methyl group in ethyl anion
s ® p-orbital conjugation in ethyl radical

51
 (b) – I - effect of the methyl group in ethyl
anion and s ® s* p-conjugation in ethyl
radical
(c) + I effect of the methyl group in both cases
(d) + I- effect of the methyl group in ethyl anion
and s ® s* conjugation in ethyl radical.

28. IUPAC name of the following compound

HO
is
(a) 1 -hydroxycyclohex-4-en-3-one
(b) 1 -hydroxycyclohex-3-en-5-one
(c) 3-hydroxycyclohex-5-en-1-one
(d) 5-hydroxycyclohex-2-en-1 one
29. The absolute configurations of the following
compounds
H CH2SH HO H
H3C CH2OH H3C CH2SH
respectively, are
(a) R and R (b) S and S
(c) R and S (d) S and R

a
30. O ,

b H
+
c ¾¾¾ ®
N
d
CH3

Identify the site, where attack of H+ is most

favourable.
(a) a (b) b
(c) c (d) d

ANSWER KEY
1 (b) 4 (c) 7 (c) 10 (d) 13 (a) 16 (a) 19 (b) 22 (b) 25 (b) 28 (d)
2 (a) 5 (c) 8 (d) 11 (c) 14 (b) 17 (a) 20 (d) 23 (d) 26 (a) 29 (d)
3 (a) 6 (d) 9 (c) 12 (d) 15 (c) 18 (b) 21 (b) 24 (d) 27 (a) 30 (a)

52
 Hints & Solutions

1. (b) It is biphenyl derivative 4. (c) Any conformation between two extreme

NH 2 COOH positions
5' 6' 2 3
i.e. eclipsed and staggered is known as Gauche
4' 4 or Skew form.
1' 1 C4
3' 2' 6 5 CH3
H
COOH NH 2 H H H3C H
2. (a) Enolic form predominates in compounds C3
H
60º C4 C3
containing two carbonyl groups separated by a C2
C2
– CH2 group. This is due to following two factors. H H
(i) Presence of conjugation which increases
stability. CH3 H3C H
C1 C1
(ii) Formation of intramolecular hydrogen
bond between enolic hydroxyl group and
second carbonyl group which leads to H
H
stablisation of the molecule.
H Hence the H H H
H
correct answer is III > C
II3> I. 60º 60º
O OH C2
C2 C
3
H H
3. (a) H3C
C4 CH3
C1
O O (Gauche conformation)
are tautomers.
a
F F
H
c CH3Br
5. (c) (I) Br H c
º H Me & b
Me
H CH3 F
a
H CH2Br
b

Enantiomer

53
 H C2H5 Cl H
Cl H
a b
(II) and
c Cl H Me Et Cl
Me
Configuration-R S S S-Configuration

diastereomers

Me Me Me
H Br Br H H Br
(III) and
Me H H Me Both are H Br
Identical
Br Br Me
Meso

+ +
6. (d) The amount of s-character in various hybrid CH2 CH2
orbitals is as follows.
sp = 50%, sp2 = 33% and sp3 = 25%
Therefore s-character of the C – H bond in
acetylene (sp) is greater than that of the C – H
bond in alkene (sp2 hybridized) which in turn NO2
NO2 intensifies Benzyl stable
has greater s character of the C–H bond than in due to resonance
+ve charge on benzyl cation
alkanes. Thus owing to a high s-character of the due to –I and –M effects
C – H bond in alkynes, the electrons constituting +
CH2 +
CH2
this bond are more strongly held by the carbon
nucleus with the result the hydrogen present on
such a carbon atom can be easily removed as
proton. The acidic nature of three types of C – H
bonds follows the following order Cl : OCH
.. 3
-C º C - H > - C = C - H > - C - C - H Cl intensifies +ve Positive charge of
charge on C benzyl cation is
Further, as we know that conjugate base of a due to –I effect more dispersed due
to +M effect of the
strong acid is a weak base, hence the correct –OCH3 group
order of basicity is 9. (c) Cl– is the best leaving group among the
- - - given option.
H - C º C < CH 2 = CH < CH 2 - CH3 10. (d) —NO2 group is electron attractive group,
.. -.. + so it is able to deactivate the benzene ring.
7. (c) CH2 = CH - Cl
.. « CH 2 - CH = Cl
: :
.. Cl
a double bond is formed between C and Cl. Hence NO2
it is less reactive due to resonance.
8. (d) The stability of carbonium ion is influenced
NO2
by both resonance and inductive effect.

54
 hence withdrawl of electrons from ortho and para 15. (c) 16. (a)
position cause easy removal of –Cl atom due to 17. (a) This is an example of S N 1 reaction
development of positive charge on o- and involving carbocation as intermediate.
p-positions.
H3C H CH3
11. (c) The stronger the acid, the weaker the
conjugate base formed. CH3O NO2
The acid character follows the order :
H Cl CH3
CH3COOH > C6H5OH > H2O > CH3OH
The basic character will follow the order
H3C H CH3
CH3COO– < C6H5O– < –OH < CH3O– hydride
shift
Hence, decreasing order of rate of given CH3O NO2
reactions with Nu– is D > C > A > B +
H CH3
12. (d) – OCH3 and – CH3 groups are activating
(A) 2° Carbocation
group while – CF3 is a deactivating group.

OCH3 CH3 CF3

H3C H CH3O
CH3O NO2
> > > +
H CH3
(i) (ii) (iii) (iv)
(B) 3° Carbocation; more stable;
(positive charge is dispersed
13. (a) due to +M effect of –OCH3)

– –
¬¾® ¬¾® This carbocation is especially stabilised
– ..
through resonance in which - O..
- CH3 group
–
–
acts as a good electron donor.
¬¾® ¬¾® ¬¾®
;
– H3C H CH3
aq .acetone
(A)¾¾¾¾¾® CH3O NO2
– (H 2O )
–
–
RCH 2 (I); (2°) H OH
CH3

14. (b) (a),(c) and (d) are resonating structures. (i)

O –
O H3C H CH3
CH3 CH 3 aq .acetone
(B)¾¾ ¾¾¾® CH3O NO2
( H 2O )

O O HO H CH3
O
(ii)
CH 3

–O
55
18. (b)
(z) ·
Highly unstable
(x) ·
Stable due to
E3 E hyper conjugation
2
H H (y)
x z
E1 · Stable due to
resonance +
y hyperconjugation
H
so bond dissociation enegy order is E1 < E2 < E3 i.e, (z) > (x) > (y)

19. (b) Increasing order of basic strength 24. (d) Tert-butyl cation is more stable than
isopropyl cation, because of better hyper
·· conjugation between s and vacant p-orbital.
N–H < N < N–H
··

·· H
O
delocalised l.p. sp2 -hybridised sp3-hybridised CH2
'N' l.p.
H3C C+
20. (d) B.P. µ extent of H bonding µ surface area
of molecule. CH2
Most acidic H
(Hyper-conjugation in tert-butyl carbocation)
H
Whereas, trans-2-butene is more stable than
21. (b) S propene because of hyper-conjugation between
C
S s and p*-orbitals.
empty 3 d orbitals H
– S
C + H+ HH
S H C
Stabilise by simple resonance C C
and 'd ' – orbital resonance. H H C H
22. (b) Structure III and I has complete octet for
all atoms III is more stable than I because 25. (b) H
O
N + > O + is the stability order..
b c
23. (d) H Cl N NCH3
a H H
H Cl N
H3C H
Cl H
H CH3 In the given compound most acidic proton will
H3C be Nb — H. This is because its conjugate base
CH3 Cl
(X) (Y) will be most stable and the most nucleophilic
nitrogen will be Nc, because the lone pair of
Both X and Y are conformers of each other, where
electrons present on this N is localised.
X is eclipsed and Y is staggered form.
56
26. (a) The reaction between haloalkane and 29. (d)
AgNO3 gives carbocation intermediate. So, H CH2SH HO H
more easily it will be formed, more readily it will
react to give precipitate. H3C CH2OH H3C CH2SH
In the given compound I II
c
Cl Cl
a Fischer projection of the above compounds are:
d d
(3)
b b
Cl Cl Cl Cl CH3
¾¾¾®
(1)
O a O + H
Cl a
CH2SH
Cl (4)
d b
Cl Cl CH2OH
¾¾¾® (2)
O I
+ So I should be 'R' but here, lower priority group
O being electronegative, will attract electron is on horizontal line. Therefore configuration will
density and cleave C–Cla bond density easily. be reversed i.e. correct configuration 'S'.
27. (a) The lower stability of ethyl anion (CH3CH2–) (3)
compared to methyl anion (CH3–) is because of + CH3
I-effect of methyl group of ethyl anion. The
(1) (4)
higher stability of ethyl radical compared to
HO H
methyl radical is due to s and p-orbital
conjugation is ethyl radical.
H CH2OH
H H (2)
C C ¬¾® H C CH2
II
H
II should be 'S', lower priority group is on
H H horizontal line i.e. 'R'
Hyper conjugation
in ethyl radical 30. (a)
O Me — N: O Me — N O
–

1 +
6 2
5 +d ––d
28. (d) 3 Me — N O
HO 4
5-Hydroxycyclohex-2-en-1-one Basic end
Me — N O—H
+ H+

57
 HYDROCARBON

1. On mixing a certain alkane with chlorine and 7. 1, 3-Butadiene when treated with Br 2 gives
irradiating it with ultraviolet light, it forms only (a) 1, 4-dibromo-2-butene
one monochloroalkane. This alkane could be (b) 1, 3-dibromo-2-butene
(a) pentane (b) isopentane (c) 3, 4-dibromo-1-butene
(c) neopentane (d) propane (d) 2, 3-dibromo-2-butene
2. cis-2-Butene has higher boiling point than the 8. Addition of Br 2 to trans-2-butene would give a
trans-analog. It is because of product which is
(a) hydrogen bonding in the cis-isomer (a) chiral (b) meso
(b) higher molecular mass of the cis-isomer (c) racemic (d) optically active
(c) van der Waal forces in the cis-isomer
9. Reaction of hydrogen bromide with propene in
(d) polarity in the cis-isomer.
the absence of peroxide is a/an
3. 2-Butene can be obtained by the electrolysis
(a) free radical addition
of an aqueous solution of
(b) nucleophilic addition
(a) 1, 2-Dimethylmaleic acid
(c) electrophilic substitution
(b) 2, 2-Dimethylbutandioic acid
(d) electrophilic addition
(c) 3, 3-Dimethylbutandioic acid
10. One mole of propanone and one mole of
(d) 2, 3-Dimethylbutandioic acid
formaldehyde are the products of ozonolysis of
4. The decreasing order of reactivity of hydrogen
one mole of an alkene. The alkene may be
bromide on the following alkenes is
(a) 2-methylpropene
CH2= CH2, CH3CH2CH = CH2, CH2= CHCl,
(b) 2, 2-dimethyl-1-butene
I II III
(c) propene
(CH3)2C = CH2
(d) 2-butene
IV
11. The compound shown below
(a) I > III > II > IV (b) IV > II > I >III O NO
2
(c) III > I > II > IV (d) II > IV > I > III
5. Which of the following reagents convert
propene to 1-propanol? can be readily prepared by Friedel-Craft’s
(a) H2O, H2SO4 reaction between
(b) Aqueous KOH (a) benzene and 2-nitrobenzoyl chloride
(c) MgSO4, NaBH4/H2O (b) benzyl chloride and nitrobenzene
(d) B2H6, H2O2, OH– (c) nitrobenzene and benzoyl chloride
6. When hydrochloric acid gas is treated with (d) benzene and 2-nitrobenzyl chloride
propene in presence of benzoyl peroxide, it gives CH2 – CH = CH2
(a) 2-Chloropropane 12.
(b) Allyl chloride
(c) n-Propyl chloride. on mercuration-demercuration produces the
(d) No reaction major product:

58
 CH2 – CH – CH3 + +
(a) +
OH (b) and

CH2 – CH2 – CH2 – OH – –

(b)
(c) and

CH2 – CH – CH2 +
(c) –
OH OH (d) and

CH2 – COOH
(d) CH3
|
16. Isopropene, CH 2 = C - CH = CH 2 is treated
with HCl, the products formed will be a mixture of
13. In the presence of peroxide, HCl and HI do not CH3
|
give anti-Markownikoff’s addition of alkenes (i) CH3 - C - CH = CH 2
because: |
Cl
(a) One of the steps is endothermic in HCl
and HI CH3
|
(b) Both HCl and HI are strong acids (ii) CH 2=C - CH = CH3
|
(c) HCl is oxidizing and the HI is reducing Cl
(d) All the steps are exothermic in HCl and HI
CH3
14. The reaction of |
(iii) CH 3 - C = CH - CH 2Cl
CH3CH=CH OH with HBr gives CH3
|
(iv) ClCH 2 - C = CH - CH 3
(a) (i) and (iii) (b) (ii) and (iii)
(a) CH3CHBrCH2 OH
(c) (ii) and (iv) (d) All the four.
17. 1, 3-Butadiene is treated with hot KMnO4/NaIO4,
the product(s) formed is(are)
(b) CH3CH2CHBr OH
(a) 2HCHO + OHC – CHO
(b) 2HCOOH + HOOC–COOH
CH3CHBrCH2 Br (c) 2CO2 + HOOC–COOH
(c)
(d) 4CO2
Ph Ph Ph Ph MeO
(d) CH3CH2CHBr Br 18.
Ph

15. Among the following sets, the most stable ionic (I) (II) (III) (IV)
species are
Order of rate of electrophilic addition reaction
+ – with HBr will be
(a) and

59
 (a) IV > I > III > II (b) I > II > III > IV (c) I atom combines with H atom to give back HI.
(c) I > III > II > IV (d) IV > I > II > III (d) Iodine atom is not reactive enough to add
CH 2 - CH = CH 2 across a double bond.

22. Which of the following alcohols cannot be

19. + HCl ¾¾
® X, X is
prepared from hydration of an alkene?

(a) OH (b) OH
CH 2 - CH - CH3
|
Cl
OH
(a) (c) (d)
OH

CH 2 - CH 2 - CH 2 Cl 23. In which of the following reaction,

Markovnikov’s rule is violated?
HBr
(b) (a) CH3— O — CH CH2 ¾¾¾
CCl4
®
HBr
Cl (b) CH3— NH — CH CH2 ¾¾¾
CCl4
®
|
CH - CH2 - CH3 HBr
(c) CH3—S—CH CH2 ¾¾¾
CCl4
®
HBr
(c) (d) O2N — CH CH2 ¾¾¾
CCl4
®

24. Me H Me
CH 2 - CH = CH 2
Cl H
(d) Me H
20. The major product of the following reaction Hydrogenation of the above compound in the
Br 1. excess alc. KOH
presence of poisoned palladium catalyst gives
¾¾¾¾¾¾¾® is (a) an optically active compound
Br 2. NaNH 2
Ph (b) an optically inactive compound
3. H3O+
(c) a racemic mixture
H
(d) a diastereomeric mixture
H
(a) Ph H (b) Ph
Br 25. The compound X in the following reaction is
Br Br 2 (i) H /Pt
CH3C º CCH3 ¾¾¾¾¾
®X
(ii) Br2
H H
(c) Ph (d) Ph (a) d-2, 3-Dibromobutane
Br H (b) l-2, 3-Dibromobutane
21. The addition of HI in the presence of peroxide (c) dl-2, 3-Dibromobutane
catalyst does not follow anti-Markovnikov's rule (d) meso-2, 3 Dibromobutane.
because
(a) HI is a strong reducing agent.
(b) H-I bond is too strong to be broken
homolytically.

60
 C 2 H5
26. C CH

(i) NaNH , NH H
(b)
¾¾¾¾¾¾® 2
(ii) CH Br
3
(A) ¾¾¾¾¾¾ 2
Linder catalyst
® (B) ;
3
Product (B) is: Br
Br
C C CH3
CH - CH 3
(c)
(a)
(d) Both (a) and (b)
29. Which of the following would not give 2-
H CH3 phenylbutane as the major product in a Friedel-
Crafts alkylation reaction ?
C C
(a) 1-butene + HF
(b) (b) 2-butanol + H2SO4
H
(c) Butanoyl chloride + AlCl3 then Zn, HCl
(d) Butyl chloride + AlCl3
H
(c) C H
C
30. In the following reaction, P gives two products
CH3
Q and R, each in 40% yield
H H
C H 1. O3
C OMe ¾¾¾¾¾®
2. Zn, H2O
Q + R

40% 40%
P
(d) (MW = 210)
If the reaction is carried out with 420 mg of P.
27. Among the following compounds, the decreasing the reaction yields 108.8 mg of Q. The amount
order of reactivity towards electrophilic of R produced in the reaction is closest to
substitution is (a) 97.6 mg (b) 108.8 mg
(c) 84.8 mg (d) 121.6 mg

CH3 OCH3 CF3

I II III IV
(a) III > I > II > IV (b) IV > I > II > III
(c) I > II > III > IV (d) II > I > III > IV
28. Bromination of ethyl benzene in presence of light
gives
C2 H5
Br
(a)

61
 Numeric Value Answer

31. On conversion into the Grignard reagent

followed by treatment with water, how many alkyl
bromides would yield isopentane?
32. Number of hydrocarbons formed when C2H5Br
and CH3–CH2–CH2–Br are treated with Na in
the presence of dry ether is ______.

33. How many number of moles of H2 is used for

the complete hydrogenation of the given
compound in the presence of a metal catalyst?
Me CN
Me CN
34. Consider the following reaction scheme

Br /CCl NaNH
¾¾¾
2
¾¾
4
® A ¾¾¾¾
2
®B
D

NaOD/D O HgSO 4/H 2SO 4

D ¬¾¾¾¾¾ 2
(excess)
¾ C

How many deutrium are present in th e

compound D?
35. Total no. of alkynes that on catalytic reduction
gives 3-ethyl-4-methylheptane ______.

ANSWER KEY
1 (c) 5 (d) 9 (d) 13 (a) 17 (c) 21 (b) 25 (c) 29 (c) 33 (7)
2 (d) 6 (a) 10 (a) 14 (b) 18 (d) 22 (d) 26 (c) 30 (c) 34 (4)
3 (d) 7 (a) 11 (a) 15 (d) 19 (c) 23 (d) 27 (a) 31 (4) 35 (3)
4 (b) 8 (b) 12 (a) 16 (a) 20 (a) 24 (b) 28 (c) 32 (7)

62
 Hints & Solutions

1. (c) In neopentane all the H atoms are same (1º). 6. (a) Peroxide effect is observed only in case of
CH3 HBr. Therefore, addition of HCl to propene even
|
CH 3 - C - CH 3 in the presence of benzoyl peroxide occurs
|
CH3 according to Markovnikoff’s rule :
2. (d) In trans-isomer polarity developed by one HCl
—CH3 group is cancelled by polarity of the CH3 - CH = CH 2 ¾¾¾¾¾¾®
(C6H 5CO)2O 2
order —CH3 group placed in opposite direction
CH3 – CHCl – CH3
while the cis-isomer is polar although weak causing
7. (a) The intermediate 2º carbocation shows
high boiling point than the trans-isomer.
resonance
3. (d)
2 1 Br +
CH3CHCOONa CH3CH CH 2 = CH - CH = CH 2 ¾¾¾
®
——® + CO2 + 2NaOH + H2
CH3CHCOONa CH3CH
3 4 2 2
4. (b) The relative reactivities of alkenes towards
HX are directly related to the stabilities ofé the + + ù
é - CH = CH+ +
intermediate carbocations. Isobutene (IV) formsê CH 2 Br - CH
ê CH Br - CH 2 -« CH
CH = 2 Br
CH - CH
« =
CH CH
2 Br--CH
CH2 ú CH - CH 2 ùú
=
ë ë û û
the most stable 3° carbocation followed by Br -
¾¾¾ ® CH 2 Br - CH = CH - CH 2 Br
butene-1 (II) which forms 2° carbocation.
1,4 - Dibromo - 2- butene
Ethylene (I) and vinyl chloride (III), both form 1°
carbocation, but the carbocation from vinyl 8. (b) Always remember cis-2-butene + Br2 ®
chloride will be less stable because electron- Racemic-2, 3-dibromobutane
withdrawing halogen intensifies the positive charge trans-2-Butene + Br2 ® Meso-2, 3-dibromobutane.
and thus destabilizes the carbocation. Hence 9. (d) Addition of hydrogen halide to alkene is
vinyl chloride will be less reactive than ethylene. an example of electrophilic addition involving
B 2H 6 carbocations as intermediates.
5. (d) 6CH3 - CH = CH 2 ¾¾¾®
ether, 0°C HBr
1-Propene CH3 CH CH2 ¾¾¾¾¾¾
In absence of
®
H O peroxide
2(CH3CH 2CH 2 )3B ¾¾¾®
2 2
OH- CH3 —CH—CH3
6CH3CH 2CH 2OH + 2H 3BO3 ½
Propanol Br
(Markownikoff 's addition)

63
 –
10. (a) +

CH3
(i) O3/CH2Cl2, 196-200K
CH2 ¾¾¾¾¾¾¾¾¾®
– –
CH3 C It has 8p e s, doesn't It has 4p e s, doesn't
(ii) Zn/H2O follow Huckel's rule follow Huckel's rule
2-Methyl propene
+
CH3 –

CH3 C O + HCHO
– –
propanone Formaldehyde It has 10 p e s, follows It has 2 pe s, follows
Huckel's rule Huckel's rule
As both the species in option (d) follow
Huckel’s rule. Thus, it is correct option.
16. (a) H+ adds to C1 to form a more stable allylic 3°
11. (a)
carbocation rather than to C2 or C3 to form a
+
nonallylic 1° carbocation (CH2—CH(CH3)CH = CH2
+
and H2C = C(CH3)CH2—CH2 , respectively) or to
C4 to yield to a 2° allylic carbocation.
CH3
1 2 3 4 +
H
CH2 = C—CH = CH2 ¾¾® CH2 = C—CH—CH3
Isoprene 2° allylic carbocation
¾® H+
(less stable, not formed)
This reaction is Friedal-Craft acylation. CH3
CH2 – CH=CH2 Cl–
(I) Hg(OAc) 2
CH3—C—CH = CH2 ¾¾®
12. (a) +
(ii) NaBH 4 3° allylic carbocation (more stable)
(also favoured by —CH3 group)
CH2–CH–CH3 CH3 CH3

OH CH3—C—CH = CH2 + CH3— C = CH—CH2

13. (a) Anti-Markownikoff addition is possible Cl Cl

(i) (iii)
only in case of HBr and not in HCl and HI. In
HBr both the chain initiation and propagation 17. (c) Hot KMnO4/NaIO4 are strong oxidising
steps are exothermic, while in HCl, first step is agents which will give CO2 and COOH–COOH.
exothermic, and second step is endothermic and 18. (d) Rate of electrophilic addition is proportional
in HI, no step is exothermic. Hence HCl and HI to nucleophilicity of alkene and stability of
do not undergo anti-Markownikoff ’s addition. carbocation, so order will be. IV > I > II > III.
14. (b) The intermediate carbocation is more 19. (c)
+
stable, because positive charge is in conjugation CH2 CH CH2 CH2 CH CH3
with the benzene nucleus, due to possibility of
resonance. HCl
¾¾¾®
15. (d) The species which follows Huckel’s rule
(4n + 2)p will be most stable species.
2° carbocation

64
 + -
+ NaNH2
CH CH2 CH3 CHCH2CH3 26. (c) C C H
–
Cl
–
Cl -
¾¾¾® NaNH - + CH3 Br
C CNa

Benzyl
Carbocation H /Pd/BaSO
C C CH3 ¾¾¾¾®
2 4

20. (a)
H
Br H /Pd/BaSO
¾¾¾¾® C
Br Excess alc. KOH NaNH 2
Br ¾¾®
Ph ¾¾¾¾¾® Ph +
H3O
C
Ph—C CH H
H3C
21. (b) Hydroboration oxidation reaction. cis

H 27. (a) :OCH3

:
BH2 CH3
(1) B 2H 6
¾¾¾¾®

>
(2) H 2O 2 , OH OH
¾¾¾¾¾¾
®
Strong electron-releasing Electron-releasing
22. (d) Corresponding alkene is not possible. group is present group is present
due to + R
HBr
23. (d) H C = CH – NO ¾¾®
2 2
+ – +
H3C – CH – NO2 + H2C – CH2 – NO2 CF3
Unstable Stable
carbocation carbocation
> >
¾¾®

¾¾®

– –
Br Br

CH3 – CH – NO2 H2C – CH2 – NO2 Electron-releasing No group Strong electron

is present withdrawing group
is present
Br Br
Unstable Stable
product product 28. (c) Bromination in presence of light leads to
24. (b) Addition on triple bond takes place by the side chain substitution. For nuclear substitution
syn-addition of hydrogen in presence of we require halogen carrier.
poisoned palladium catalyst. 29. (c) The Friedel-crafts alkylation reaction will
Since the configuration of the double bond give propyl phenyl ketone which further on
already present is cis, the compound formed will Clemmenson’s reduction will give butyl benzene.
have a plane of symmetry and hence optically AlCl
inactive. C6H6 + CH3CH2CH2COCl ¾¾¾®
3

25. (c) Alkynes add hydrogen in cis-manner the Zn-Hg/HCl

cis-alkene adds bromine in anti manner forming C6H5COCH2CH2CH3 ————®
racemic product.
C6 H5CH 2 CH 2CH 2CH3
Butyl benzene

65
 31. (4) All alkyl bromides having carbon skeleton of
isopentane (2-methylbutane (CH3)2CHCH2CH3)
30. (c) OMe will give isopentane via Grignard reagent.
CH3 CH3
P
(MW = 210) BrCH2CHCH2CH3 CH3CBrCH2CH 3
1. O 3
CH3 Br CH3
2. Zn, H2O
CH3CH CHCH3 CH3CHCH2CH2Br
O
32. (7)
Na
O Et — Br + Br ¾¾¾¾ ®
+ dry ether

OMe Et — Et, , Et
Given weight
No. of moles of P = CH3 — CH3, CH2 = CH2, ,
M.W. 33. (7)
420 C ºN
= = 2 milimol ¾¾¾
2® 7H
210
C ºN
40 4
No. of milimoles of Q formed = 2 ´ = milimol
100 5 NH2
mass
Now, calculating M.W. of Q = NH2
mol
34. (4) ‘4’-Deuterium exchange occur.
10.8.8mg
= = 136 g\mol
4 Br Br NaNH2
m mol ¾¾®
2
CCl4
Br ¾¾¾®
D
5
O
M.W. 136 g/mol suggests that compound Q will D O
NaOD 1% HgSO4
O ¾¾¾®
CD3 D2O
¾¾¾¾®
dil. H2SO 4

35. (3) CH3 - CH 2 - CH 2 - CH - CH - CH 2 - CH3

| |
OMe CH 3 CH 2 - CH 3
3-Ethyl-4-methylheptane
Then R will be O
CH º C - CH 2 - CH - CH - CH 2 - CH 3
C7H6O | |
CH 3 CH 2CH3
Mol. wt = 106 g/mol
40 4 CH3 - CH 2 - CH 2 - CH - CH - CH 2CH3
Moles of R = 2 ´ = milimol | |
100 5 CH3 C º CH
4
Mass of R = × 10–3 mol × 106 × 103 mg/mol CH3 - C º C - CH - CH - CH 2CH3
5 | |
= 84.8 mg. CH3 CH 2CH3

66