Chemistry Target Soln


Chapter 1: Solid State
01 Solid State
Hints
Classical Thinking Critical Thinking

8. Calcite is a polymorphic form of calcium 3. Isomorphous pairs have same crystal structure.
carbonate, while others are polymorphic forms
of silica. 11. Ionic solids are hard and brittle. They are
nonconductors of electricity in solid state.
25. The given unit cell of tungsten is body-centred However, they are good conductors when
cubic (bcc) unit cell. melted. Hence, the given solid is an ionic solid.
bcc unit cell has 2 particles per unit cell.
12. Ionic solids become good conductors only at
33. Metals such as Mg, Zn, etc. have hcp crystal
high temperature, above their melting points.
structure. Polonium is the only metal that
crystallizes in simple cubic closed packed 17. There are two atoms in a bcc unit cell.
structure. So, number of atoms in 12.08 × 1023 unit cells
48. = 2 × 12.08 × 1023 = 24.16 × 1023
Atom/ion Location Contribution
to a unit cell 18. For bcc unit cell, n = 2.
A Corners of cube ⅛×8=1 400 pm = 400 × 10⁻10 cm
B Centre of cube 1 n M
ρ= 3
Ratio A:B=1:1 a NA
Formula AB 2 × 100
=
( 400 ) × 10−30 × ( 6.0 × 1023 )
3
49.
Atom/ion Location Contribution = 5.2 g / cm3
to a unit cell
W Corners of cube ⅛×8=1 19. For fcc unit cell, n = 4.
O Centres of edges ½×6=3 Mn
Density (ρ) = 3
Na Centre of cube 1 a NA
Ratio Na : W : O = 1 : 1 : 3
192.2 g mol−1 × 4 atom
Formula NaWO3 22.4 g cm-3 =
a × 6.022 × 1023 atom mol−1
3
56. Brass is an alloy of Cu and Zn. In brass, host Cu 192.2 × 4

a3 =
atoms are replaced by impurity of Zn atoms. 22.4 × 6.022 × 1023
The Zn atoms occupy regular sites of Cu atoms. = 5.7 × 10−23 cm3
It shows substitutional impurity defect.
22. (A) Two dimensional hexagonal close packed
67. Oxygen is paramagnetic while others are layer has triangular voids which is formed
diamagnetic substances. by three spheres.
68. CrO2 and Co are ferromagnetic, N2 is (C) Square close packing in two dimensions
diamagnetic while Cr3+ is paramagnetic. is less efficient as compared to hexagonal
close packing in two dimensions.
69. Schottky defect is a type of point defect.
(D) In three dimensional hexagonal close
70. (A) Metallic glass : Amorphous solid packed structure, the spheres of the third
(B) Sodium : Conductor layer align with the spheres of the first
(C) Solid O2 : Molecular solid layer.
1

MHT-CET Triumph Chemistry (Hints)

24. In fcc unit cell, the number of tetrahedral voids 36.
is equal to twice the number of atoms per unit Atom/ion Location Contribution
cell. to a unit cell
The number of atoms in fcc unit cell = 4 Au Corners of cube ⅛×8=1
∴ No. of tetrahedral voids per unit cell = 8 Cu Centres of faces ½×6=3
∴ 5 × 104 unit cells have 8 × 5 × 104 = 4 × 105 Ratio Au : Cu = 1 : 3
tetrahedral voids Formula AuCu3
27. Simple unit cell, r = a / 2 37. There is one octahedral hole per oxide ion and
rd
a 3 2
Body-centred unit cell, r = only   of these holes are occupied.
4 3
 
2 2
Face-centred unit cell, r = a ∴ the ratio should be :1=2:3
4 3
30. In fcc, r = 0.3535 a 38. Let the number of oxide ions in ccp unit cell
Where r = radius of the sphere be n.
a = edge length of the unit cell = 620 pm ∴ Number of tetrahedral voids = 2n
r = 0.3535 × 620 = 219.2 pm As 1/6th of the tetrahedral voids are occupied
by cation A,
31. For fcc unit cell, r = 0.3535 × a 1 n
r 0.14 Number of cation A = 2n × =
∴ Edge length (a) = = 6 3
0.3535 0.3535 Number of octahedral voids = n
= 0.396 ≈ 0.4 nm As 1/3rd of the octahedral voids are occupied
xn by cation B,
32. Number of particles in ‘x’ g = 1 n
ρ a3 Number of cation B = n × =
3 3
Number of atoms in 100 g
4 × 100 ∴ Ratio of cation A : cation B : Oxide ions
= −8 3
= 4 × 1025
10 × (10 ) n n
= : : n = 1: 1 : 3
3 3
33. a = 3 Å = 3 × 10–8 cm,
Density of the element = 8 g cm–3, The formula of the solid is ABO3.
Mass of the element (x) = 108 g 41. Nonstoichiometric defect does not cause any
x change in the crystal structure.
Number of unit cells in x g of metal =
ρ a3 47. For n-type, impurity added to silicon should
∴ Number of unit cells in 108 g of element have more than 4 valence electrons.
108
= 53. Calcite and aragonite are two polymorphic
8 × (3 × 10−8 )3
forms of calcium carbonate.
= 5 × 1023 unit cells
54. Ferromagnetic substances can be permanently
34. Number of unit cells in volume (V) of metal magnetised.
V
=
a3 Competitive Thinking
∴ Number of unit cells in 1.00 cm3 of Al
1.00 5. Number of atoms per unit cell in fcc = 4
= = 2.26 × 1022 Number of atoms per unit cell in bcc = 2
( 3.536 × 10 ) –8 3
∴ Difference = 4 − 2 = 2
35. 6. Mass of a single Ag atom = m
Atom/ion Location Contributi ∴ Mass of fcc unit cell of silver = 4m
on to a (Since, fcc type unit cell contains total 4 atoms)
unit cell Edge length of fcc unit cell = a
Cu Forms ccp lattice 4 Volume of fcc unit cell = a3
Ag Centres of edges ¼ × 12 = 3 Mass of fcc unit cell
Density of silver (Ag) =
Au Body centre 1 Volume of fcc unit cell
Ratio Cu : Ag : Au = 4 : 3 : 1 4m
Formula Cu4Ag3Au ∴ Density of silver (Ag) =
a3
2


7. For fcc unit cell, n = 4 ∴ Total volume occupied by the atoms
Edge length = a = x Å = 10–8 x cm, 4 16 3
M = 63.5 g mol–1 present in fcc unit cell = 4 × πr 3 = πr
3 3
n M
Density = 3 g cm–3 16. Radius of Na (in bcc lattice)
a NA
= 0.4330 a = 0.4330 × 4.29 = 1.86 Å
4 × 63.5 g mol−1
=
17. Radius of atom (in bcc lattice)
(10 x cm ) × 6.0 × 1023 mol −1
−8 3
= 0.4330 a = 0.4330 × 400 = 173.2 pm

423
= g cm–3
x3 18. Since, there are four metal atoms in one unit
423 cell, the given metal crystallizes in fcc lattice.
∴ Density of copper at T (K) = g cm–3. For fcc lattice:
x3
r = 0.3535 a = 0.3535 × 361
8. For bcc structure, n = 2
= 127.6 pm. ≈ 127 pm
n M
Density of unit cell = 3 19. Distance between two oppositely charged ions
a NA
1 3a 387 × 3
 n × M 3 (r+ + r−) = = = 335.14 pm
∴ a=   2 2
 ρ × NA 
1 20. Closest distance in fcc = 2r
 2 × 6.94 g mol−1 3
∴ a= −1  2 2a
−3 23
 0.530 g cm × 6.02 × 10 mol  =
4
1
= ( 43.5 × 10−24 ) 3 = 3.517 × 10⁻8 cm 2a
=
= 351.7 pm ≈ 352 pm 2
a
9. Metal has fcc lattice, =
2
∴ n=4
n M xn
ρ= 3 21. Number of particles in ‘x’ g =
a NA ρ a3
4×M For bcc structure, n = 2.
2.72 =
( 4.04 × 10 )
−8 3
× 6.02 × 10 23 Number of atoms in 2.4 g
2.4 × 2
2.72 × ( 4.04 ) × 6.02 × 10−1
3 = = 6 × 1022
10 × ( 200 × 10−10 )
3
M=
4
= 27 g mol–1 22. a = 300 pm = 300 × 10–10 cm,
10. Density of the element = 7.2 g cm–3,
For bcc, For fcc, Mass of the element (x) = 194.4 g
4r = 3 a 4r = 2 a Number of unit cells in x g of metal =
x
4r 4r ρ a3
a= a=
3 2 ∴ Number of unit cells in 194.4 g of element
194.4 194.4
2×M = =
3 7.2 × ( 300 × 10 )
−10 3 7.2 × 27 × 10−24
Zbcc ×M  4r 
N 0 ×  27
d bcc N 0 ×a 3  3 = = 1.0 × 1024 unit cells
= = 4×M 27 × 10 −24
d fcc Zfcc ×M
N 0 ×a 3  4r 
3
23.
N 0 ×  Atom/ion Location Contribution
 2
to a unit cell
3 3
= A Corners of cube ⅛×8=1
4 2
B Centres of 5 ½ × 5 = 5/2
15. Volume occupied by one atom of radius ‘r’ faces (since one
4 3 atom is missing)
= πr
3 Ratio A : B = 1 : 5/2 = 2 : 5
In fcc unit cell, there are 4 atoms present. Formula A2B5
3
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24. Let the number of atoms of element Y in hcp 31. One Sr2+ cation will create one Na+ vacancy.
unit cell be n. Hence, number of cation vacancies
∴ Number of tetrahedral voids = 2n = 1 × 10–5 × 6.022 × 1023 = 6.022 × 1018
As 2/3rd of the tetrahedral voids are occupied 32. Let Ni3+ be x. Hence, Ni2+ will be 0.98 – x.
by atoms of element X,
∴ 3x + 2(0.98 – x) – 2 = 0
2 4n
Number of atoms of element X = 2n × = ∴ x = 0.04
3 3
∴ Fraction of nickel existing as Ni3+
∴ Ratio of atoms of element X : atoms of element
0.04
4n = = 0.04
Y = :n=4:3 0.98
3
∴ Fraction of nickel existing as Ni2+ = 0.96
The formula of the compound is X4Y3.
33. The spinning of unpaired electron gives rise to a
25. The number of ions of ‘Y’ in ccp unit cell = 4.
magnetic moment.
Number of octahedral voids in ccp unit cell
= Number of ions of ‘Y’ in ccp unit cell = 4 Na+ ⇒ 1s2 2s2 2p6
Ions of ‘X’ occupy all the octahedral voids. Mg ⇒1s2 2s2 2p6 3s2
The number of ions of ‘X’ in ccp unit cell = 4 F− ⇒ 1s2 2s2 2p6
∴ The ratio of number of ions of ‘X’ to the Ar+ ⇒ 1s2 2s2 2p6 3s2 3p5
number of ions of ‘Y’ = 4 : 4 i.e., 1 : 1. Thus, Ar+ contains an unpaired electron. Hence,
Hence, the molecular formula of the given it will have non-zero magnetic moment.
compound is XY. 34.
26. In cubic close packing (i.e., in ccp structure) Substance Magnetic property
there are 4 octahedral voids and 8 tetrahedral (A) Dioxygen Paramagnetic
voids in a unit cell. (B) Chromium(IV) oxide Ferromagnetic
The number of ‘B’ atoms in ccp unit cell = 4 (C) Benzene Diamagnetic
Since, ‘A’ occupies half of the octahedral voids, (D) Dihydrogen monoxide Diamagnetic
the no. of atoms of ‘A’ in ccp unit cell = 2.
Also, oxygen atoms occupy all the tetrahedral 35. According to the given condition,
voids = 8 Edge length (a) = 3 Volume of one CsCl ion pair
∴ The ratio of number of atoms of A, B and
oxygen (O) = 2 : 4 : 8 = 1 : 2 : 4 = 3 7.014 × 10−23 cm3
Hence, the structure of bimetallic oxide is = 4.12×10−8 cm
AB2O4. = 4.12×10−10 m
= 4.12 Å ≈ 4 Å
27. For hexagonal close packed (hcp) lattice, the
So, the smallest Cs to Cs internuclear distance is
number of atoms present in unit cell = 6
nearly 4 Å.
Octahedral voids = 6
Number of cations : Number of anions
75
6× :6
100
3: 4
Hence, the formula is C3A4.
28. The number of particles of Y in ccp unit cell = 4.
The formula of the solid is XY3. Therefore, the
ratio of number of X particles to the number of Y
particles is 1 : 3. So, for the unit cell, the number
4 ×1
of X particles = = 1.33
3
Number of octahedral voids in ccp unit cell
= Number of Y particles in ccp unit cell = 4
∴ Percentage of octahedral voids occupied by
1.33
X particles = × 100 = 33%
4
29. In Frenkel defect, smaller ion (generally cation)
is dislocated from its normal site to the
interstitial site.
4
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Hints to Evaluation Test
3. For bcc unit cell,

Total volume occupied by particles in the unit
cell = 0.68 a3
= 0.68 × (4.08 × 10–8)3
= 4.62 × 10–23 cm3
4. Number of atoms in 0.5 mol = 0.5 × NA
= 0.5 × 6.022 × 1023 = 3.011 × 1023
Number of octahedral voids = Number of atoms
= 3.011 × 1023
7. In fcc, r = 0.3535 a
Where r = radius of the sphere
a = edge length of the unit cell = 353.6 pm
r = 0.3535 × 353.6 = 125 pm
8. Let the number of atoms of P in ccp unit cell
be n.
∴ Number of octahedral voids = n
All octahedral voids are occupied by atoms Q.
Number of atoms Q in octahedral voids = n
Number of tetrahedral voids = 2n
Half of the tetrahedral voids are occupied by
atoms Q.
Number of atoms Q in tetrahedral voids
= 2n/2 = n
Total number of atoms Q = 2n
∴ Ratio of atoms P : atoms Q = n : 2n = 1 : 2.
The formula of the compound is PQ2.
10. For bcc unit cell, r = 0.4330 a
a = r / 0.4330
= 124.7 / 0.4330 = 288 pm
20.
Atom/ion Location Contribution
to a unit cell
A Corners of cube ⅛×8=1
B Centres of faces ½×6=3
Ratio A:B=1:3
Formula AB3
5
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Std. XII: Triumph Chemistry
02 Solutions
Hints
48. Due to dissociation, the number of particles

Classical Thinking increases. Hence, van’t Hoff factor also
increases.
10. When gases are dissolved in water, the gas
molecules in liquid phase are condensed. The 49. π = iMRT = i W2 RT
condensation is an exothermic process. Hence, M 2V
the solubility of gases in water decreases with
50. Methyl alcohol is a volatile liquid. Therefore, it
increase in temperature. increases the vapour pressure of a solution at a
P10 − P1 50 − 45 5 given temperature.
20. x2 = = = = 0.1
P1
0
50 50 52. Salt water contains relatively a smaller number
of water molecules per unit volume, as
25. For ideal solution, compared to the number of water molecules per
∆Tb = Kb × molality of the solution unit volume in our body. Salts in sea water are
∆Tb in larger proportion than salts in our body.
∴ Kb =
molality Solvent water flows out from the cells of our
body into sea water. The cells of our body
∆Tb 373.23 − 373.15 0.08 shrink in size making the skin appear wrinkled.
27. Kb = = =
m 0.15 0.15 This is due to osmosis.
= 0.53 K kg mol–1
1
53. Vapour pressure ∝
33. ∆Tf = Kf × m Boiling point
∴ 0.184 = m × 18.4 When vapour pressure decreases then boiling
m=
0.184 point increases and vice-versa.
= 0.01
18.4
41. Osmotic pressure is a colligative property i.e., Critical Thinking

depends only on the number of solute particles
in the solution. When mole fraction of the 1. The component of a solution which is in smaller
solvent decreases, mole fraction of solute proportion is called solute.
increases, which in turn results in increase in
osmotic pressure. 2. All the three states of matter i.e., solid, liquid and
gas may play role of either solvent or solute
42. If π is the osmotic pressure of a dilute solution
when forming a solution.
then, πV = nRT where n = moles of solute
6. Sugar dissolves in water because the dissolution
nRT
∴ π= of sugar in water is due to intermolecular
V hydrogen bonding between sugar and water.
1
∴ at constant T : π ∝ 9. Henry’s law states that the solubility of a gas in
V a liquid is directly proportional to the pressure
at constant V and n : π ∝ T and of the gas over the solution.
πV = constant if T and n are constant
12. Gases like NH3 and CO2 react with water as
∴ The incorrect statement is π ∝ V when T is
follows:
constant.
 NH +4 + OH–
NH3 + H2O 
46. Na3PO4 gives a maximum of four ions, thus, it
will show highest van’t Hoff factor. CO2 + H2O 
 H2CO3
6

Chapter 02: Solutions

13. According to Henry’s law, S = KHP P10 − P1
23. = N2
Given S = 3.12 ×10–4 mol L−1, P = 0.24 bar P10
S 3.12 × 10−4 mol L−1 But N1 + N2 = 1
KH = =
P 0.24bar ( sum of the mole fractions of the solute
= 13 × 10−4 mol L−1 bar–1 and solvent is equal to one)
= 1.3 × 10–3 mol L−1 bar–1 ∴ N1 = 1 − N2
14. According to Henry’s law, S = KH P P10 − P1
−4 −1
∴ N1 = 1 −
S 13.6 × 10 mol L P10
∴ KH = =
P 2 bar P10 − P10 + P1
−4 −1 −1 N1 =
= 6.8 × 10 mol L bar P10
Solubility of N2 if partial pressure of N2 is ∴ P1 = P10 N1
1.56 bar,
S = KHP P10 − P1
S = 6.8 × 10−4 mol L−1 bar−1 × 1.56 bar 24. = x2
P10
= 1.0608 × 10−3 mol L−1 0.2
∴ = 0.25 = x2
15. Vapour pressure is independent of volume of 0.8
the container. Since, all other factors remain
25. P1 = 750 mm Hg
same, vapour pressure of water remains
unchanged. P10 = 760 mm Hg at 373 K
P0 − P 760 − 750 10 1
17. P1 = P x10 x2 ==
1 1
= =
1 0
P1 760 760 76
P1 = 40 mm Hg × 0.40 = 16 mm Hg
26. Mass of CCl4 = Density of CCl4
18. P1 = P10 x1 × Volume of CCl4
3 3
78 ∴ W1 = 1.58 g/cm × 100 cm = 158 g
∴ P1 = 75 × 78 P10 − P1 W × M1
78 46 = 2
+ P10
M 2 × W1
78 92
143 − P1 0.5 × 154
∴ P1 = 50 torr =
143 65 × 158
19. There are two volatile liquids A and B. Using 0.5 × 154
143 − P1 = × 143
Dalton’s law of partial pressure, 65 × 158
∴ Psolution = PA + PB ∴ P1 = 141.93 mm
∴ Psolution = xA PA0 + xB PB0
27. Mass of benzene = volume × density
∴ xA = 1 − xB = 1 − 0.2
= 56.8 × 0.889 = 50.495 g
∴ xA = 0.8
50.495
PA0 = 70 Torr Moles of benzene = = 0.6474
78
Psolution = 84 Torr (1 Torr = 1 mm of Hg) P10 − P1 n
Now, Psolution = 0.8 × 70 + 0.2 × PB0 = 2
P10 n1
∴ 84 = 0.8 × 70 + 0.2 × PB0 100 − 98.88 n2
∴ =
84 − (0.8 × 70) = 0.2 × PB0 100 0.6474
84 − ( 0.8 × 70 ) 84 − 56 28 ∴ n2 = 0.007251 mol
∴ PB0 = = = = 140 Torr Number of molesof solute
0.2 0.2 0.2 ∴ Molality =
P = vapour pressure of pure B = 140 Torr.
0 Massof solvent in kg
B
0.007251
21. Refractive index is an intensive property, which = = 0.144 m
50.495 × 10−3
does not depend on the number of particles in
solution. P10 − P1 W ×M
28. = 2 1
22. The relative lowering of vapour pressure of a P10 W1 × M 2
solution is equal to mole fraction of the solute. 640 − 600 2.175× 78
∴ =
0
P − P1 P 640 39.08× M 2
1
= 0 = x2
P10 P1 ∴ M2 = 69.5 g mol−1
7


13. According to Henry’s law, S = KHP P10 − P1
23. = N2
Given S = 3.12 ×10–4 mol L−1, P = 0.24 bar P10
S 3.12 × 10−4 mol L−1 But N1 + N2 = 1
KH = =
P 0.24bar ( sum of the mole fractions of the solute
= 13 × 10−4 mol L−1 bar–1 and solvent is equal to one)
= 1.3 × 10–3 mol L−1 bar–1 ∴ N1 = 1 − N2
14. According to Henry’s law, S = KH P P10 − P1
−4 −1
∴ N1 = 1 −
S 13.6 × 10 mol L P10
∴ KH = =
P 2 bar P10 − P10 + P1
−4 −1 −1 N1 =
= 6.8 × 10 mol L bar P10
Solubility of N2 if partial pressure of N2 is ∴ P1 = P10 N1
1.56 bar,
S = KHP P10 − P1
S = 6.8 × 10−4 mol L−1 bar−1 × 1.56 bar 24. = x2
P10
= 1.0608 × 10−3 mol L−1 0.2
∴ = 0.25 = x2
15. Vapour pressure is independent of volume of 0.8
the container. Since, all other factors remain
25. P1 = 750 mm Hg
same, vapour pressure of water remains
unchanged. P10 = 760 mm Hg at 373 K
P0 − P 760 − 750 10 1
17. P1 = P x10 x2 ==
1 1
= =
1 0
P1 760 760 76
P1 = 40 mm Hg × 0.40 = 16 mm Hg
26. Mass of CCl4 = Density of CCl4
18. P1 = P10 x1 × Volume of CCl4
3 3
78 ∴ W1 = 1.58 g/cm × 100 cm = 158 g
∴ P1 = 75 × 78 P10 − P1 W × M1
78 46 = 2
+ P10
M 2 × W1
78 92
143 − P1 0.5 × 154
∴ P1 = 50 torr =
143 65 × 158
19. There are two volatile liquids A and B. Using 0.5 × 154
143 − P1 = × 143
Dalton’s law of partial pressure, 65 × 158
∴ Psolution = PA + PB ∴ P1 = 141.93 mm
∴ Psolution = xA PA0 + xB PB0
27. Mass of benzene = volume × density
∴ xA = 1 − xB = 1 − 0.2
= 56.8 × 0.889 = 50.495 g
∴ xA = 0.8
50.495
PA0 = 70 Torr Moles of benzene = = 0.6474
78
Psolution = 84 Torr (1 Torr = 1 mm of Hg) P10 − P1 n
Now, Psolution = 0.8 × 70 + 0.2 × PB0 = 2
P10 n1
∴ 84 = 0.8 × 70 + 0.2 × PB0 100 − 98.88 n2
∴ =
84 − (0.8 × 70) = 0.2 × PB0 100 0.6474
84 − ( 0.8 × 70 ) 84 − 56 28 ∴ n2 = 0.007251 mol
∴ PB0 = = = = 140 Torr Number of molesof solute
0.2 0.2 0.2 ∴ Molality =
P = vapour pressure of pure B = 140 Torr.
0 Massof solvent in kg
B
0.007251
21. Refractive index is an intensive property, which = = 0.144 m
50.495 × 10−3
does not depend on the number of particles in
solution. P10 − P1 W ×M
28. = 2 1
22. The relative lowering of vapour pressure of a P10 W1 × M 2
solution is equal to mole fraction of the solute. 640 − 600 2.175× 78
∴ =
0
P − P1 P 640 39.08× M 2
1
= 0 = x2
P10 P1 ∴ M2 = 69.5 g mol−1
7


K f × 1000 × W2 6 1 × 82.1 × 3
49. M2 = ∴ M2 = ×0.821×300 = = 40.05 × 3
∆Tf × W1 12.3 2.05
5.12 × 1000 × 1 ∴ M2 = 120.15 g/mol
= = 256 g mol−1
0.40 × 50
58. AlCl3 furnishes more ions than CaCl2 and thus
K × 1000 × W2 shows higher boiling point i.e., t1 > t2.
50. M2 = f
∆Tf × W1
59. NaCl gives maximum ions; hence, it will show
5.12 × 1000 × 0.440
= = 178.9 g mol−1 highest osmotic pressure.
0.567 × 22.2
60. BaCl2 ⇒ Ba2+ + 2Cl− = 3 ions
51. ∆Tf = 0.186 K NaCl ⇒ Na+ + Cl− = 2 ions
∆Tf = Kf × m Glucose ⇒ No ionization
ΔTf 0.186K ∴ Order of osmotic pressure:
∴ m= = = 0.1 mol kg−1 BaCl2 > NaCl > Glucose
Kf 1.86K kg mol−1
∆Tb = Kb × m 61. Lesser the number of particles in solution, lesser
the depression in freezing point, i.e., freezing
∴ ∆Tb = 0.512 K kg mol−1 × 0.1 mol kg−1
point is higher. As the number of particles
= 0.0512 K obtained in case of dissolving of sugar to form a
Boiling point of solution solution is least compared to the others, 0.1 m
= Boiling point of water + ∆Tb sugar solution will have a higher freezing point.
= (373 + 0.0512) K = 373.0512 K
62. 0.5 M (3.0 g L–1) urea solution and 0.5 M
53.
n
π = MRT = 2 RT (17.10 g L–1) sucrose or sugar solution exhibit
V same osmotic pressure, hence, termed as
1.75 isotonic solution.
= 342 × 0.0821 × 290 63. CaCl2 gives maximum ions in solution hence, it
150
1000 has minimum freezing point.
= 0.81 atm. 65. NaCl → Na+ + Cl− = 2 ions
54. Isotonic solution means molar concentrations K2SO4 → 2K+ + SO 24 − = 3 ions
are same. K2SO4 gives maximum ions in solution, so it
Mboric acid = Msucrose shows maximum depression in freezing point.
1.63 20
66. As the number of particles increases, colligative
∴ m = 342
properties increases.
450 1000
where m = molar mass of boric acid ∴ Vapour pressure decreases.
Sodium phosphate gives maximum ions in
1.63 × 342 × 1000
∴ m= solution, so it shows lowest vapour pressure.
20 × 450
colligative property of electrolyte solution
55. π=M×R×T 67. i=
colligative propertyof nonelectrolyte solution
π 2.5
∴ M= = = 0.1025 M For KCl, i = 2 and for sugar it is equal to 1.
RT 0.0821 × 297
56. T = 273 + 15 = 288 K 68. KCl undergoes complete dissociation in water.
π = MRT ∴ The reaction is KCl → K+ + Cl–
W2 RT 3 × 0.0821 × 288 1 mole of KCl dissociates to form 2 mole
π= = = 6.57 atm particles.
M 2V 180 × 0.060
∴ i=2
∆Tf = i × Kf × m
W2 1
57. π= × RT ∆Tf = 0 – (–10) = 10 °C = 10 K
M2 V
∴ 10 = 2 × 1.86 × m
0.6g 1
∴ 1.23 atm = × 10
M 0.1L m= = 2.68 mol/kg
2 × 1.86
× 0.0821 L atm K−1 mole−1 × 300 K ∴ Grams of KCl = 2.68 × 74.5 = 199.66 g per kg
0.6 1 ∴ 199.66 g KCl should be added to one kg of
∴ M2 = × × 0.0821 × 300 g/mole
0.1 1.23 water.
9


13.44 3. y1 = 0.61, y2 = 0.39,
69. m= = 0.1 mol/kg
134.4 × 1 P10 = 50 mm Hg, P20 = 32 mm Hg,
CuCl2 → Cu+2 + 2Cl– P = 41 mm Hg
i = 3 (taking 100 % ionisation) Pbenzene = y1 P
∴ ∆Tb = i.Kb.m = 3 × 0.52 × 0.1 = 0.156  0.16 K x1 P10 = y1 P
70. Na2SO4 → 2Na+ + SO 24 − ∴ x1 =
0.61 × 41
= 0.50
1 0 0 50
(1–α) 2α α Ptoluene = y2 P
∴ i = (1 – α) + α + 2α = 1 + 2α x2 P20 = y2 P
0.39 × 41
71. As solids are incompressible, change of pressure ∴=x2 = 0.50
32
has no effect on solubility of solids in liquids.
4. P10 = 92 torr, P20 = 31 torr, n1 = 1, n2 = 4
72. Step I:
n1 1 1
Calculation of molar mass of sulfur: x1 = = = = 0.2
n1 + n 2 1 + 4 5
∆Tb = elevation of boiling point = 0.81 K
n2 4
Kb = molal elevation of boiling point constant x2 = = = 0.8
n1 + n 2 5
= 2.53 K kg mol−1
PT = P10 x1 + P20 x2 = 92 × 0.2 + 31 × 0.8
WB = mass of sulfur = 3.24 g
= 43.2 torr
= 3.24 × 10−3 kg
WA = mass of benzene = 40 g = 40 × 10−3 kg 6. Relative lowering of vapour pressure,
MB = molar mass of sulfur W2 9
P M2 180
∆Tb = Kb
WB
; = x2 = =
P10 W1 W2 90 9
M B WA + +
M1 M 2 18 180
3.24 × 10−3 0.05
0.81 = 2.53 ; = = 0.0099
M B × 40 × 10−3 5 + 0.05
MB = 0.253 kg/mol = 253 g/mol
ΔP W2 M1
Step II: 7. =
P10 M 2 W1
Calculation of the number of atoms present in
sulfur molecule: W2 18
0.002 = ×
Molar massof sulphur M B M 2 1000
Number of atoms =
Atomic massof sulphur W2
= = 0.111 mol
253 M2
= ≅8
32 W2 1000 1000
Molality = × = 0.111 ×
∴ The molecular formula of sulfur is S8. M2 W1 1000
73. Due to higher pressure inside the pressure = 0.111 m

cooker, the boiling point is elevated. 8. Vapour pressure of pure solvent i.e., water ( P10 )
= 17.53 mm
Competitive Thinking Vapour pressure of solution (P1) = 17.22 mm
2. For two components A and B, total vapour Mass of solvent (W1) = 100 g = 100 × 10−3 kg
pressure (pT) is given by, Molar mass of solvent (M1)
PT = PA + PB = 18 g mol−1 = 18 × 10−3 kg mol−1
= PA0 xA + PB0 xB Mass of solute (W2) = 18 g = 18 × 10−3 kg
P10 − P1 W2 M1
= 400 × 0.5 + 600 × 0.5 =
= 200 + 300 = 500 mm Hg P10 W1M 2
Mole fractions of components A (yA) and B (yB) 17.53 − 17.22 18 × 10−3 × 18 × 10−3
∴ =
in vapour phase are given as, 17.53 100 × 10−3 × M 2
PA 200
yA = = = 0.4 18 × 10−3 × 18 × 10−3
PT 500 ∴ Molar mass of solute (M2) =
100 × 10−3 × 0.0177
PB 300 = 0.183 kg mol−1
yB = = = 0.6
PT 500 = 183 g mol−1
10


9. Vapour pressure of pure acetone P10 = 185 torr  PH2 O = xH2 O PH0 2 O
Vapour pressure of solution, P1 = 183 torr 9.9
Molar mass of solvent i.e., acetone ∴ PH2 O = × 760 mm (considering at boiling
10
(CH3COCH3), M1 = 58 g mol–1 point of water)
P10 − P1 W ×M ∴ PH2 O = 752.4 mm = 752.4 torr
0
= 2 1
P1 W1 × M 2
( 1 torr = 1 mm of Hg)
185 − 183 1.2 × 58
∴ =
185 100 × M 2 13. ∆Tb = Boiling point of solution
1.2 58 − Boiling point of pure solvent (water)
∴ M2 = × ×185
2 100 = 100.052 °C − 100 °C
= 63.38 g mol–1 ≈ 64 g mol–1 = 0.052 °C or 0.052 K
∆Tb = Kb × m
P10 − P1 W ×M
10. = 2 1 ∆Tb 0.052K
P10 W1 × M 2 ∴ m= = = 0.1 m
Kb 0.52kg mol−1K
660 − 600 3.6 × 10−3 × 78
=
660 40 × 10−3 × M 2 14. ∆Tb = Kb⋅m (where, m = molarity)
−3
3.6 × 10 × 78  W2 1 
M2 = = 78.0 g mol−1 = Kb ⋅  × 
−3
40 × 10 × 0.09 M
 2 W1
11. Step I: Calculate vapour pressure of benzene: Rearranging,

Vapour pressure of solution = P1 = 3.00 kPa K b × W2
M2 =
Vapour pressure of pure benzene (solvent) = P10 ∆Tb × W1
where,
P10 − P1 W / M2
0
= 2 Kb = Ebullioscopic constant
P1 W1 / M1
∆Tb = Elevation of boiling point
P10 − 3.00 6 / M2 1.2 M2 = Molar mass of solute
= = …. (i)
P10 390 / 78 M2 W2 = Mass of solute
On adding 78 g of benzene to the solution, the W1 = Mass of solvent
resulting solution (390 + 78 = 468 g) has vapour
1000W2
pressure of 3.02 kPa at 298 K. 15. ∆Tb = Kb ;
M 2 W1
P10 − 3.02 6 / M2 1
= = …. (ii) ∆Tb M 2 W1 ∆Tb × 100 × 500
P10 468 / 78 M2 Kb = = = ∆Tb
1000W2 1000 × 50
Divide equation (i) by (ii)
P10 − 3.00 16. Kf is independent of solution concentration. Kf
= 1.2
P10 − 3.02 depends only on the nature of the solvent.
P10 − 3.00 = 1.2 P10 − 3.624 ∆Tf M 2 W1 0.15 × 60 × 100
17. Kf = = = 0.15 K kg mol–1
∴ P10 − 3.00 = 1.2 P10 − 3.624 W2 × 1000 6 × 1000
∴ P10 = 3.12 kPa 18. ∆Tf = T0 − T
Step II: Calculate the molar mass of solute: ∆Tf = 0 °C − (−0.186 °C)
1 P 0 − 3.02 3.12 − 3.02 0.1 ∆Tf = + 0.186 °C or 0.186 K
= 1 0 = =
M2 P1 3.12 3.12 ∆Tf = Kf × m
3.12 0.186 = 1.86 × m
∴ M2 = = 31.2 g mol−1
0.1 ∴ m = 0.1
Substituting the value of m in,
12. Molecular weight of glucose (C6H12O6) = 180
∆Tb = Kb × m
18
∴ Number of moles of glucose (nB) = = 0.1 ∆Tb = 0.521 × (0.1) = 0.0521 K
180
∴ Molecular weight of water (H2O) = 18 19. ΔTf = 0.70 K, Kf = 5.1 K kg mol–1,
178.2 Mass of benzene = 300 g = 0.3 kg
∴ Number of moles of water (nA) = = 9.9 ΔTf = Kf.m
18
∴ Mole fraction of water xH2O( ) =
nA ΔTf = Kf × number of moles of solute
nA + nB mass of solvent in kg
9.9 9.9 0.70 × 0.3
= = ∴ number of moles = = 0.0412
9.9 + 0.1 10 5.1
11


Let the mass of naphthalene be ‘x’ and that of 30 × 10−4 × 342 × 1
anthracene be ‘y’. Wcane sugar =
60 × 0.5
Total mass is 6 g. = 0.0342 kg = 34.2 g
∴ x+y=6 …(i)
But, total number of moles is 0.0412. 26. On dissolution in water, one molecule of KCl,
x y C6H12O6, Al2(SO4)3 and K2SO4 gives two, one,
Hence, + = 0.0412 …(ii) five and three particles respectively. Depression
128 178
in freezing point is a colligative property and
from (i), x = 6 – y …(iii)
depends on the number of particles. Among the
6− y y
∴ + = 0.0412 given options, all the aqueous solutions are of
128 178 the same concentrations i.e., 0.10 m but
178 ( 6 − y ) + 128 y Al2(SO4)3 gives the highest number of particles
∴ = 0.0412
128 × 178 and hence, shows the largest freezing point
1068 – 178 y + 128 y = 128 × 178 × 0.0412 depression.
1068 – 50 y = 938.70 28. On complete dissociation, barium hydroxide
∴ 50 y = 129.30 Ba(OH)2 gives three ions. Hence, van’t Hoff
∴ y = 2.59 ≈ 2.60 factor (i) is 3.
Substituting value of y in (iii)
x = 6 – 2.60 = 3.40 29. Aluminium chloride (AlCl3); i = 4
∴ The composition of naphthalene and anthracene Potassium sulphate (K2SO4); i = 3
in the mixture is 3.40 g and 2.60 g respectively. Ammonium chloride (NH4Cl); i = 2
Urea (NH2CONH2); i = 1
20. For isotonic solutions, the number of moles of Since urea is a non-electrolyte, it has the lowest
solutes are equal (i.e., molar concentrations are value of van’t Hoff factor.
same).
0.06 % (W/V) aqueous solution of urea means 30. Considering 100% ionisation of given species,
100 mL of solution contains 0.06 g of urea. Al2(SO4)3 dissociates as 2Al3+ + 3SO 24 − thus
Let volume of solution = 100 mL 1 molecule dissociates into five particles. In the
∴ Mass of urea = 0.06 g similar way K4[Fe(CN)6] also gives five
0.06 particles per molecule by dissociating as
Number of moles of urea = = 0.001 mol 4K+ + [Fe(CN)6]4−.
60
Number of molesof solute i −1
∴ Molarity = 31. Degree of dissociation (α) =
Volumeof solution in L n −1
0.001 n=2
= = 0.01 M
0.1 i −1
α= ⸫ α=i–1
∴ Among the given options, 0.01 M glucose 2 −1
solution is isotonic with the given solution of i=α+1
urea.
32. For Ba(NO3)2, i = 2.74 ….(given)
22. π = MRT n=3
n 2 RT 34.2
× 0.082 × 293 Degree of dissociation (α)
π= = 342
= 2.40 atm
V 1 i −1 2.74 − 1
== = 0.87
n −1 3 −1
23. π1 = MRT1 and π2 = MRT2
Hence, ∴ Degree of dissociation = 87 %
π1 T1
= 33. K3[Fe(CN)6] → 3K+ + [Fe(CN)6]3−
π2 T2 ∴ n=4
π1T2 4 × 546 i −1
π
= = = 8 atm Degree of dissociation (α) =
2
T1 273 n −1
3.333 − 1
24. For isotonic solutions, the number of moles of = = 0.78
4 −1
solutes are equal (i.e., molar concentrations are ∴ Percent dissociation = 0.78 × 100 = 78%
same).
Wurea Wcane sugar 34. Mole fraction of water vapour = 0.02
= Mole fraction of dry air = 1 – 0.02 = 0.98
M urea × Vurea solution M cane sugar × Vcane sugar solution
According to Dalton’s law,
30 × 10−4 Wcane sugar PDry air = PTotal × xDry air
=
60 × 0.5 342 × 1 = 1.2 × 0.98 = 1.176 atm
12


36. According to Henry’s law, ‘the solubility of a gas Now, ∆Tf = i.m.Kf
in a liquid at constant temperature is proportional ∆Tf = 0.45 °C or 0.45 K
to the pressure of the gas above the solution. mass(solute) = 0.2 g
S∝P mass(solvent) = 20 g = 0.02 kg
Where S is the solubility of the gas in mol dm−3  0.2 
and P is the pressure of the gas in atmosphere.  
If several gases are present, then the solubility 0.45 = i  60  5.12 ∴ i = 0.527
0.02 
of any gas may be evaluated by using P as  
 
partial pressure of that gas in the mixture. α
From given graph it is gas-A i.e., 0.527 = 1 − ∴ α = 0.946
gas-B 2
observed that at any Partial pressure
gas-C ∴ Degree of association = 94.6 %
given partial pressure,
gas-D
gas-A has the least 40. PA0 = 760 mm Hg
solubility. PT = 732 mm Hg
Solubility ∴ relative lowering of vapour pressure will be,
i −1 P10 − P1 W2 M1
37. α= =
n −1 P10 M 2 W1
i −1 W2 M1P10
0.8 = (Since solute tetramerises, n = ¼) ∴ M2 =
1
−1 W1 (P10 − P)
4
6.5 ×18× 760
i = 0.4 = = 31.757 g mol–1
i × K f × W2 × 1000 100(760 − 732)
ΔTf = W21000
M 2 × 100 Now, ∆Tb = K b
0.4 × 1.86 × 2.5 × 10 M 2 W1
M2 = 6.5×1000
0.3 = 0.52× 1.06
=
–1 31.757 ×100
M2 = 62 g mol
38. ∆Tb = Kb.m ∴ Boiling point of solution = 100 + 1.06
Substituting the given values in above equation, = 101.06 °C ≈ 101 °C
0.05 = 0.5 × m 41. ∆Tf = 0.413 °C, V2 = 10 mL,
0.05 M1 = 500 g = 0.5 kg, Kf = 1.86 K kg mol−1,
∴ m= ∴ m = 0.1
0.5 M2 = 60 g mol−1
number of molesof thesolute ∆Tf = Kf.m
But molality =
massof solvent in kg ∆Tf 0.413
Also, number of moles of solute ∴ m= = = 0.222
Kf 1.86
Amount of solutein grams
= W2 1
Molecular weight of solute Molality(m) = ×
M 2 M1 (in kg)
Let ‘x’ be the amount of solute dissolved.
W2 1
x 0.222 = ×
60 0.5
∴ molality (m) = 100
100 ×10−3 ∴ W2 = 0.222 × 60 × 0.5 = 6.66 g
W2 1
( 100 g of water is taken as solvent and Molarity (M) = ×
M 2 Volume of solution (in L)
molecular weight of solute is 100). Total volume of the solution
x
∴ 0.1 = ×10 ∴ x=1g = Volume of solvent + Volume of non-volatile
100 solute
∴ To observe an elevation of boiling point of = 500 + 10 = 510 mL = 0.51 L
0.05 °C, the amount of solute (Mol. Wt. = 100) 6.66 1
to be added to 100 g of water (Kb = 0.5) is 1 g. ∴ Molarity (M) = × = 0.218 M
60 0.51
39. 2CH3COOH 
 (CH3COOH)2 d
=
1
+
MB
x=2 M m 1000
1 1 M M × MB 0.218 0.218 × 60
i = 1 +  − 1 α i = 1 +  − 1 α ∴ d= + = +
x  2  m 1000 0.222 1000
α = 0.982 + 0.013
i = 1−
2 = 0.995 ≈ 0.993 g mL−1
13

1. ∆Tf = Kf × m 12. The number of moles of particles/ions obtained

⸫ (∆Tf)0 = 1.86 × 0.2 = 0.372 K from dissociation of 1 mole of the given solute:
ΔTf 0.680 glucose (C6H12O6) = 1,
i= = = 1.83
( ΔTf )0 0.372 sodium chloride (NaCl) = 2,
sodium sulphate (Na2SO4) = 3,
W2 sodium phosphate (Na3PO4) = 4.
3. πV = RT
M2 ∴ The ratio = 1 : 2 : 3 : 4
3.56
5.2 × 10−4 × 1 = × 0.082 × 300 13. Relative lowering of vapour pressure,
M2
W2 18
3.56 × 0.082 × 300 P M2
M2 = = 1.68 × 105 g mol−1 = x2 = = 180
5.2 × 10−4 P10 W1 W2 90 18
+ +
M1 M 2 18 180
P10 − P1 WM
6. = 2 1 0.1
P10 W1M 2 = = 0.0196
5 + 0.1
P10 − P1 25 × 78
=
180 250 × 342 π2 T
14. = 2
Vapour pressure lowering π1 T1
25 × 78 × 180 546 × 2.5
= P10 − P1 = = 4.1 mm Hg π2 =
250 × 342 276
7. The extent of depression in freezing point varies = 4.94 ≈ 5.0 atm
with the number of solute particles for a fixed K f W2 5.1 × 1
solvent only, and it is a characteristic feature of 15. M XY2 = =
∆Tf W1 2.3 × 20 × 10−3
the nature of solvent also. So, for two different
= 110.87 g mol−1
solvents the extent of depression may vary even
K f W2 5.1 × 1
if number of solute particles dissolved be same. M XY4 = =
∆Tf W1 1.3 × 20 × 10−3
8. PA = PA0 xA ….(i) = 196.15 g mol−1
PB = PB0 xB ….(ii) Let x and y be the atomic masses of ‘X’ and ‘Y’
respectively.
Equal moles of A and B in the vapour means
M XY2 = x + 2y = 110.87 ….(i)
PA = PB
∴ PA0 xA = PB0 xB ….(iii) M XY4 = x + 4y = 196.15 ….(ii)
Substituting xA = x and xB = 1 − x in (iii), Subtracting (i) from (ii),
0.95 × x = 0.15 (1 − x) M XY4 − M XY2 = (x + 4y) − (x + 2y)
0.95x = 0.15 − 0.15x = 196.15 − 110.87
0.95x + 0.15x = 0.15 ∴ 2y = 85.28
1.1x = 0.15 y = 42.64 g mol−1
0.15
x= = 0.1363 ≈ 0.14 substituting y = 42.64 in (i)
1.1
x + (2 × 42.64) = 110.87
1000K b W2 x + 85.28 = 110.87
11. ∆Tb =
M 2 W1 x = 110.87 − 85.28 = 25.59 g mol−1
=
(1000 g kg −1
× 1.94 K kg mol−1 × 0.524g ) 17. For two isotonic solutions, C1 = C2
−1
152g mol × 36.8g Wglucose Wsolute
∴ =
= 0.18 K M glucose × Vglucose solution M solute × Vsolution of solute
Boiling point of ether = (34.6 + 273) K 9.2 3 × 1000
= 307.6 K =
180 × 1 M solute × 100
The boiling point of solution
= boiling point of ether + ∆Tb 3 × 1000 × 180 × 1
Msolute = = 587 g mol−1
= 307.6 K + 0.18 K = 307.78 K 9.2 × 100
14


W2 RT
18. π= ×
M2 V
600 10 R × 300
= ×
760 M 2 250 × 10−3
10 × 300 × 760 × R 22800 × R
M2 = −3
=
250 × 10 × 600 1.5
19. S = KHP = 0.159 mol dm−3 atm −1 × 0.164 atm
= 0.026 M
20. Vapour pressure of a solvent is lowered by the
presence of solute in it. Lowering in vapour
pressure is a colligative property i.e., it depends
on the number of particles present in the
solution. Cu(NO3)2 gives the maximum number
of ions. (i.e., 3) so it causes the greatest
lowering in vapour pressure of water.
25. Molar mass of ascorbic acid = 176 g mol−1
∆Tf M 2 W1 1.5 × 176 × 100
W2 = = = 6.6 g
K f × 1000 4 × 1000
15

03 Ionic Equilibria
Hints
25. (NH4)2CO3 is a salt of weak acid H2CO3 and

Classical Thinking weak base NH4OH.
6. In aqueous solutions, H+ ion is always hydrated 26. Copper sulphate (CuSO4) is a salt of strong acid
and it exists in the form of hydronium ion H2SO4 and weak base Cu(OH)2. On dissolution
(H3O+). in water, it dissociates completely.
CuSO4(aq) → Cu (aq) 2+
+ SO 24(aq)
−
8. According to Arrhenius theory, base is a

substance that contains OH group. Hence, as per Water dissociates to a little extent.
this theory, NH3 is not a base. 2H2O(l) 
 H 3O(aq)
+
+ OH (aq)
−
10. The chemical species whose formulae differ SO 24 − ions of CuSO4 do not react with H+ ions of
only by one proton are called conjugate acid- water because the possible product is a strong
base pairs. Conjugate acid is formed when a electrolyte, i.e., H2SO4.
Bronsted-Lowry base accepts a proton. Hence, In the hydrolysis reaction, Cu2+ ions interact
the conjugate acid of NH3 is NH +4 . with OH− ions of water to form unionized
Cu(OH)2 molecule.
11. Conjugate base is formed when a Bronsted- Due to the formation of sparingly soluble
Lowry acid donates a proton. Cu(OH)2, the solution of CuSO4 becomes
 H3O+ + SO 24 −
HSO −4 + H2O  turbid.
Therefore, conjugate base of HSO −4 is SO 24 − . 27. Potassium cyanide (KCN) is a salt of KOH and
HCN which are strong base and weak acid
16. 1 mole of the base is initially present in volume respectively. When a salt of a weak acid and a
V dm3 of the solution and the fraction strong base is dissolved in water, it gives basic
dissociated to equilibrium is α, where α is the solution i.e., the pH of the solution is greater
degree of dissociation of the base. The fraction than 7.
of the base that remains undissociated at
equilibrium is (1 − α). Hence, the equilibrium 32. pH of the buffer solution does not depend on the
1− α volume of solution.
concentration of BOH is mol/dm3.
V
37. The solubility equilibrium for Ag2CrO4 is
17. Kb = 1.8 × 10−5 , c = 0.01 M  2Ag+(aq) + CrO24(aq)
Ag2CrO4(s)  −
Kb = α2c
∴ Ksp = [Ag+]2 [ CrO24 − ]
−5
Kb 1.8 × 10
∴ α= = = 1.8 × 10−3
c 0.01 39. Al(OH)3(s) 
 Al3(aq)
+
+ 3OH (aq)
−
18. Kw = [H3O+] [OH−] x = 1, y = 3

Also, at 298 K, [H3O+] = [OH−] = 1 × 10−7 M Ksp = xx yy Sx+y = (1)1 (3)3 S1+3 = 27S4
∴ Kw = (1 × 10−7) (1 × 10−7) = 1 × 10−14 40. For a sparingly soluble salt AX,
20. pH = – log10[H+] = – log10[0.01] AX(s) 
 A (+aq ) + X (−aq )
= – log10[10−2] = 2.0 ∴ x = 1 and y = 1

∴ Ksp = xx yy Sx+y = S2
21. pH + pOH = 14
∴ pOH = 14 – 3.12 = 10.88 ∴ S= K sp
16

Chapter 3: Ionic Equilibria
41. For MX2  M2+ + 2X– HCl and NH+4 are proton donors. They act as
x = 1, y = 2 acids. Cl− and NH3 are proton acceptors. They
Ksp = xx × yy × Sx+y = 11 × 22 × S1+2 behave as bases. The reaction has two conjugate
Ksp = 4S3 acid-base pairs. HCl (acid1) and Cl− (base1)
1.0 × 10–11 = 4S3 forms one pair, NH+4 (acid2) and NH3 (base2)
1.0 × 10−11 forms another pair.
S= 3 mol/L
4
6. (A) BF3 is a Lewis acid.
42. Ksp does not change with concentrations of the (C) All Lewis acids are not Bronsted acids.
ions. (D) When water reacts with ammonia, OH–
44. The ionization of CH3COOH is suppressed due ions are formed.
to the presence of CH3COONa containing a
common CH3COO− ion. 7. α = 0.001 % = 10–5
46. The solubility of a sparingly soluble compound Ka = α2c = (10–5)2 × 0.1 = 1.0 × 10–11
decreases with the presence of a common ion in 8. α = 4.0% = 4 × 10–2
solution.
Ka = α2c = (4 × 10–2)2 × 0.1 = 1.6 × 10–4
47. pH = 13
pH = −log10 [H+] 9. CH3COOH is a weak acid with Ka = 1.8 × 10−5.
∴ [H+] = 10−13 M Ka = α2c
i.e., 1000 cm3 of acidic solution will contain 10− K a 1.8 × 10−5
13 ∴ c= = 2 = 0.045 M
moles of H+ ions. a2 ( 0.02 )
∴ 1 cm3 of solution will contain 10–16 moles of H+
ions. 10. Ka = α12c1 = α 22c2
∴ Number of H+ ions in 1 cm3 solution
∴ α12c1 = α 22c 2
= 10–16 × NA = 10–16 × 6.022 × 1023
= 6.022 × 107 α1 = 16 = 0.16
100
48. AgCl is a strong electrolyte. ∴ (0.16)2 × 0.03 = α 22 × 0.12
(0.16) 2 ´ 0.03
α 22 = = 0.0064
Critical Thinking 0.12
1. The equilibrium between solid salt and its ions Hence, α2 = 0.08
in water is an example of ionic equilibrium. ∴ Percent dissociation in 0.15 M solution
= 0.08 × 100 = 8 %
2. Weak electrolytes dissociate only partially in
dilute aqueous solutions. HF is a weak 11. The pH of water decreases with increase in
electrolyte. temperature.
The dissociation of water into H+ and OH– is an
3. Percent dissociation = α × 100
endothermic reaction.
1.3
∴ α= = 1.3 × 10–2
100 12. pH = – log10[H+]
+
Equilibrium concentration of H ions  1 millimolar = 1 × 10–3 M
=α×c
∴ pH = – log10 [1 × 10–3] = 3
= 1.3 × 10–2 × 0.1
= 1.3 × 10–3 mol L–1 13. For 0.05 M H2SO4 solution,
[H+] = 2 × 0.05 = 0.1 M
4. In forward reaction, HCO3− donates proton while
For 0.005 M H2SO4 solution,
in the reverse reaction, H2O donates proton.
[H+] = 2 × 0.005 = 0.01 M
Hence, Bronsted-Lowry acids are HCO3− and
pH = −log10 [H+]
H2O.
∴ pH of 0.05 M H2SO4 solution
5. The acid-base reaction between HCl with NH3 = −log10 [0.1] = 1.0
is given as: pH of 0.005 M H2SO4 solution
HCl + NH3 
 NH +4 + Cl− = −log10 [0.01] = 2.0
Acid1 Base2 Acid2 Base1 ∴ Ratio of pH of 0.05 M and 0.005 M H2SO4
H+donor H+acceptor H+donor H+acceptor solutions is 1 : 2.
17


14. pH = −log10[H+] ∴ (20 × 5) mL of acidic solution will contain
−log10 [H+] = 6 2 × 10−5 moles of H+ ions.
[H+] = Antilog (−6) ∴ [H+] = 2 × 10–5 moles/100 mL
[H+] = 10−6 = 2 × 10–4 moles/1000 mL
[H+] [OH−] = 1.0 × 10−14 = 2 × 10–4 M
1.0 × 10−14 1.0 × 10−14 20. 10–8 M indicates a very dilute solution.
∴ [OH−] = = = 10−8 M
[H + ] 10−6 Thus, H+ of water cannot be ignored.
But dissociation of water is suppressed due to
15. The given compound is a monoacidic strong
common ion effect.
base, hence ‘a’ moles of it will give ‘a’ moles of
∴ [H+] ≠ 10–7 but less than 10–7.
OH− ions. Hence, pH of 10−8 M of HCl is less than 7.
As the volume is 1 litre, [OH−] = a mol/L
21.
∴ − log10[OH−] = − log10a
∴ pOH = − log10a Salt Nature of acid and Nature of
But pH = 14 − pOH = 14 − (− log10a) base from which the salt solution
= 14 + log10a salt is derived
KCN Weak acid HCN + Basic
16. Strong base KOH
Solution [H+] OR [OH−] pOH KCl Strong acid HCl + Neutral
(A) 1×10−6 M HCl [H+] = 1×10−6 M 8.0 Strong base KOH
(B) 1×10−3 M HCl [H+] = 1×10−3 M 11.0 NH4Cl Strong acid HCl + Acidic
(C) 1×10−3 M NaOH [OH−] = 1×10−3 M 3.0 Weak base NH4OH
(D) 1×10−5 M NaOH [OH−] = 1×10−5 M 5.0 CH3COONa Weak acid CH3COOH Basic
−3 + Strong base NaOH
Hence, among the given solutions, 1 × 10 M
HCl will have pOH equal to 11 at 298 K. 22. Aqueous solutions of salts of strong bases and
weak acids are basic. For example, HCOOK.
17. For a weak acid, [H+] = c.α Such solutions will turn red litmus blue.
= 0.01 × 10−3 = 1 × 10−5 M
∴ pH = 5 23. Aqueous solutions of salts of weak acids and
weak bases are acidic, basic or neutral
∴ pOH = 14 – 5 = 9
depending on the relative strength of weak acid
18. pH = 9.0 and weak base. The salt for which Ka < Kb, the
pOH = 14 – pH = 14 – 9.0 = 5.0 aqueous solution is basic (pH > 7).
pOH = −log10 [OH−] 24. A basic buffer solution consists of a mixture of
∴ [OH−] = 10–5 M a weak base and its salt of strong acid. Hence,
The monoacidic base BOH dissociates as (C) is basic buffer.
BOH(aq) 
 B(+aq ) + OH(−aq )
[Salt]
[OH−] = αc 25. pOH = pKb + log10
[Base]
[OH − ] 10−5
∴ α= = = 1 × 10−4 [NH 4+ ]
c 0.1 = pKb + log10
[NH 3 ]
Kb = α2c
= (1 × 10−4)2 × 0.1 = 1 × 10−9 0.30
= 4.74 + log10
pKb = −log10 Kb = −log10 (1 × 10−9) = 9.0 0.30
= 4.74 + 0 = 4.74
19. pH = 3 ∴ pH = 14 – 4.74 = 9.26
pH = − log10 [H+]
∴ [H+] = 10–3 M [Salt]
26. pOH = pKb + log10
i.e., 1000 mL of acidic solution will contain 10−3 [Base]
moles of H+ ions. [NH 4Cl]
= pKb + log10
∴ 20 mL of acidic solution will contain [NH 4OH]
20 × 10−3 0.2
= = 2 × 10–5 moles of H+ ions = 4.8 + log10
1000 0.02
This solution is diluted 5 times. = 4.8 + 1 = 5.8
18


28. For CaSO4, 36.
CaSO 4(s)  Ca (aq)

2+
+ SO 24(aq)
−
3
[Y]/mM
∴ x = 1, y = 1
Ksp = xx yy Sx+y = (1)1 (1)1 S1+1 = S2 2
∴ S = K sp = 6.4 × 10−5 = 8 × 10–3 1
2+
29. Ca3(PO4)2(s) 
 3Ca + 2PO34−
1 2 3
Ksp = [Ca2+]3 [PO34− ]2 [X]/mM
= (2.0 × 10–8)3 × (1.6 × 10–5)2
XY2(s) → X(+aq ) + 2Y(−aq )
= 8.0 × 10–24 × 2.56 × 10–10
= 20.48 × 10–34 10–3 2 × 10–3
= 2.048 × 10–33 Ksp = [X+] [Y–]2
30. Cr(OH)3(s) 
 Cr(3aq+ ) + 3OH (−aq ) Ksp = 10–3 × (2 × 10–3)2
Ksp = 4 × 10–9
x = 1, y = 3 So, correct answer is option (C).
Ksp = xx.yy.Sx+y
= (1)2.(3)3.(S)1+3
∴ Ksp = 27 S4 Competitive Thinking
K −31
2.7 × 10 −8 1. The conjugate acid and base differ with respect
∴ S = 4 sp
= 4 = 4
10−32 = 10
27 27 to each other by proton. For example, HCl and
31. For precipitation to occur, IP > Ksp. Cl− are conjugate acid-base pair.
Ksp for AgCl is 1.8 × 10–10. 2. Conjugate base of an acid always has one fewer
Ionic product (IP) i.e., [Ag+][Cl−] is greater than proton.
Ksp when [Ag+] = 10–4 M and [Cl−] = 10–4 M Acid ¾¾¾
-H +
® Conjugate base
32. Precipitation will occur if IP (ionic product) is H2O -H
¾¾¾ ®
+
OH−
greater than Ksp. +
So, for precipitation not to occur, ionic product HF -H

¾¾¾ ® F−
should be less than Ksp. 3. Bronsted acid ⇒ proton donor
[A+] = 10–5 M Bronsted base ⇒ proton acceptor
Ksp = [A+] [B−] Among given options, only HCl cannot act as a
K sp 1×10−10 Bronsted base.
∴ [B−] = = = 1 × 10−5 M
[A ]
+
10−5
4.
When the concentration of B is 5 × 10–6 M (i.e.,
less than 1 × 10−5 M), the ionic product of Species Conjugate acid Conjugate base
5 × 10–11 is obtained. H2O H3O+ OH–
(Here, IP is less than Ksp 1 × 10–10). HSO4− H2SO4 SO24 −
34. The dissociation of water molecules into ions is 8. [OH−] = 10−4 M ∴ pOH = 4
bond breaking and is therefore an endothermic pH + pOH = 14, ∴ pH = 14 − 4 = 10
process (energy must be absorbed to break the
bonds). Endothermic processes are favoured by 9. [OH−] = 0.01 M
an increase in temperature and so as the pOH = −log10[OH−] = −log10[0.01] = 2
temperature rises the equilibrium moves further pH = 14 − pOH = 14 − 2 = 12
to the right hand side and Kw gets larger.
10. (I) H+ = 6 × 10–3 mol, OH– = 4 × 10–3 mol
Ka Excess H+ = 2 × 10–3 mol
35. For weak acids, [H3O+] = α c = ×c
Total volume = 0.06 + 0.04 = 0.1 L
c
= Ka × c 2 × 10−3
∴ [H+] = = 2 × 10–2 M
0.1
Let concentration of acetic acid be c1 and formic
∴ pH = –log10 [H+] = –log10 (2 × 10–2)
acid be c2.
= 1.7
∴ 1.8 × 10−4 × 0.002 = 1.8 × 10−5 × c 2 (II) H+ = 5.5 × 10–3 mol, OH– = 4.5 × 10–3 mol
−4
1.8 × 10 × 0.002 Excess H+ = 0.001 mol
c2 = = 0.02 M Total volume = 0.055 + 0.045 = 0.1 L
1.8 × 10−5
19


0.001 In the hydrolysis reaction, NH4+ ions of the salt
∴ [H+] = = 0.01 M
0.1 interact with OH− ions of water to form
∴ pH = –log10 [H+] = – log10 (0.01) unionized molecules of weak base NH4OH.
= –log10 (10–2) = 2.0 Thus, the following equilibrium is established.
(III) H = 0.015 mol, OH– = 0.005 mol
+
NH +4(aq) + H2O(l) 
 NH4OH(aq) + H (aq)
+
Excess H+ = 0.01 mol An excess of H+ ions are produced in the

Total volume = 0.075 + 0.025 = 0.1 L process and the solution becomes acidic
0.01 (pH < 7).
∴ [H+] = = 0.1 M
0.1
∴ pH = –log10 [H+] = – log10 (0.1) 15. KCl and NaCl are salts of strong acids and
= –log10 (10–1) = 1.0 strong bases. Hence, their salt solutions are
(IV) [H+] = [OH–] ⇒ Neutral solution (pH = 7) neutral (i.e., pH = 7). CuSO4 is a salt of strong
acid and weak base and hence, its salt solution is
11. c = 1 mM = 10−3 M acidic (i.e., pH < 7). Na2CO3 is a salt of weak
For a weak base, acid and strong base and hence, its salt solution
[OH−] = c × α is basic (i.e., pH > 7). So, among the given salts,
20 Na2CO3 will give the highest pH in water.
[OH−] = 10–3 ×
100 16. Acidic buffer contains weak acid and its salt.
[OH−] = 2 × 10−4 M HClO4 is a strong acid, hence, option (C) will
pOH = −log10 [OH−] = − log10 (2 × 10–4) not form an acidic buffer.
pOH = 3.699
pH + pOH = 14 17. Basic buffer contains weak base and its salt. In
∴ pH = 14 – pOH = 14 – 3.699 option (B), half of the weak base NH4OH reacts
pH = 10.301 with HCl to form salt NH4Cl. Hence, the
reaction mixture contains equal amount of weak
12. pH = 3 base and its salt.
pH = −log [H+] HCI + NH4OH → NH4Cl + H2O
∴ [H+] = 10–3 M
The acid HQ dissociates as 18. For MxXy,
Ksp = xx.yy.Sx + y
HQ(aq) 
 H(+aq ) + Q(−aq )
K sp
[H+] = αc ∴ Sx + y =
xx.y y
[H + ] 10−3
∴ α= = = 0.01 1
c 0.1  K  x+ y
∴ S =  x sp y 
Ka = α2c [ (1 − α) ≈ 1]  x .y 
= (0.01)2 × 0.1 = 1 × 10−5 19. For Zr3(PO4)4, x = 3 and y = 4
13. pH = −log[H+] Ksp = xx.yy.Sx + y
∴ [H+] = antilog (−pH) ∴ Sx + y =
K sp
= antilog (−5) xx.y y
[H+] = 1 × 10−5 M  K sp 
17
A weak monobasic acid (HA) dissociates as, ∴ S=  

 6912 
HA(aq) 
 H (aq)
+
+ A (aq)
−
∴ [H+] = α c 20.  3Ca2+ + 2PO34−

Ca3(PO4)2 
 H +  1 × 10−5 3S 2S
∴ α=  = = 1 × 10−4
c 0.1 Ksp = [Ca2+]3 [ PO34− ]2 = [3S]3 [2S]2 = 108 S5
∴ Percent of degree of dissociation
= α × 100 = 1 × 10−4 × 100 21. A2X3(s) 
 2A 3( aq+ ) + 3X (2aq− )
= 1 × 10−2 % x = 2, y = 3
Ka = α2c = (1 × 10−4)2 × 0.1 Ksp = xx yy Sx+y
= 1 × 10−9 ∴ Ksp = (2)2 (3)3 S2+3
= 108 S5
14. Ammonium chloride (NH4Cl) is a salt of strong 1/5 1/5
acid HCl and weak base NH4OH. On dissolution K   1.08 × 10−13 
S =  sp  =  
in water, it undergoes complete ionization.  108   108 
NH4Cl(aq) → NH +4(aq) + Cl(aq)
−
= 1 × 10−3 M
20

22. For MX2  M2+ + 2X– ∴ 1.6 × 10−10 = (S) (S + 0.1)
x = 1, y = 2 ∴ 1.6 × 10−10 = S × 0.1 ( S << 0.1)
Ksp = xx × yy × Sx+y = 11 × 22 × S1+2 ∴ S = 1.6 × 10−9 M
Ksp = 4S3
1.0 × 10–11 = 4S3 29. Ksp(CaF2) = 5.3 × 10–11
1.0 × 10−11 10 × 10−12 CaF2 
 Ca2+ + 2F–
S= 3 = 3 = 3
2.5 × 10 −12
0 0.1
4 4 Initial (M)
–4 –1 Equilibrium (M) S 2S + 0.1
= 3
2.5 × 10 = 1.36 × 10
−4
mol L
23. Ag2C2O4(s) 
 2Ag (+aq ) + C 2O −4( aq ) Ksp = [Ca2+][F–]2 = (S) (2S + 0.1)2 = (S) (0.1)2
(∵ 2S + 0.1 = 0.1)
S 2S S
K sp 5.3 ´ 10-11
2S = 2.2 × 10–4 mol L–1 S= 2
= 2
= 5.3 × 10–9 mol L–1
∴ S = 1.1 × 10–4 mol L–1 (0.1) (0.1)
Ksp = 4S3 = 4 (1.1 × 10–4)3 31. In BF3, B atom is electron deficient and can
Ksp = 5.3 × 10–12 accept a share in an electron pair. Hence, BF3 is
24. pH = 9 a Lewis acid.
pOH = 14 − 9 = 5  Mg2+ + 2OH–
32. Mg(OH)2 
[OH−] = 1 × 10 −5M
Ca(OH)2(S) 
 Ca (2+aq ) + 2OH(−aq ) Ksp = [Mg2+] [OH–]2
K sp 1.0 × 10−11
S 2S = 1 × 10−5M ∴ [OH–]2 = 2+
= = 1.0 × 10–10
[Mg ] 0.1
Since, 2S = 1 × 10−5, S = 0.5 × 10−5 M
Now, ∴ [OH ] = 1.0 × 10–5
–
(Taking square root)
Ksp = [Ca2+] [OH−]2 = S × (2S)2 pOH = –log10[OH–] = –log10 [1.0 × 10–5]
= 0.5 × 10−5 (1 × 10−5)2 = – (–5) log10 10 = 5
= 0.5 × 10−15 pH + pOH = 14
∴ pH = 14 – 5 = 9
25. Ba(OH)2(s) 
 Ba (aq)
2+
+ 2OH (aq)
−
33. For MY, x = 1, and y = 1

pH of saturated solution of Ba(OH)2 is 12. ∴ Ksp = xx ⋅ yy ⋅ Sx+y
∴ pH + pOH = 14 ∴ = 1 × 1 × S2 = S2
∴ pOH = 14 − pH = 14 − 12 = 2 ∴ S = (6.2 × 10−13 )1/2 = (62 × 10−14 )1/2
 pOH = −log10[OH−] = 7.87 × 10−7 mol dm−3
For NY3, x = 1, and y = 3
∴ log10[OH−] = −pOH ∴ Ksp = 11 × 33 × S4 = 27S4
∴ [OH−] = antilog (−pOH) 1 1
 6.2 × 10−13  4  0.62 × 10−12  4
= antilog (−2) = 0.01 M ∴ S=   =  

 27   27 
1 1
∴ [Ba2+] = 5 × 10−3 M
[OH − ] =× 0.01 = 1
2 2  0.62  4
=  × 10
−3
Ksp = [Ba2+] [OH−]2  27 

= 5 × 10−3 M × (0.01)2 M2 = 0.389 × 10−3 mol dm−3
Thus, the molar solubility of MY in water is
= 5 × 10−7 M3
lesser than that of NY3.
26. The solubility of a sparingly soluble salt
decreases due to the presence of a common ion. 34. C5H5N + H2O 
 C5 H 5 N H
+
+ OH−
Since AgCl and KCl have common ion (Cl–), the Pyridine Water Pyridinium
solubility of AgCl will be minimum in 0.1 M KCl. ion
27. This is due to a common ion effect. Three
chloride ions (Cl–) will be produced per The degree of dissociation is given by
molecule of AlCl3 (which is maximum amongst α=
Kb
=
1.7 ×10−9
= 1.3 × 10−4
given options). C 0.10
28. AgCl(s) 
 Ag (aq)
+
+ Cl(aq)
− ∴ Percent dissociation = α × 100
Concentration
= 1.3 × 10−4 × 100 = 0.013 %
S S + 0.1
(M) ∴ Percentage of pyridine that forms pyridinium
Ksp = [Ag+] [Cl−] ion in the given solution = 0.013 %
21

1. For A3B2, x = 3 and y = 2 14. Ksp(CaF2) = 5.3 × 10–11

Ksp = xx ⋅yy Sx+y CaF2 
 Ca2+ + 2F–
∴ 1.08 × 10−8 = 33 × 22 × S3+2 Initial (M) 0 0.2
5 1.08 × 10−8 Equilibrium (M) S 2S + 0.2
∴ S =
108
Ksp = [Ca2+][F–]2 = (S) (2S + 0.2)2 = (S) (0.2)2
∴ S5 = 1 × 10−10
(∵ 2S + 0.2 = 0.2)
∴ S = (1 × 10−10)1/5
K sp 5.3 ´ 10-11
= 10−2 mol L−1 S= 2
= 2
= 1.3 × 10–9 M
(0.2) (0.2)
3. [OH−] = 10−5 M ∴ pOH = 5
+
pH + pOH = 14, ∴ pH = 14 − 5 = 9 15. Base ¾¾¾
+H
® Conjugate acid
+ H+
4. Bronsted acid is a proton donor. NH 2 ¾¾¾
-
® NH3
5. Percent dissociation = α × 100 18. H+ is a Lewis acid.

percent dissociation 60 20. pH = −log10[H+]
∴ α= = = 0.60
100 100 ∴ [H+] = antilog10 (−pH)
[H+] = c. α = 0.2 × 0.60 = 0.12 M = antilog10 (−5)
6. pH of an acidic buffer is given by Henderson- [H+] = 1 × 10−5 M
Hasselbalch equation as: A weak monobasic acid (HA) dissociates as,
salt  HA(aq) 
 H (aq)
+
+ A (aq)
−
pH = pKa + log10  
acid  ∴ [H+] = α c
0.1  H +  1 × 10−5
pH = pKa + log10 ∴ α=  = = 1 × 10−4
0.1 c 0.1
∴ pH = 4.74 ∴ Percent of degree of dissociation
= α × 100 = 1 × 10−4 × 100
7.  Cr(aq)
Cr(OH)3(s)  3+
+ 3OH (aq)
−
= 1 × 10−2 %
Here, x = 1, y = 3
∴ Ksp = xx yy Sx+y
= (1)2 (3)3 S1+3
= 1 × 27 × S4 = 27S4
8. pH = − log10 [H+] = − log10 (10−1) = 1
11. The degree of dissociation of a weak monobasic
acid is inversely proportional to the square root
of its concentration or directly proportional to
the square root of volume of the solution.
Ka
α= KaV =
c
12. pH = 11
∴ [H+] = 10–11 M
1 × 10−14
∴ [OH–] = −11
= 10–3 M
10
No. of moles
Molarity =
Vol. of solution
No. of moles
10–3 =
1
∴ No. of moles of NaOH = 10–3 mol
∴ Mass of NaOH = 10–3 × 40
= 0.04 g
22

Chapter 4: Chemical Thermodynamics
04 Chemical Thermodynamics
Hints
30. Enthalpy change that occurs when one mole of a

solid is converted into liquid without change in
Classical Thinking
temperature at constant pressure is enthalpy of
5. Internal energy is an extensive property (whose fusion.
magnitude depends on the amount of matter 36. For exothermic reactions, ∑ HP < ∑ HR.
present in the system) while surface tension,
For endothermic reactions, ∑ HP > ∑ HR.
viscosity and temperature are examples of
intensive property (whose magnitude is 37. A negative ∆H indicates that reaction is
independent of the amount of matter present in exothermic while a positive ∆H indicates that
the system). reaction is endothermic.. Thus, reaction (i) is
exothermic while reaction (ii) is endothermic.
10. For isothermal process, ∆T = 0
∴ ∆U = 0 38. Combustion of carbon releases energy in the
form of heat, so it is exothermic reaction.
11. In an isobaric process, pressure of the system
remains constant. 39. For endothermic reaction, ∆H = + ve
40. Standard state of water is H2O(l).
16. This is an irreversible process.
∴ W = − Pext(V2 − V1) 41. Thermochemical equation is the balanced
= − Pext(x − y) bar dm3 chemical equation in which the enthalpy
change, physical states and the number of moles
23. For isochoric process, ∆V = 0, So Qv = ∆U i.e., of reactants and products, have been specified.
heat given to a system under constant volume is Option (A): physical states not mentioned.
used up in increasing its internal energy. Option (C): Unbalanced equation
Option (D): Enthalpy change not mentioned
24. ∆U = QP + W The equation in option (B),
∆U = QP − Pext.∆V ( W = − Pext.∆V) CH4(g) + 2O2(g) → CO2(g) + 2H2O(l),
∴ QP = ∆U + Pext ∆V ∆rH° = −890 kJ is a thermochemical equation
which signifies that when 1 mole of gaseous
25. Enthalpy is defined by the equation, CH4 and 2 moles of O2 in their standard states
H = U + PV produce 1 mole of CO2 gas and 2 moles of
liquid water also in their standard states, the
26. Enthalpy (H) is defined as the sum of internal enthalpy change would be –890 kJ.
energy and energy equivalent to PV work,
43. The standard enthalpy of formation of a
H = U + PV
compound is the enthalpy change that
28. For reactions involving solids and liquids, ΔV accompanies a reaction in which one mole of
usually is very small (solids or liquids do not pure compound in its standard state is formed
show volume change with change of pressure) from its elements in their standard states.
and ΔH = ΔU. 45. Enthalpies of elements i.e, enthalpies of
29. Δng is the difference between the number of formation of elements is zero at standard state
moles of products and those of reactants. i.e., 298 K and external atmospheric pressure of
1 bar.
15
C6H6(g) + O2(g) → 6CO2(g) + 3H2O(g)
2 3600
47. n= = 200 mol
15 1 18
∆ng = 6 + 3 – 1 – =+
2 2 ∴ ∆H for 200 moles = − 284.5 × 200 = − 56900 kJ
23


48. i. It cannot be called as heat of combustion, ∴ W = − 2 bar × (2.5 dm3− 0.3 dm3)
since, 2 moles of reactants are present. = − 4.40 dm3 bar
ii. It cannot be heat of formation, since, Now, 1 dm3 bar = 100 J
2 moles of products are formed. 100 J
Hence, −4.40 dm3 bar × = − 440 J
Thus, the given ∆H represents heat of reaction. 1 dm3 bar
−3.77 × 56 12. W = − Pext ∆V
49. ∆fH of FeS = = − 100.5 kJ/mol
2.1 W 9.09 × 103 J 1dm3 bar
∴ Pext = − =
− ×
51. Reaction A + B → E can be obtained by ∆V (8 − 23) dm3 100 J
addition of reactions (i) and (ii). Hence, ∴ Pext = 6.06 bar
∆H = − 10.0 kcal + 15.0 kcal = 5 kcal
13. W = − Pext ∆V
54. ∆S = + ve then the system is more disordered. = − 3.039 bar × (20 – 30) dm3
= 30.39 dm3 bar = 3039 J
56. In case of gas, randomness is maximum,
= (3039 × 0.239) cal = 726.3 cal
therefore entropy is maximum in case of steam
(water vapour). 15. The work done in reversible isothermal
expansion process
57. CaCO3 changes to one solid product and one
P1
gaseous product. Gases have greater disorder = − 2.303nRT log10
than liquids and hence, entropy of the system P2
increases or ∆S is positive. 5
= − 2.303 × 2 × 8.314 × 330 × log10
1
62. Spontaneous change shows ∆G = – ve. = − 2.303 × 8.314 × 660 × log10 5 J
63. When ∆G = – ve, then the reaction is 16. P1 = 10 atm, P2 = 1 atm, T = 300 K, n = 1,
spontaneous in nature. R = 8.314 J K−1 mol−1
66. H2O(s) → H2O(l), above 273 K By using the formula,
i. ∆H = + ve (i.e., enthalpy increases) P1
Wmax = −2.303 nRT log10
ii. ∆G = − ve (i.e., free energy decreases) P2
= −2.303 × 1 × 8.314 × 300 log10 10
67. ∆G° = ∆H° – T∆S° = −5744.1 Joules
∆G° = – 382.64 – (– 145.6) × 10–3 × 298
= – 339.3 kJ mol–1 V2
17. Wmax = − 2.303 nRT log10
V1
 20 
− 831.4 = − 2.303 × 1 × 8.314 × T × log10  
Critical Thinking  2 
1. Closed system is the type of system, which can 831.4
∴ T= = 43.42 K
exchange energy but not matter with the 2.303 × 8.314
surroundings. The boundary between the system 18. Mass of oxygen = 16 g
and surrounding is sealed but not insulated.
∴ n = 0.5 mol
6. The process in which pressure remains constant Wmax = − 2.303nRT log10
V2
is known as isobaric process. Reversible process V1
is one in which change is carried out so slowly ∴ Wmax = − 2.303nRT log10 3 (V2 = 3V1)
that the system and surrounding are always in
= − 2.303 × 0.5 × 8.314 × 300 × 0.4771
equilibrium with each other.
= − 1370.26 J = − 1.370 kJ
10. W = −Pext∆V
Massof O 2 1.6 × 10−2 kg
= −1 bar (11 – 1) dm3 = −10 dm3 bar 19. n= = = 0.5 mol
Molar massof O 2 3.2 × 10−2 kg
Now, 1 dm3 bar = 100 J
⸫ W = − 10 × 100 = −1000 J  V2 
Wmax = –2.303 nRT log10  
 V1 
11. Initial volume (V1) = 300 cm3 = 0.3 dm3
Final volume (V2) = 2500 cm3 = 2.5 dm3  100 
= −2.303 × 0.5 × 8.314 × 300 × log10  
From formula,  10 
W = − Pext ΔV = − Pext (V2 − V1) = − 2,872 J
24


20. Expression for work, when an ideal gas expands 35. In the given reaction, ∆ng = 3 − (5 + 1) = −3
isothermally and reversibly is given by ∴ ∆H = ∆U − 3RT
V2 ∴ ∆H − ∆U = −3RT
Wmax = − 2.303nRTlog10 .
V1
1
For same mass, temperature, V1 and V2 36. In the reaction, H2(g) + O2(g) → H2O(l) ;
2
Wmax ∝ n ;
Mass  1
where, n = number of moles = ∆ng = 0 – 1 +  = –1.5
Molar mass  2 
1 ∴ ∆H = ∆U − 1.5 RT
n∝ ∴ ∆H < ∆U
Molar mass
∴ Lower the molar mass, higher is the magnitude 13
of work. 37. C4H10(g) + O2(g) → 4CO2(g) + 5H2O(l)
2
21. If a system releases 450 J of heat, this quantity 13
is removed from internal energy and if 600 J of ∆ng = 4 − 1+  = − 3.5
 2
work is done on the system, this quantity is
added to the system. Hence, ∴ ∆U > ∆H ( ∆n = −ve)
U2 = U1 + (− 450) + 600
38. For the reaction, 2CO(g) + O2(g) → 2CO2(g);
∴ U2 = U1 + 150 J
∆ng = 2 – 3 = −1
22. A 
40
→B A ←
− 40
B ∴ ∆H = ∆U − RT
∆U = 40 – 40 = 0 ∴ ∆H < ∆U
26. As the system is closed and insulated, no heat 39. In the reaction, PCl5(g) → PCl3(g) + Cl2(g) ;
enters or leaves the system, i.e., Q = 0; ∆ng = 2 – 1 = +1
∴ ∆U = Q + W = W ∆H = ∆U + ∆ngRT ∴ ∆H > ∆U
27. In adiabatic expansion, no heat is allowed to
enter or leave the system, hence Q = 0. 40. In reaction (C), ∆ng = 0 so, ∆U = ∆H
According to first law of thermodynamics; 41. ∆ng = 1 – 0 = 1
∆U = Q + W ∆U = ∆H − ∆ngRT
∴ ∆U = W 8.314
Work is done at the expense of internal energy. ∆U = +176 – 1 × × 1250 = 165.6 kJ
1000
Hence, the system gets cooled.
28. Q = 920 J, ∆U = +460 J, 42. ∆H = ∆U + ∆ngRT
According to first law of thermodynamics for ∆ng = 6 − 9 = −3
compression; R = 0.002 kcal = 2 × 10−3 kcal, T = 298 K,
∆U = Q + W ∆H = − 936.9 kcal
∴ W = ∆U − Q = 460 − 920 = − 460 J Substituting the values:
− 936.9 = ∆U − (2 × 10−3 × 298 × 3) kcal
29. ∆U = Q + W
Q = 54 J and W = − 238 J (work done by a 43. In the given reaction, ∆ng = 0
system or work done on the surroundings) ∴ ∆H = ∆U = 2.8 kJ
∴ ∆U = 54 – 238 = – 184 J
Thus, the system loses its internal energy. 44. For this reaction, ∆ng = 0 ∴ ∆U = ∆H
30. ∆U = Q + W = 200 + (− 1000) = − 800 cal 45. 7.8 g C6H6 gives 40 kJ heat
40 × 78
31. Since work is done by the system, W is taken as 78 g C6H6 (1 mol) gives = 400 kJ heat
7.8
negative. Thus, ∆U = – 400 kJ mol−1 at 300 K for
∆U = Q + W = 2500 – 3500 = –1000 cal 15
C6H6(l) + O2(g) → 6CO2(g) + 3H2O(l)
33. ∆ng = number of moles of product − number of 2
moles of reactant = 2 − 3 = −1 15 3
Now, ∆ng = 6 – = –
∆H = ∆U + ∆ngRT i.e., ∆H = ∆U + (− 1) RT 2 2
∆H = ∆U − RT ∆H = ∆U + ∆ngRT
3 8.314 × 300 
34. ∆H = ∆U + ∆ngRT = – 400 –  × 3
–1
 kJ mol .
 2 10 
Since ∆ng = – 2
Then ∆H = ∆U – 2RT ∆H = – 403.74 kJ mol–1
25


46. The reaction for the combustion can be given as 57. 2C2H6(g) + 7O2(g) → 4CO2(g) + 6H2O(l) ;
15 ∆rH° = – 3119 kJ
C6H5COOH(s) + O2(g) → 7CO2(g) + 3H2O(l)
2 ∆rH° = ∑ ΔfH° (Products) – ∑ ΔfH° (Reactants)
15 1 – 3119 = [4(–393.5) + 6(–286)] –
∆ng = 7 − = −
2 2 [2 ∆fH° (C2H6) + 0]
Here, T = 27 + 273 = 300 K [ ΔfH°(O2) = 0]
∆H = ∆U + ∆ngRT = – 1574 – 1716 – 2x
1 2x = – 1574 – 1716 + 3119 = – 171
∴ ∆H = −321.30 +  −  × 300 × R
 2 x = – 85.5 kJ
= (− 321.30 − 150 R) kJ 58. The molar mass of CO2 is 44 g. If 11 g yield
100 kJ of heat, 44 g will yield 400 kJ heat. Since
 1 the reaction is exothermic, it is − 400 kJ.
47. In the given reaction, ∆ng = 1 −  = + 0.5
2  
59. CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)
∆H = ∆U + ∆ngRT
Molecular mass of CH4 = 12 + 4 = 16 g/mol
∆H − ∆U = ∆ngRT ∴ Heat liberated on the combustion of 2.0 g of
= 0.5 × 0.002 kcal × T methane = 25.0 kcal
= 1 × 10–3 kcal × T = T cal ∴ Heat liberated on the combustion of 16.0 g
25 × 16
49. The reaction for combustion of methane gas is: = = 200 kcal
2
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) Enthalpy of combustion = − 200 kcal/mol
Methane Oxygen Carbon dioxide
1
60. CO(g) + O2(g) → CO2(g)
∆ng = 1 − (1 + 2) = −2 2
W = −∆ngRT  1 
∆rH° = ∆ f H° (CO2) – Δ f H°(CO) + Δ f H°(O 2 ) 
= −[−2 × 8.314 × 298] = + 4955 J ≈ + 5 kJ  2 
This is the work done for combustion of 1 mole = – 94.0 – (– 26.4) = – 67.6 kcal/mol
of methane.
61. 78 g of benzene on combustion produces heat
52. ∆fusH = 1.435 kcal.mol −1 = 3264.6 kJ
3264.6
i.e., 1 mole of H2O (for fusion) ≡ 1.435 kcal ∴ 39 g of benzene will produce =
2
18 g of H2O ≡ 1435 cal required
= 1632.3 kJ
∴ 1 g of H2O ≡ 80 cal required
∆freezH = − ∆fusH 62. Enthalpy of combustion of 1 mole (i.e., 16 g) of
CH4 = –800 kJ
53. ΔsolnH = ∆LH + ∆hydH ∴ Enthalpy of combustion of 4 × 10–4 kg of
= +790 kJ mol–1 + (–786 kJ mol–1) = +4 kJ mol–1 4 × 10−4 × (−800)
CH4 = = –20 kJ
16 × 10−3
54. ΔfH° refers to the formation of one mole of
NH3. 63. Adding equation (i) + equation (ii) and dividing
∴ ΔrH°for 4 moles = 4 × − 46 = −184 kJ 499 + 428 927
by 2; =
2 2
55. S + O2 → SO2; ∆rH = −298 kJ
Heat of formation for 1 mole (i.e., 64 g) of SO2 64. PH3(g) → P(g) + 3H(g), ∆rH = 228 kcal mol−1
= −298 kJ For breaking three P–H bonds ≡ 228 kcal mol−1
4 × (−298) 228
∴ Heat of formation for 4 g of SO2 = ∴ One P–H bond ≡ ≡ 76 kcal mol−1
64 3
= −18.6 kJ P2H4(g) → 2P(g) + 4H(g),
∆rH = 355 kcal mol−1
56. ∆rH° = ∑ ∆ f H°(products) – ∑ ∆ f H°(reactants) ΔrH° = ∑ΔH°(reactant bonds)
∆ f H°(Si) = 0, ∆ f H°(Mg) = 0 because they are in – ∑ΔH°(product bonds)
⸫ 4[P–H bonds] + 1[P–P bond] – 0
their standard states.
= 355 kcal mol−1
∆rH° = 2 ∆ f H o(MgO) – ∆ f H°(SiO2 ) ∴ 4 (76) + P–P bond = 355 kcal mol−1
= 2 (– 34.7) – (– 48.4) = – 21.0 kJ ∴ P–P bond = 355 − 4(76) = 51 kcal mol−1
26


H 70. The required reaction is 2C(s) + H2(g) → C2H2(g),
|
65. N ≡ N + 3H − H 
→ 2N − H Applying the operation (i) + (ii) + (–iii), by Hess’s
945 + 3× 436 = 2253 |
H law of constant heat summation; we get,
Energy absorbed 2 × (3 × 391) = 2346
∆rH = ∆H1 + ∆H2 + ∆H3
Energy released = (– 767) + (– 266) + (1290) = 257 kJ
Enthalpy of the reaction = 2253 − 2346
71. Given:
= − 93 kJ
1
66. Adding equation (i) + equation (ii) gives i. H2(g) + O2(g) → H2O(l); ∆rH = – 240 kJ
2
–110.5 + (−283.2) kJ = −393.7 kJ 17
ii. C6H10(l) + O2(g) → 6CO2(g)+ 5H2O(l);
67. 2C(s) + 3H2(g) → C2H6(g) ; ∆H = −30.2 kcal 2
… (i) ∆rH= –3800 kJ
2C(s) + 2H2(g) → C2H4(g) ; ∆H = +12.5 kcal iii. C6H12(l) + 9O2(g) → 6CO2(g) + 6H2O(l);
… (ii) ∆rH= – 3920 kJ
Required equation: Required equation is C6H10(l) + H2(g) → C6H12(l);
C2H4(g) + H2(g) → C2H6(g) ; is obtained by ∆rH = ?
reversing equation (ii) and adding it to (i), It may be achieved by the operation (i) + (ii) – (iii).
C2H4(g) → 2C(s) + 2H2(g); ∆H = −12.5 kcal ∆rH = (– 240) + (– 3800) – (− 3920)
2C(s) + 3H2(g) → C2H6(g); ∆H = −30.2 kcal = – 4040 + 3920 = – 120 kJ
C2H4(g) + H2(g) → C2H6(g) ; ∆H = −42.7 kcal 72. Reverse equation (iv), rewrite equation (i),
68. CH4 + 2O2 → CO2 + 2H2O, ∆H = – 890.4 kJ multiply equation (iii) and (ii) by 3, and adding
….(i) all the equations, we get,
C + O2 → CO2, ∆H = – 395.5 kJ ....(ii) B2H6(g) → 2B(s) + 3H2(g) ; ∆H = − 36 kJ mol−1
1 3
H2 + O2 → H2O, ∆H = – 285.8 kJ ....(iii) 2B(s) + O2(g) → B2O3(s);
2 2
from (i), (ii), (iii). ∆H = − 1273 kJ mol−1
∆cH (CH4) = ∆fH (CO2) + 2∆fH (H2O) 3H2O(l) → 3H2O(g) ;
– ∆fH (CH4) – 2∆fH (O2) ∆H = 44 × 3 = 132 kJ mol−1
– 890.4 = – 395.5 + 2(– 285.5) – ∆fH (CH4) 3
3H2(g) + O2(g) → 3H2 O(l) ;
–2×0 2
∆fH (CH4) = – 76.1 kJ mol −1 ∆H = − 286 × 3 = − 858 kJ mol−1
69. 2C(s) + 3H2(g) → C2H6(g); ∆rH = −21.1 kcal B2H6(g) + 3O2(g) → B2O3(g) + 3H2O(g)
….(i) ∆cH = − 36 − 1273 + 132 − 858
C(s) + O2(g) → CO2(g); ∆rH = −94.1 kcal = − 2167 + 132 = − 2035 kJ mol−1
….(ii)
3
73. 2B(s) + O2(g) → B2O3(s), ∆fH°
1 2
H2(g) + O2(g) → H2O(l); ∆rH = −68.3 kcal 3 1
2 B(s) + O2(g) → B2O3(s), ∆cH°
….(iii) 4 2
Required equation: 1
∆cH° (of solid boron) = ∆ f H°(B2O3 )
7 2
C2H6(g) + O2(g) → 2CO2(g) + 3H2O(l) ;
2
74. When ∆Stotal = + ve, the change is spontaneous
∆H = ?
Required equation is obtained by reversing 76. Randomness decreases in the case of
equation (i), multiplying equation (ii) by 2 and crystallization of sucrose from solution.
equation (iii) by 3 and adding all the equations.
C2H6(g) → 2C(s) + 3H2(g); ∆rH= +21.1 kcal o ( −238.6 kJ )
78. ΔSsurr = – ∆H = –
2C(s) + 2O2(g) → 2CO2(g) ;∆rH = −188.2 kcal T 298 K
3 = +0.8007 kJ K–1 = +800.7 J K–1
3H2(g) + O2(g) → 3H2O(l);∆rH = –204.9 kcal
2 ΔStotal = ΔSsys + ΔSsurr
= +36.7 J K–1 + 800.7 J K–1
7
C2H6(g) + O2(g) → 2CO2(g) + 3H2O(l) ; = +837.4 J K–1
2
∆rH = –372 kcal 79. For reverse reaction, sign will change.
27


80. ∆G = ∆H – T∆S = 145600 – 300 × 116 3. W = – Pext ∆V
= 145600 – 34800 = 1 × 105 × (1 × 10–2 – 1 × 10–3)
= 110.8 kJ mol−1 = – 1 × 105 × 9 × 10–3 N m = – 900 J
82. If ∆G = – ve, reaction is spontaneous. 5. ∆U = Q + W
84. ∆G = ∆H – T∆S = 9.08 – (298 × 0.0357) 0=Q+W
= –1.56 kJ mol−1 (∆U = 0, for isothermal process)
Since, the value of ∆G is negative, the reaction ∴ Q=–W
is spontaneous at 298 K.
Also, ∆H = + ve, therefore, the reaction is 6. ∆U = Q + W
endothermic. ∆U = Q − Pext.∆V ( W = −Pext.∆V)
85. ∆G = 0, for equilibrium process. For an isochoric process, ∆V = 0,
∴ ∆U = Qv
86. W = −Pext.∆V
= −1 bar (6 dm3 – 2 dm3) = −4 dm3 bar 7. In an adiabatic process, no heat is allowed to
= −4 × 100 J = −400 J enter or leave the system. Hence, Q = 0.
∆U = Q + W= 800 J + (−400) J = +400 J According to first law of thermodynamics,
∆U = Q + W
87. Since one mole of an ideal gas is compressed
∴ ∆U = W
isothermally, ∆U = 0 for reversible process.
∴ ∆U = Q + W = 0 8. In an adiabatic process, no heat is allowed to
∴ Q = −W enter or leave the system.
 P1  Hence, Q = 0
Wmax = − 2.303 nRT log10   From the 1st law of thermodynamics,
 P2 
ΔU = Q + W
 2 ∴ ΔU = W
= −2.303 × 1 × 8.314 × 302 × log10  
 10 
9. In an adiabatic process, there is no exchange of
= –2.303 × 1 × 8.314 × 302 × (–0.6989)
= 4041.74 J heat between the system and its surroundings.
So, Q = 0.
= (4041.74 × 0.239) cal = 966 cal
According to first law of thermodynamics,
∴ Q = −966 cal
∆U = Q + W
88. 50% of 880 kJ = 440 kJ ∴ ∆U = W or −∆U = −W (For adiabatic process)
Since ∆evpH = 44 kJ mol−1 , 440 kJ will require Since, the given process is adiabatic expansion,
440 the work is done by the system on the
= 10 moles of water.
44 surroundings at the expense of system’s internal
One mole of water = 18 g energy. Hence, the internal energy of the system
∴ 10 moles = 10 × 18 = 180 g decreases in this process.
89. In the formation of acetaldehyde from its ∴ For adiabatic expansion, −∆U = −W.
constituent elements, i.e., ∆U < 0
1 10. ∆U = Q + W = –15 kJ + (–10 kJ) = –25 kJ
2C(s) + 2H2(g) + O2(g) → CH3CHO(l);
2
 1 11. ∆H = ∆U + ∆ngRT
∆ng = 0 −  2 +  = −2.5 H2 − H1 = U2 − U1 + n2 − n1(RT)
 2
∴ H2 − H1 + U1 − U2 = n2RT − n1RT
90. As formation of graphite is an exothermic
reaction, there is lowering of energy. So, 12. ΔH = ΔU + ΔngRT
graphite is more stable than diamond. In the reaction given in option (D),
Δng = 1 – 0 = 1
∴ ΔH > ΔU
Competitive Thinking 13. ∆H = ∆U + ∆ngRT
2. 1 dm = 0.1 m ∴ ∆U = ∆H – ∆ngRT
1 dm3 = 0.001 m3 = 19 – (5–3) × 2.0 kcal mol–1
∴ 10 dm3 = 0.01 m3 × 10–3 kcal K–1 mol–1× 300 K
W = – Pext ∆V = 19 kcal – 1.19 kcal
= – 100 kPa (0.01 –1) m3 = 99 kJ = 17.8 kcal
28


15 H H H H
14. C6H6(l) + O2(g) → 6CO2(g) + 3H2O(l);
2
∆H = –781.1 kcal 21. H – C = C – H + H – H → H – C– C – H
∆H = ∆U + ∆ngRT Ethene Hydrogen
H H
∆U = ∆H − ∆ngRT Ethane
15
(Here ∆ng = 6 – = –1.5, ∆rH = Σ∆H(reactant bonds) – Σ∆H(product bonds)
2
= [∆H(C = C) + 4 ∆H(C – H) + ∆H(H – H)]
R = 1.98 × 10–3 kcal K–1 mol–1) – [6∆H(C – H) + ∆H(C – C)]
⸫ ∆U = –781.1 – (–1.5 × 1.98 × 10–3 × 298) = [1 mol × 600 kJ mol–1 + 4 mol × 410 kJ mol–1
= –780.1 kcal/mol + 1 mol × 400 kJ mol–1] – [6 mol × 410 kJ mol–1
15. CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) + 1 mol × 350 kJ mol–1]
Methane Oxygen Carbon dioxide = [600 + 1640 + 400] – [2460 + 350]
= 2640 – 2810
∆ng = 1 − (1 + 2) = −2 = – 170 kJ
W = −Pext∆V = −∆ngRT = −[−2 × 8.314 × 300] 22. i. C(Graphite) + O2(g) → CO2(g);
= + 4988.4 J ∆rH° = −393.5 kJ mol−1
This is the work done for combustion of 1 mole 1
of methane. ii. H2(g) + O2(g) → H2O(l);
2
∴ Work done for combustion of 0.5 mole of
∆rH° = −285.8 kJ mol−1
methane will be = + 4988.4 × 0.5 = + 2494.2 J
iii. CO2(g) + 2H2O(l) → CH4(g) + 2O2(g);
16. The work done in chemical reaction is given as, ∆rH° = +890.3 kJ mol−1
W = – ∆ng RT Required equation is
For a combustion of ethane, the reaction is, C(graphite) + 2H2(g) → CH4(g) ; ∆rH° = ?
2C2H6(g) + 7O2(g) → 4CO2(g) + 6H2O(l) This can be obtained by applying the operation:
∆ng = 4 – (2 + 7) = –5 (i) + 2(ii) + (iii)
W = –∆ng RT ∴ ∆rH° = −393.5 + 2(−285.8) + 890.3
= – (–5) × 8.314 × 300 = −74.8 kJ mol−1
= 12471 J = 12.471 kJ 3
 The work done during combustion of 23. S+ O2 → SO3; ∆H = −2x kJ. ....(1)
2
2 moles (i.e. 2 × 30 g) of C2H6 = 12.471 kJ 1
SO2 + O2 → SO3; ∆H = −y kJ. ....(2)
∴ The work done during combustion of 90 g of 2
90 × 12.471 For reaction (2),
C2H6 = = 18.706 kJ ≈ 18.71 kJ
2 × 30 ∆H = ∆ f H (SO3 ) − ∆ f H (SO2 )
18. Amount of water decomposed by 272 kJ = 18 g ∴ ∆ f H (SO2 ) = ∆ f H (SO3 ) − ∆H
= 1 mole = − 2x + y or y − 2x
Amount of water decomposed by 750 kJ
18 × 750 49.6 24. C(s) + O2(g) → CO2(g) ; ∆H° = − x kJ
= = = 2.75 mol … (i)
272 18
2CO(g) + O2(g) → 2CO2(g) ; ∆H° = − y kJ
19. ∆rH° = Σ∆fH°(products) – Σ∆fH°(reactants) … (ii)
= [∆fH°(CaO) + ∆fH°(CO2)] 1
– ∆fH°(CaCO3) Required equation: C(s) + O2(g) → CO(g) ;
2
= [– 635 + (–393)] – (–1207) is obtained by multiplying equation (i) by 2 and
= – 1028 + 1207 subtracting reverse of equation (ii) from it and
= + 179 kJ mol–1 dividing the equation so formed by 2.
2C(s) + 2O2(g) → 2CO2(g) ; ∆H° = −2x kJ
20. C + O2 → CO2 ; ∆H = −393.5 kJ
2CO2(g) → 2CO(g) + O2(g) ; ∆H° = +y kJ
Heat released in the formation of 1 mole (i.e., 44
g) of CO2 is −393.5 kJ 2C(s) + O2(g) → 2CO(g) ; ∆H° = (y – 2x) kJ
∴ Heat released in the formation of 35.2 g of CO2 Required equation:
−393.5 × 35.2 1 (y − 2x)
= = − 314.8 kJ ≈ − 315 kJ C(s) + O2(g) → CO(g); ∆H° = kJ
44 2 2
29


25. i. C(s) + O2(g) → CO2(g) ; 35. ∆G = ∆H – T∆S
∆H = −393.5 kJ mol−1 ∆H = 30.58 kJ, ∆S = 66.1 J K–1 = 0.0661 kJ K–1
ii. CO(g) +
1
O2(g) → CO2(g) ; At equilibrium, ∆G = 0
2 ∴ 0 = ∆H – T∆S
∆H = −283.5 kJ mol−1 ∆H 30.58
T= = = 462.6 K
Required equation is ∆S 0.0661
1
C(s) + O2(g) → CO(g) ; ∆H = ? 36. ∆H = − 400 kJ mol−1
2
∆S = − 20 kJ mol−1 K−1
It may be achieved by applying the operation:
Since, both ∆H and ∆S are negative, the reaction
(i) + (−ii).
will be spontaneous at lower temperatures.
∴ ∆H = −393.5 + (+283.5) = −110.0 kJ mol−1 The temperature at which change over between
1 spontaneous and nonspontaneous behaviour
26. H2(g) + O2(g) →H2O(l) ; ∆H = –286 kJ ….(i)
2 ∆H
occurs is calculated as : T =
H2O(s) → H2O(l); ∆fusH = +6 kJ ….(ii) ∆S
Equation (i) + Reverse of Equation (ii) gives, −400 kJ mol−1
1 ∴ T=
H2(g) + O2(g) →H2O(s) ; ∆H = (–286 – 6) kJ −20 kJ mol−1 K −1
2
= –292 kJ ∴ T = 20 K
∴ ∆H for formation of 1 mol of ice is –292 kJ. Thus, the given reaction is spontaneous below 20 K.
i.e, ∆H for formation of 18 g of ice is –292 kJ. 37. ΔH = 400 kJ mol–1,
∴ ∆H for formation of 100 g of ice ΔS = 400 J K–1 mol–1 = 0.4 kJ K–1 mol–1
100 ΔH 400
= –292 × = –1622 kJ T= = = 1000 K
18 ΔS 0.4
28. 2H(g) → H2(g) Thus, the given reaction is spontaneous above
Here, the number of gaseous moles decreases. 1000 K (i.e. option A is the correct answer).
Hence, entropy change is negative. 38. ∆H = 35.5 kJ mol–1
29. ∆H = ∆U + ∆ngRT ∆S = 83.6 J K–1 mol–1
∆H = 2.1 + ( 2 × 1.98 × 10–3 × 300) = 0.0836 kJ K–1 mol–1
∴ ∆H = 3.28 kcal Since, both ∆H and ∆S are positive, the reaction
∆G = ∆H − T∆S will be spontaneous at higher temperatures. The
= 3.28 − (300 × 20 × 10–3) temperature at which change over between
= –2.72 kcal ≈ –2.7 kcal spontaneous and non–spontaneous behaviour
occurs is calculated as:
30. For the given reaction, X2Y4(l) → 2XY2(g) ΔH 35.5 kJ mol−1
∆ng = 2 − 0 = 2 T= = = 425 K
ΔS 0.0836 kJ K −1 mol−1
For the given reaction,
Thus, the given reaction is spontaneous at
∆H = ∆U + ∆ngRT ….(i)
T > 425 K.
Substituting the values in equation (i),
∆H = 2 + [2 × (2 × 10−3) × 300] 39. ∆G = ∆G° + RT ln Q ….(i)
( R = 1.987 cal K−1 mol−1 ≈ 2 cal K−1 mol−1 At equilibrium ∆G = 0 and Q = K,
thus equation (i) becomes,
≈ 2 × 10−3 kCal K−1 mol−1) 0 = ∆G° + RT ln K
∆H = 2 + [1.2] = 3.2 kCal = 3.2 × 103 Cal ∴ ∆G° = −RT ln K = − 2.303 RT log10 K
∆G = ∆H − T∆S ….(ii)
Substituting the values in equation (ii), 40. K < 1.0 indicates that the concentration of
∆G = 3.2 × 103 − (300 × 20) = 3200 − 6000 reactants is greater than that of the products, i.e.,
∆G = − 2800 Cal the reaction does not proceed in the forward
direction. Hence, the reaction is nonspontaneous
32. At equilibrium, ∆G = 0. Hence, ∆H = T∆S. and ∆G° is positive.
33. During the adsorption of gas, degree of 41. ∆G° = –2.303 RT log10 Ksp
randomness decreases as the gas molecules 63.3 = −2.303 × 8.314 × 10–3 × 298 × log10 Ksp
adhere together. Thus, ∆S is negative which 63.3
implies that ∆H is also highly negative log10 Ksp =
2.303 × 8.314 × 10−3 × 298
( ∆G = ∆H − T∆S and for spontaneous process, log10 Ksp = −11.09
∆G < 0) Ksp = Antilog (−11.09) = 8.0 × 10–12
30


42. The entropy change of a system in a process is 48. Combustion of benzene:
equal to the amount of heat transferred to it in a 15
reversible manner divided by the temperature at C6H6(l) + O2(g) → 6CO2(g) + 3H2O(l)
2
which the process occurs.
15
∴ ∆S =
Q rev ∆ng = (np – nr)g =  6 −  = –1.5
 2
T
Now, Qrev for an isothermal change is given as: Heat of combustion at constant pressure = ∆H
 Pi  Heat of combustion at constant volume = ∆U
Qrev = −Wmax = nRT ln  
 Pf  ∆H = ∆U + ∆nRT
P  = –3263.9 + (–1.5) × 8.314 × 10–3 × 298
nRT ln  i 
 Pf  = nR ln  Pi  = –3267.6 kJ mol–1
∴ ∆S =  
T  Pf 
49. The ratio of bond dissociation energies of X2,
44. Enthalpy change of a reaction is given as Y2 and XY is 1:0.5:1.
∆H (oreaction ) = Energy required to break reactant ⸫ ∆H (X–X) = x, ∆H (Y–Y) = 0.5x
bonds – energy required to break product bonds ∆H (X–Y) = x
∴ o
∆H =
( reaction ) ∑H (
o
reactant bonds )
−∑H o
( product bonds ) The chemical equation for formation of XY is
1 1
45. ∆solnH = ∆LH + ∆hydraH X2 + Y2 → XY
2 2
= 777.8 – 774 = 3.8 kJ mol–1
The free energy change (∆G) in dissolving one ∆H = Σn∆H(reactant bonds)
mole of NaCl is calculated as follows: – Σn∆H(product bonds)
∆G = ∆H – T∆S 1 1
⸫ –200 =  ΔH ( X − X ) + ΔH ( Y − Y ) 
∆H = 3.8 kJ mol−1 ; ∆S = 0.043 kJ K−1 mol−1 2 2 
∴ ∆G = 3.8 – (298 × 0.043) – ∆H (X – Y)
= – 9.014 kJ mol–1
1 1 
≈ – 9.1 kJ mol–1 ⸫ –200 =  x + × 0.5 x  – x
2 2 
46. In liquid state, the constituent particles are held
⸫ x = 800 kJ mol–1
together by intermolecular forces of attraction.
Energy is required to overcome these attractive
50. ∆G° = –RT ln K
forces between the particles in liquid state and
to convert it to gaseous state. The value of heat Now, ∆G° = ∆H° – T∆S°
of vaporization gives the quantity of heat ⸫ ∆H° – T∆S° = –RT ln K
absorbed when one mole of a substance in liquid ΔH o ΔSo
state is converted to its gaseous state. Larger the ⸫ ln K = – +
RT R
value of heat of vaporization, stronger is the
intermolecular forces between the particles. When the temperature range is small, ∆H° and
Hence, the order of intermolecular forces in the ∆S° can be considered constant, hence the
given liquids is H2O > C2H5OH > CS2. equation gives in K as a linear function of
1
T
V2
47. Qrev = – Wmax = 2.303 × nRT log10  −ΔH o  1 ΔSo
V1 ln K =  × +
 R  T R
n = 2, R = 8.314 J K–1 mol–1, T = 27 + 273 = 300 K
V1 = 10 L, V2 = 100 L
Slope Intercept
 100 
∴ Qrev = 2.303 × 2 × 8.314 × 300 × log10  
 10  For an exothermic reaction, enthalpy change is
= 2.303 × 2 × 8.314 × 300 × log10 (10) 1
negative. Therefore, the plot of ln K versus
= 2.303 × 2 × 8.314 × 300 T
Q rev will have a positive slope.
∆S =
T Hence, the lines A and B correctly show the
2.303 × 2 × 8.314 × 300 temperature dependence of equilibrium constant
∴ ∆S = (K) for an exothermic reaction.
300
= 38.3 J K–1
31


H 70. The required reaction is 2C(s) + H2(g) → C2H2(g),
|
65. N ≡ N + 3H − H 
→ 2N − H Applying the operation (i) + (ii) + (–iii), by Hess’s
945 + 3× 436 = 2253 |
H law of constant heat summation; we get,
Energy absorbed 2 × (3 × 391) = 2346
∆rH = ∆H1 + ∆H2 + ∆H3
Energy released = (– 767) + (– 266) + (1290) = 257 kJ
Enthalpy of the reaction = 2253 − 2346
71. Given:
= − 93 kJ
1
66. Adding equation (i) + equation (ii) gives i. H2(g) + O2(g) → H2O(l); ∆rH = – 240 kJ
2
–110.5 + (−283.2) kJ = −393.7 kJ 17
ii. C6H10(l) + O2(g) → 6CO2(g)+ 5H2O(l);
67. 2C(s) + 3H2(g) → C2H6(g) ; ∆H = −30.2 kcal 2
… (i) ∆rH= –3800 kJ
2C(s) + 2H2(g) → C2H4(g) ; ∆H = +12.5 kcal iii. C6H12(l) + 9O2(g) → 6CO2(g) + 6H2O(l);
… (ii) ∆rH= – 3920 kJ
Required equation: Required equation is C6H10(l) + H2(g) → C6H12(l);
C2H4(g) + H2(g) → C2H6(g) ; is obtained by ∆rH = ?
reversing equation (ii) and adding it to (i), It may be achieved by the operation (i) + (ii) – (iii).
C2H4(g) → 2C(s) + 2H2(g); ∆H = −12.5 kcal ∆rH = (– 240) + (– 3800) – (− 3920)
2C(s) + 3H2(g) → C2H6(g); ∆H = −30.2 kcal = – 4040 + 3920 = – 120 kJ
C2H4(g) + H2(g) → C2H6(g) ; ∆H = −42.7 kcal 72. Reverse equation (iv), rewrite equation (i),
68. CH4 + 2O2 → CO2 + 2H2O, ∆H = – 890.4 kJ multiply equation (iii) and (ii) by 3, and adding
….(i) all the equations, we get,
C + O2 → CO2, ∆H = – 395.5 kJ ....(ii) B2H6(g) → 2B(s) + 3H2(g) ; ∆H = − 36 kJ mol−1
1 3
H2 + O2 → H2O, ∆H = – 285.8 kJ ....(iii) 2B(s) + O2(g) → B2O3(s);
2 2
from (i), (ii), (iii). ∆H = − 1273 kJ mol−1
∆cH (CH4) = ∆fH (CO2) + 2∆fH (H2O) 3H2O(l) → 3H2O(g) ;
– ∆fH (CH4) – 2∆fH (O2) ∆H = 44 × 3 = 132 kJ mol−1
– 890.4 = – 395.5 + 2(– 285.5) – ∆fH (CH4) 3
3H2(g) + O2(g) → 3H2 O(l) ;
–2×0 2
∆fH (CH4) = – 76.1 kJ mol −1 ∆H = − 286 × 3 = − 858 kJ mol−1
69. 2C(s) + 3H2(g) → C2H6(g); ∆rH = −21.1 kcal B2H6(g) + 3O2(g) → B2O3(g) + 3H2O(g)
….(i) ∆cH = − 36 − 1273 + 132 − 858
C(s) + O2(g) → CO2(g); ∆rH = −94.1 kcal = − 2167 + 132 = − 2035 kJ mol−1
….(ii)
3
73. 2B(s) + O2(g) → B2O3(s), ∆fH°
1 2
H2(g) + O2(g) → H2O(l); ∆rH = −68.3 kcal 3 1
2 B(s) + O2(g) → B2O3(s), ∆cH°
….(iii) 4 2
Required equation: 1
∆cH° (of solid boron) = ∆ f H°(B2O3 )
7 2
C2H6(g) + O2(g) → 2CO2(g) + 3H2O(l) ;
2
74. When ∆Stotal = + ve, the change is spontaneous
∆H = ?
Required equation is obtained by reversing 76. Randomness decreases in the case of
equation (i), multiplying equation (ii) by 2 and crystallization of sucrose from solution.
equation (iii) by 3 and adding all the equations.
C2H6(g) → 2C(s) + 3H2(g); ∆rH= +21.1 kcal o ( −238.6 kJ )
78. ΔSsurr = – ∆H = –
2C(s) + 2O2(g) → 2CO2(g) ;∆rH = −188.2 kcal T 298 K
3 = +0.8007 kJ K–1 = +800.7 J K–1
3H2(g) + O2(g) → 3H2O(l);∆rH = –204.9 kcal
2 ΔStotal = ΔSsys + ΔSsurr
= +36.7 J K–1 + 800.7 J K–1
7
C2H6(g) + O2(g) → 2CO2(g) + 3H2O(l) ; = +837.4 J K–1
2
∆rH = –372 kcal 79. For reverse reaction, sign will change.
27


80. ∆G = ∆H – T∆S = 145600 – 300 × 116 3. W = – Pext ∆V
= 145600 – 34800 = 1 × 105 × (1 × 10–2 – 1 × 10–3)
= 110.8 kJ mol−1 = – 1 × 105 × 9 × 10–3 N m = – 900 J
82. If ∆G = – ve, reaction is spontaneous. 5. ∆U = Q + W
84. ∆G = ∆H – T∆S = 9.08 – (298 × 0.0357) 0=Q+W
= –1.56 kJ mol−1 (∆U = 0, for isothermal process)
Since, the value of ∆G is negative, the reaction ∴ Q=–W
is spontaneous at 298 K.
Also, ∆H = + ve, therefore, the reaction is 6. ∆U = Q + W
endothermic. ∆U = Q − Pext.∆V ( W = −Pext.∆V)
85. ∆G = 0, for equilibrium process. For an isochoric process, ∆V = 0,
∴ ∆U = Qv
86. W = −Pext.∆V
= −1 bar (6 dm3 – 2 dm3) = −4 dm3 bar 7. In an adiabatic process, no heat is allowed to
= −4 × 100 J = −400 J enter or leave the system. Hence, Q = 0.
∆U = Q + W= 800 J + (−400) J = +400 J According to first law of thermodynamics,
∆U = Q + W
87. Since one mole of an ideal gas is compressed
∴ ∆U = W
isothermally, ∆U = 0 for reversible process.
∴ ∆U = Q + W = 0 8. In an adiabatic process, no heat is allowed to
∴ Q = −W enter or leave the system.
 P1  Hence, Q = 0
Wmax = − 2.303 nRT log10   From the 1st law of thermodynamics,
 P2 
ΔU = Q + W
 2 ∴ ΔU = W
= −2.303 × 1 × 8.314 × 302 × log10  
 10 
9. In an adiabatic process, there is no exchange of
= –2.303 × 1 × 8.314 × 302 × (–0.6989)
= 4041.74 J heat between the system and its surroundings.
So, Q = 0.
= (4041.74 × 0.239) cal = 966 cal
According to first law of thermodynamics,
∴ Q = −966 cal
∆U = Q + W
88. 50% of 880 kJ = 440 kJ ∴ ∆U = W or −∆U = −W (For adiabatic process)
Since ∆evpH = 44 kJ mol−1 , 440 kJ will require Since, the given process is adiabatic expansion,
440 the work is done by the system on the
= 10 moles of water.
44 surroundings at the expense of system’s internal
One mole of water = 18 g energy. Hence, the internal energy of the system
∴ 10 moles = 10 × 18 = 180 g decreases in this process.
89. In the formation of acetaldehyde from its ∴ For adiabatic expansion, −∆U = −W.
constituent elements, i.e., ∆U < 0
1 10. ∆U = Q + W = –15 kJ + (–10 kJ) = –25 kJ
2C(s) + 2H2(g) + O2(g) → CH3CHO(l);
2
 1 11. ∆H = ∆U + ∆ngRT
∆ng = 0 −  2 +  = −2.5 H2 − H1 = U2 − U1 + n2 − n1(RT)
 2
∴ H2 − H1 + U1 − U2 = n2RT − n1RT
90. As formation of graphite is an exothermic
reaction, there is lowering of energy. So, 12. ΔH = ΔU + ΔngRT
graphite is more stable than diamond. In the reaction given in option (D),
Δng = 1 – 0 = 1
∴ ΔH > ΔU
Competitive Thinking 13. ∆H = ∆U + ∆ngRT
2. 1 dm = 0.1 m ∴ ∆U = ∆H – ∆ngRT
1 dm3 = 0.001 m3 = 19 – (5–3) × 2.0 kcal mol–1
∴ 10 dm3 = 0.01 m3 × 10–3 kcal K–1 mol–1× 300 K
W = – Pext ∆V = 19 kcal – 1.19 kcal
= – 100 kPa (0.01 –1) m3 = 99 kJ = 17.8 kcal
28

V2 19. For the given reaction, X2Y4(l) → 2XY2(g)

3. Wmax = −2.303 nRT log10
V1 ∆ng = 2 − 0 = 2
∆H = ∆U + ∆ngRT
 Mass  V2
= −2.303   RT log10 ∆H = 20 + [2 × (2 × 10−3) × 400]
 Molar mass  V1
= 20 + 1.6 = 21.6 kCal
1 ∆G = ∆H − T∆S
Wmax ∝
Molar mass ∆G = 21.6 × 103 − (400 × 60) = 21600 − 24000
∴ Lower the molar mass, higher the magnitude of ∆G = − 2400 Cal
work.
∴ Maximum work is done in the case of CH4. 20. Wmax = − 2.303nRT log10 V2
V1
5. ∆rH° = ∑H o
− ∑H o = − 2.303 × n × 8.314 × 298
( reactant bonds ) ( product bonds )
= (433 + 192) – (364) × log10 40 J/mole
= – 103 kJ 20
= − 2.303 × 8.314 × 107 × 298 × log10 2
7. Required equation is × n ergs/mole. ( 1 Joule = 107 ergs)
C(graphite) + O2(g) → CO2(g)
Adding equation (i) + equation (ii) gives
–110.5 + (−283.2) kJ = −393.7 kJ
8. ∆G = ∆H – T∆S
∆G = 0 at equilibrium
∴ ∆H = T∆S or 30.56 = T × 0.06
T = 509 K
9. According to first law of thermodynamics,
∆U = Q + W
= (+5 kJ) + (–2 kJ)
= +3 kJ
11. Reversing equation (i),
SiO2(s) → Si(s) + O2(g) ; ∆rH° = 911 kJ
Adding equation (ii) and (iii) to this equation,
SiO2(s) + 3C(s) → SiC(s) + 2CO(g)
∆rH° = 911 + (– 221) + (– 65.3)
= 624.7 kJ
12. ∆G° = ∆H° – T∆S°
∆G° = – 364.5 – (– 200 × 10–3 × 298)
= – 304.9 kJ mol–1
13. In the given reaction, ∆ng = 3 − (5 + 1) = −3
∴ ∆H = ∆U − 3RT
15. The enthalpy of a reaction can be positive or
negative depending on ΣHproducts and ΣHreactants.
16. V2 = 100 cm3 = 0.1 dm3
V1 = 1 dm3
W = − pex ∆V = −3.2 × (0.1 − 1)
= + 2.88 dm3 bar = + 2.88 × 102 J
18. Qp, G and S are state functions.
32

Chapter 5: Electrochemistry
13. When molten metal chloride undergoes E ocell E ocathode − E anode
19. =
o
= E oCo − E oMn
electrolysis, at cathode, X3+ ions from MF3 get
reduced as follows: = 1.82 V – (–1.18 V) = 3.00 V
X3+ + 3e– → X
1 mol 20. Mg ( s ) Mg (2aq+ ) Cl(−aq ) Cl2( g ) (1atm ) Pt
Hence, Mole ratio =
3 mol e − Oxidation : Mg → Mg2+ + 2e−
Mass of X formed, Reduction : Cl2 + 2e− → 2Cl−
I ( A ) × t (s)
W= −
× mole ratio × molar mass of X
96500 (C / mol e )
Cell reaction: Mg(s) + Cl2(g) → Mg (2aq+ ) + 2Cl(−aq )
0.75 = 3.9 ×9.65 × 60 × 1 × Molar mass of X
96500 3 Nernst equation:
0.75 × 96500 × 3 2
Molar mass of X = 0.0592 Cl−   Mg 2 + 
log10   
o
3.9 × 9.65 × 60 Ecell = E cell −
= 96.15 g mol−1 2 PCl2
2
14. 2H+ + 2e− → H2 0.0592 Cl−   Mg 2 + 
log10   
o
= E cell –
molesof product 1 2 1
(mole ratio)1 = =
molesof e −
2 o 0.0592
= E cell – log10 [Cl–]2 [Mg2+]
Ca2+ + 2e− → Ca 2
molesof product 1
(mole ratio)2 = =
molesof e − 2 E ocell E ocathode − E anode
21. =
o
W1 W2 o o
= = E Ag − E= 0.800V + 0.136 V = 0.936 V
( mole ratio )1 × M1 ( mole ratio )2 × M 2 Sn
W1 2 1
The cell potential is given by
= = 0.0592 V [Sn 2 + ]
W2 40 20 Ecell = E ocell − log10
∴ H : Ca = 1:20 2 [Ag + ]2
0.0592 V 1
15. Cell I: Ecell = 0.936 V – log10 2
Mercuric perchlorate Hg(ClO4)2 → Hg2+ 2 (1)
Cell II: = 0.936 V [since log10 (1) = 0]
Mercuric nitrate Hg(NO3)2 → Hg2+
Cell III: The cell potential equals standard cell potential
Mercurous perchlorate Hg2(ClO4)2 →Hg+ if the concentrations of reactants and products
Hg2+ + 2e− → Hg are 1 M each.
Hg+ + e− → Hg
W 2+ : W 2+ : W + 0.0592 [Zn]
Hg Hg Hg 22. Eel = E oel − log
n [Zn 2 + ]
= ( mole ratio )Hg2 + : ( mole ratio )Hg2 + :
0.0592 1
( mole ratio )Hg+ = − 0.76 − log
2 0.1
1 1
= : :1 = − 0.76 − 0.0296 = − 0.789 V
2 2
∴ The amount of mercury deposited, will be same 23. Overall cell reaction for a Daniel cell can be
in cell I and II but more in cell III. given as,
16. The anode (–) is written at the extreme left and Zn(s) + Cu (aq)
2+
→ Zn (aq)
2+
+ Cu (s)
cathode (+) at extreme right.
At 298 K,
18. 2+
Cu (s) | Cu (aq) 2+
Hg (aq) Hg ( l )
0.0592  Zn 2 + 
∴ Ecell = E cell – log
Oxidation always occurs at anode while 2 Cu 2 + 
reduction occurs at cathode.
∴ When the concentrations of both Zn2+ and Cu2+
Oxidation
 Zn  2+
2+ 2+ are doubled, the ratio  2 +  remains unaltered.

Cu + Hg 
→ Cu + Hg Cu 
Reduction ∴ e.m.f of the cell remains constant.

35

25. E° = 0.0592 log10 K 5. k = 5.76 × 10−3 S cm−1

n k × 1000 5.76 × 10−3 × 1000
0.0592 ∧ = =
= log10 K c 0.5
3 = 11.52 S cm2 mol−1
0.0592
0.592 = log10 K 1000k
3 6. ∧=
c
0.592 × 3
log10 K = = 30 L 1000cm3L−1
0.0592 = = 105 cm3 mol–1
K = 1030 k 0.01molL−1
28. The overall reaction involves only solid 7. The conductivity of solution decreases on dilution.
substances. 8. According to Kohlrausch law,
29. The species on the left side of half reactions in ∧ 0m (CH3COOH) = λ 0m (CH3COO–) + λ 0m (H+)
electrochemical series are oxidizing agents.
∴ ∧ 0m (CH3COOH)
30. Lower is the reduction potential, greater is the 1 0
0
reducing power. Hence, the increasing order of = ∧ m (CH3COOK) +
∧ m (H2SO4)
2
reducing power is Au < Pb < Mg.
1
31. Cell reaction is: − ∧ 0m (K2SO4)
2
Sn + Pb2+ → Sn2+ + Pb x y x − y
 
E ocell E ocathode − E anode
= o
= –0.13 – (– 0.14) = 0.01 V =z+ − =z+  
2 2  2 
Nernst equation is:
2.303 RT [Product] ∧
Ecell = E ocell − log10 9. Degree of dissociation (α) =
nF [Reactant] ∧0
At equilibrium, Ecell = 0 150
= = 0.3
2.303 RT [Product] 500
∴ E ocell = log10
nF [Reactant] α 2c
Dissociation constant of HF (Ka) =
0.06 [Sn 2 + ] 1− α
∴ 0.01 = log10
2 [Pb 2 + ] (0.3) 2 × 0.007
=
[Sn 2 + ] 1 1 − 0.3
∴ log10 = = 9 × 10−4
[Pb 2 + ] 3
[Sn 2 + ] 1 10. The cell constant is determined by using 1 M,
∴ =2+
10
= 3 3
10
0.1 M (i.e., 10−1 M) or 0.01 M (i.e., 10−2 M) KCl
[Pb ]
solution.
0.0592
32. Eox = E oox − log10 ([H + ]4 × Po 2 ) l
n 12. Cell constant =
a
0.0592
∴ Eox = – 1.23 – × log10 [H+]4 l 0.98
4 a= = = 1.96 cm2
cell constant 0.5
0.0592
= – 1.23 – × 4 × log10 [H+]
4 13. i. For given 0.2 M solution,
= – 1.23 + 0.0592 × pH Resistance (R) = 50 Ω,
= – 1.23 + 0.0592 × 5 Specific conductance (k) = 1.4 S m−1
= – 1.23 + 0.296 = – 0.934 V Cell constant = k × R
= 1.4 S m−1 × 50 Ω = 70 m−1
ii. For given 0.5 M solution,
Competitive Thinking Resistance (R) = 280 Ω
Specific conductance (k)
a
2. G=k cell constant 70 m −1
l = = = 0.25 S m−1
R 280 Ω
∴ G = k. a . l−1
mol
4. Molar conductivity (∧) Concentration (c) = 0.5
dm3
1000k 1000cm3L−1 × 1.41 × 10−3 Scm −1 mol
= = = 0.5 × 103
c 0.1molL−1 m3
= 14.1 S cm2 mol–1 = 500 mol m−3
36

Molar conductivity (∧) Electricity required (Q)
k = Moles of electrons actually passed
= S m2 mol−1
c × 96500 C / mol e–
0.25 Sm −1 ∴ Q = 2 mol e × 96500 C / mol e–
–
= = 5 × 10−4 S m2 mol−1 = 1.93 × 105 C
500 molm −3
15. In the electrolysis of concentrated aqueous 21. Ca2+ + 2e− → Ca

solution of NaCl, Na+ ions combine with OH– 2 F will deposit 1 mole Ca (i.e., 40 g of Ca)
ions to form NaOH solution. Thus, the resulting Hence, 0.5 F of electricity will be required to
solution is basic and it turns red litmus into blue. deposit 10 g of Ca from molten CaCl2 when
inert electrodes are used.
16. Number of moles of electrons passed
I×t 2 × 20 × 60 22. Cu2+ + 2e− → Cu
= = = 2.487 × 10–2 mol e− So, 2 F charge deposits 1 mol of Cu.
96500 96500
∴ Mass deposited = 63.5 g.
17. Mn+ + ne− → M
1 mole of Mn+ ions carries a charge 23. At anode: 2Cl− → Cl2 + 2e−
= n × 96500 C ∴ 2 F (i.e., 2 × 96500 C) of electricity is required
∴ 1 millimole of Mn+ ions will carry charge to produce 1 mol of Cl2 gas.
= n × 96500 × 10−3 C ∴ 0.2 F (i.e., 0.2 × 96500 C) of electricity will be
However, charge carried by 1 millimole of Mn+ required to produce 0.1 mol of Cl2 gas.
ions is given to be 193 C. Now, Q = I × t
∴ 193 = n × 96500 × 10−3 ∴ 0.2 × 96500 = 3 × t
∴ n= 193
=2 ∴ t = 6433.3 seconds = 107.2 minutes
96500 × 10−3 ≈ 110 minutes
18. The magnitude of charge on an electron 24. At cathode Ca2+ ions from CaCl2 get reduced as
= 1.6 × 10−19 C follows:
∴ One coulomb equals the charge of Ca2+ + 2e– → Ca
1 1 mol
= 6.25 × 1018 electrons Hence, Mole ratio =
1.6 × 10−19 2 mol e −
1C = 1 Ampere × 1 second Mass of Ca formed,
∴ 6.25 × 1018 electrons ≡ 1 Ampere × 1 second I ( A ) × t (s)
W= × mole ratio × molar mass of Ca
∴ Current of 1 ampere in 60 seconds 96500 (C / mol e )
−
≡ 6.25 × 1018 × 60 = 3.75 × 1020 electrons

W = 0.005 ×200 × 1 × 40 = 0.0002073 g of Ca
19. 0.1 M FeSO4 is given i.e., 1000 mL of solution 96500 2
contains 0.1 mole of FeSO4
25. Cu2+ + 2e− → Cu
∴ 20 mL of solution will contain = 2 × 10−3 moles So, 2 F charge deposits 1 mol of Cu
of FeSO4
i.e., 2 × 96500 C charge deposits 1 mol of Cu
2 × 10−3 moles of FeSO4 contains 2 × 10−3
19296
moles of Fe2+. ∴ 19296 C will deposit =
2 × 96500
The oxidation reaction of Fe2+ can be given as,
Fe2+ → Fe3+ + e− = 99.979 ≈ 0.1 mol
∴ 1 mole of Fe2+ gives 1 mole of e– on oxidation. 1 mol of Cu ≡ 63.5 g
∴ Moles of electrons required to oxidise 2 × 10−3 ∴ 0.1 mol of Cu = 63.5 × 0.1 = 6.35 g
moles of Fe2+ ∴ Mass of Cu deposited at the cathode is 6.35 g.
= 1 × 2 × 10−3 Alternate method:
= 2 × 10−3 moles of electrons Mass of Ca formed,
∴ Number of electrons Q(C)
W= −
× mole ratio × molar mass of Cu
= 2 × 10−3 × 6.022 × 1023 96500 (C / mol e )
= 12.04 × 1020 W = 19296 × 1 × 63.5 = 6.35 g of Cu

= 1.204 × 1021 electrons. 96500 2
1 26. Q = It = 1.93 × 500 = 965 coulombs

20. H2O → 2H+ + 2e− + O2
2 1 mole of electron = 96500 coulombs
For the oxidation of one mole of water to 965
∴ 965 coulombs = = 0.01 mole of electrons
dioxygen, 2 mole electrons are required. 96500
37


∴ At cathode; Cu2+ + 2e− → Cu W1 18
=
2 moles of electron give 1 mole of Cu. 1
2 × 58.5 13 × 27
0.01 18 58.5
∴ 0.01 mole of electron will give = = 0.005 W1 = × =58.5 g
2 9 2
mole of Cu.
Mass of Cu deposited 31. Salt bridge maintains electrical neutrality in
= no. of moles of Cu × atomic mass of Cu both the solutions by transfer of ions. It is a tube
= 0.005 × 63.5 = 0.3175 ≈ 0.315 g containing a saturated solution of an inert
At cathode, Ag+ + e− → Ag electrolyte such as KCl or NH4NO3 and 5 %
1 mole of electron gives 1 mole of Cu. agar solution.
∴ 0.01 mole of electron will give = 0.01 mole of 32. The cell is galvanic cell, hence, the +ve
Ag electrode is the cathode, where the reduction
Mass of Ag deposited = 0.01 × 107.87 = 1.08 g reaction occurs.
27. Zn2+ + 2e– → Zn ∴ The reaction that occurs at +ve electrode is
Al3+ + 3e– → Al Fe3+ + e− → Fe2+
Ag+ + e– → Ag Since, the electrode is Fe3+, Fe2+ | Pt
∴ The quantity of electricity needed to separately
electrolyze 1 M solution of ZnSO4, AlCl3 and 33. For the given cell,
AgNO3 completely is in the ratio of 2 : 3 : 1. At Anode : Pb → Pb2+ + 2e– (oxidation)
At Cathode : 2Ag + 2e– → 2Ag (reduction)
28. Al3+ + 3e– → Al
∴ Pb is undergoing oxidation and hence, acting as
Ag+ + e– → Ag a reducing agent.
Mg2+ + 2e– → Mg
If one mole of electron is passed, then the ratio 34. E° = 1.5 V
Au3 + |Au
of mass of Al, Ag, Mg deposited will be
1 1 1 E°
Sn 4 + |Sn 2 +
= 0.15 V
: : =2:6:3
3 1 2 Since E °Au3+ |Au is greater than ESn 4 + |Sn 2 + ,
°
29. At STP, Au3+ will undergo reduction while Sn2+ will

22,400 mL of O2 ≡ 32 g of O2 (1 mol of O2). undergo oxidation.
∴ 5600 mL of O2 ≡ 8 g of O2 at STP. Au3+ → Au
∴ Weight of O2 displaced = 8 grams Sn2+ → Sn4+
2O2− → O2 + 4e−
∴ net reaction is,
molesof product 1
(mole ratio)1 = = Sn2+ + Au3+ → Sn4+ + Au
molesof e −
4
Ag+ + e– → Ag 35. For the given electrochemical cell, the oxidation
molesof product reaction at anode, reduction reaction at cathode
(mole ratio)2 = =1 and overall cell reaction are as follows:
molesof e −
2Ag → 2Ag+ + 2e− (Oxidation at anode)
W1 W2 +2 −
= Zn + 2e → Zn (Reduction at cathode)
( mole ratio )1 × M1 ( mole ratio )2 × M 2
8 W2
= 2Ag + Zn+2 → 2Ag+ + Zn
1
4 × 32 1 × 108 (Overall cell reaction)
W2 = 108 g ∴ The emf of the cell is given by
30. Nickel chloride: NiCl2 0.0592 [Ag + ]2
Ecell = E cell − log10
Ni2+ + 2e– → Ni n [Zn +2 ]
molesof product 1 Substituting the values in above equation,
(mole ratio)1 = =
molesof e − 2 0.0592 ( 0.1) 2
Aluminium chloride : AlCl3 Ecell = − 1.562 − log10
2 (0.1)
Al3+ + 3e– → Al 0.0592
molesof product 1 = − 1.562 − log10 10−1
(mole ratio)2 = = 2
molesof e − 3
0.0592
W1 W2 = − 1.562 − (−1)
= 2
( mole ratio )1 1 (
× M mole ratio )2 × M 2 = −1.562 + 0.0296 = − 1.5324 V
38

36. pH = 3 nRT [C ]
∴ Ecell = E ocell − log10 2
− log10 [H+] = 3 F [C1 ]
∴ [H+] = 10−3 E value of the cell will be maximum for the
The half cell reaction can be given as C2
Fe → Fe2+ + 2e− (oxidation) lowest value of .
C1
2H+ + ½ O2 + 2e− → H2O (reduction)
C1 = 0.1 M, C2 = 0.01 M
Multiply both the equations by 2.
C 0.01 M
2Fe → 2Fe2+ + 4e− ∴ =2
= 0.1
C1 0.1 M
4H+ + O2 + 4e− → 2H2O
40. Fe2+ | Fe, E° = – 0.44 V and
Fe3+ | Fe2+, E° = 0.77 V.
2Fe + 4H+ + O2 → 2Fe2+ + 2H2O
Since, Fe3+ | Fe2+ electrode has higher potential
0.592 [Fe 2 + ]2 than Fe2+ | Fe, Fe3+ | Fe2+ acts as cathode and
Ecell = E°cell − log10 + 4
n [H ] × P( O2 ) Fe2+ | Fe acts as anode.
0.0592 [10−3 ]2 Oxidation at anode: Fe → Fe2+ + 2e–, E° = 0.44 V
= 1.67 − log10 −3 4
4 [10 ] × 0.1 Reduction at cathode: 2Fe3+ + 2e–→ 2Fe2+, E° = 0.77 V
0.0592 10−6
= 1.67 − log10 −13 Overall reaction: Fe + 2Fe3+ → 3Fe2+, E° = 1.21 V
4 10
0.0592 E° for overall reaction is positive, hence the overall
= 1.67 − ×7
4 reaction is spontaneous. Therefore, if Fe2+, Fe3+ and Fe
= 1.67 − 0.103 blocks are kept together, it will lead to decrease in
Ecell = 1.57 V Fe3+.
37. For H2 electrode, 2H+ + 2e– → H2(g) 41. Mn2+ + 2e− → Mn E° = −1.18 V
0.0591 P 2Mn2+ → 2Mn3+ + 2e− E° = −1.51 V
∴ E H+ / H = E° – × log H2 2
2
2  H +  3Mn2+ → 2Mn3+ + Mn E° = −2.69 V
Now, E° = 0 for H2 electrode. As E° value is negative, the reaction will not
occur.
To make the potential of H2-electrode,
E + = 0, 42. ∆ r G o = –nF E ocell = –2 × 96500 × 0.24
H /H 2
0.0591 PH2 = –46320 J mol–1 = –46.32 kJ mol–1

0=0– × log
(10−7 )
2
2 43. 2Ag+ + Cu → 2Ag + Cu2+
0.0591 PH n=2
log −214 = 0 o
2 10 ΔG° = −nFE cell = − 2 × 96500 × 0.46
PH2 = − 88780 J ≈ − 89 kJ
log −14 = 0
10
44. Cr → Cr3+ + 3e− …(i)
PH2
∴ −14
= 1 ∴ PH2 = 10 atm Fe2+ + 2e− → Fe …(ii)
10−14 Multiply equation (i) by 2 and equation (ii) by 3
38. The cell reaction is Zn + Cu2+ → Zn2+ + Cu 2Cr → 2Cr3+ + 6e−
0.059 [Zn 2 + ] 3Fe2+ + 6e− → 3Fe
Ecell = E ocell – log10 . o
E= E oFe − E oCr
2 [Cu 2 + ] cell
When [Zn2+] is increased and [Cu2+] is decreased, = (−0.440) − (−0.740) = 0.3 V

2+
[Zn ] ∆G° = −n F E ocell
the term log10 increases.
[Cu 2 + ] = − 6 × 96500 × 0.3
Thus, E1 > E2. = −173700 J = −173.7 kJ
39. According to Nernst’s equation, 45. ΔG° = –nFE°
nRT [Products] Mn7+ + 5e– → Mn2+ …(i)
Ecell = E ocell − log10 [E° = 1.5 V]
F [Reactants]
For the given reaction: ΔG° = – 5 × F × 1.5 = −7.5F …(ii)
2+ 2+ Mn2+ → Mn4+ + 2e– …(iii)
Zn(s) + Cu (aq) 
 Cu(s) + Zn (aq) [E° = −1.2 V]
C1 = [Cu2+] and C2 = [Zn2+] ΔG° = – 2 × F × (−1.2) = 2.4F …(iv)
39


Adding equation (i) and (iii), 59. Strongest oxidizing agent will have higher
Mn7+ + 3e– → Mn4+ positive value of standard reduction potential.
On adding equation (ii) and (iv),
−7.5F + 2.4F = −5.1F 60. From the electrochemical series of standard
reduction potentials, Li is the strongest reducing
E° for Mn7+ + 3e– → Mn4+
agent. Therefore, Li+ is the weakest oxidizing
∆G o −5.1F
= = agent.
− nF −3F
E° = 1.7 V 61. Copper is placed above hydrogen in
2+ – electrochemical series and has reduction
46. Cu + 2e → Cu …. (i), E° = 0.34 V
potential of +0.153 V while zinc is placed below
∆G° = – 2 × F × 0.34 = – 0.68 F …. (ii)
hydrogen and has potential of –0.763 V.
Cu → Cu+ + e– …. (iii), E° = – 0.522 V
∴ The cell potential with Zn as electrode will be
∆G° = – 1 × F × (– 0.522) = 0.522 F …. (iv)
0.763 V while the cell potential with copper as
Adding equation (i) and (iii),
electrode will be 0.153 V. Hence the cell
Cu2+ + e– → Cu potential will decrease.
On adding equation (ii) and (iv),
– 0.68 F + 0.522 F = – 0.158 F 62. For hydrogen–oxygen fuel cell,
E° for Cu2+ + e– → Cu 1
Overall reaction: H2(g) + O2(g) → H2O(l)
∆G o − 0.158 F 2
= = Number of electrons (n) = 2
−nF −1F
E° = 0.158 V ∆G° = −nF E°cell
−∆G° −(−240 ×103 )
47.
o
ΔG° = −nFE cell = –RT ln K ∴ E°cell = = = 1.24 V
nF 2 × 96500
RT 1
∴ E ocell = × 2.303 × log10 K 63. Q = It = 1 × 965 = 965 coulombs
F n
1 1 mole of electron = 96500 coulombs
∴ 0.59 = 0.059 × log10 K 965
1 ∴ 965 coulombs = = 0.01 mole of electrons
0.59 96500
∴ log10 K = Mg2+ + 2e− → Mg
0.059
∴ log10 K = 10 2 moles of electron give 1 mole of Mg.
∴ K = 1 × 1010 0.01
∴ 0.01 mole of electron will give =
2
0.0592
48. E° = log K = 5 × 10–3 mole of Mg.
2
0.0592 Therefore, one litre solution had 5 × 10–3 moles
0.295 = log K of Mg.
2
0.295 × 2
So, the original concentration of MgCl2 solution
log K = = 9.96 = 5 × 10–3 M
0.0592
log K ≈ 10 64. Ca2+ (E° = −2.87 V) has lower reduction
K = Antilog [10] = 1 × 1010 potential than water (E° = −0.83 V). Hence it
cannot be reduced in aqueous solution. Instead
49. E ocell < 0, so it is a non-spontaneous process.
water will get reduced to liberate H2.
∴ ∆G° > 0 and Keq < 1. 1
H2O + e− → H2 + OH−
52. At cathode, the following reaction occurs: 2
PbO 2(S) + 4H (aq)
+
+ SO 24(aq)
−
+ 2e − → Ag+ (E° = 0.80 V), Cu2+ (E° = 0.34 V) and Cr3+
PbSO4(s) + 2H2O(l) (E° = −0.74 V) have higher reduction potential
Therefore, Pb4+ is reduced to Pb2+. than water. Hence, they can be reduced in
aqueous solution to obtain metals.
57. Lesser is the reduction potential, greater is the Cr3+ + 3e− → Cr
reducing power.
Ag+ + e− → Ag
∴ The correct order is B > C > A.
–0.80 V –0.46 V 0.34 V Cu2+ + 2e− → Cu
58. Lesser is the reduction potential greater is the b Molar conductivity S cm 2 mol−1
65. Slope = = =
reducing power. Hence, the decreasing order of a Concentration 1
reducing power is K > Al > Cr > Ag. ( mol L−1 ) 2

40


33. Since, Cu2+ undergoes reduction it is cathodic 6. ∧0 (CaCl2) = λ 0Ca 2+ + 2λ 0Cl−
reaction while Mg undergoes oxidation and
hence it is anodic reaction. = 104 Ω–1 cm2 mol–1 + 2 × 76.4 Ω–1 cm2 mol–1
Ecell = E °Cu 2 + |Cu − E °Mg2 + |Mg = 0.337 − (−2.37) = 256.8 Ω–1 cm2 mol–1
= 0.337 + 2.37 = 2.707 V ≈ 2.7 V 7. ∧0 (HA) = ∧0 (HCl) + ∧0 (NaA) – ∧0 (NaCl)

= 425.9 + 100.5 – 126.4
36. Electric work = amount of charge passed × cell
= 399.7 ≈ 400 S cm2 mol–1
potential
1000k
= nF × Ecell = nFEcell ∧=
c
37. E° is independent of the amount of substance 1000(cm3 L−1 ) × 5 × 10−5 (S cm −1 )
and is an intensive property. ∧=
0.001(mol L−1 )
39. SHE is used as a primary reference electrode to = 50 S cm2 mol−1
determine the standard potentials of other ∧c 50 S cm 2 mol−1
electrodes. The standard potential of this α= = = 0.125
electrode has arbitrarily been taken as zero. ∧0 400 S cm 2 mol−1
41. For hydrogen gas electrode, H(+aq ) | H 2 (g,PH2 ) | Pt, Cell constant 1.15
8. k= = = 0.0046 ohm−1 cm−1
+
[H ] and pressure of hydrogen gas differ from Resistance 250
unity. The molar conductance of the solution is given
Electrode reaction: by,
2H (+aq ) + 2e −  (
→ H 2 g,PH2 ) ∧=
1000k
=
1000(cm3 L−1 ) × 0.0046(ohm −1cm −1 )
c 0.1(mol L−1 )
From the Nernst equation
0.0592 PH2 0.0592 PH2 = 46 ohm−1 cm2 mol−1
E oH2 −
E H2 = log10 2
=
− log10 2
2  H +  2  H +  9. Depending upon the type of electrochemical cell,
anode and the cathode may be positive or
(since E oH2 = 0) negative.
45. The overall cell reaction occurring when lead 11. Al3+ + 3e− → Al
storage cell provides current is:
∴ 3 Faraday charge is required to deposit 27 g of Al.
Pb(s) + PbO2(s) + 2H2SO4(aq) → 2PbSO4(s) + 2H2O(l)
∴ x Faraday of charge is required to deposit
54. The strongest oxidising agent (F2) has the 4.5 × 10−5 g of Al.
largest (positive) standard reduction potential. 3 × 4.5 × 10−5
∴ x= Faraday
55. The fuel cells differ from ordinary galvanic cells 27
in that the reactants are not placed within the 1 Faraday = charge on 6.022 × 1023 electrons
cell. They are continuously supplied to ∴ Number of electrons required
electrodes from a reservoir.
3 × 4.5 × 10−5
= × 6.022 × 1023
27
Critical Thinking = 3.0 × 1018 electrons.
1. A reaction in which oxidation and reduction 12. At cathode:
occurs simultaneously is called a redox reaction.
Ni2+ + 2e– → Ni
In dry cells, chemical energy of spontaneous
reaction is converted to electrical energy. 1 mol
Hence, Mole ratio =
Electroplating is used for coating one metal on 2 mol e −
surface of another. Mass of Ni formed,
I ( A ) × t (s)
4. ∧ = 1000k W= −
× mole ratio × molar mass of Ni
c 96500 (C / mol e )
1000 × k
c= = 1000 × 2.428 × 10−3 = 0.02 M 5.85 = 10 ×t × 1 × 58.5
∧ 121.4 96500 2
5. Molar conductivity increases with decrease in 5.85 × 96500 × 2

Time (t) = = 1930 s
concentration of solution. 10 × 58.5
34

06 Chemical Kinetics
Hints
0.125 Ms–1 = k × 2.0 M × (0.4 M)2

Classical Thinking ∴ k=
0.125M / s
= 0.39 M–2 s–1
2M × 0.16M 2
2. As the reaction progresses, the concentration of
the reactants decreases and the concentration of 12. Rate = 3.25 × 10–6 mol L–1 s–1
the product increases. [NOBr] = 1 × 10–3 mol L–1
3. Negative sign indicates the decrease in Rate = k[NOBr]2
concentration of the reactant with time. rate
k=
[NOBr]2
6. N2(g) + 3H2(g) → 2NH3(g)
3.25 × 10−6 mo L−1s −1
d[N 2 ] 1 d[H 2 ] 1 d[NH 3 ] =
rate = − =
− = (1 × 10−3 mol L−1 ) 2
dt 3 dt 2 dt
1 d[H 2 ] 1 d[NH 3 ]
= 3.25 mol–1 L1 s–1
∴ − =
3 dt 2 dt 13. (rate)1 = k [A] [B]
d[NH 3 ] 2 d[H 2 ] (rate)2 = k [2A] [B]
= −
dt 3 dt = 2 k [A] [B]
= 2 × (rate)1
∆[A] 0.1 − 0.2  0.1
7. Rate of reaction = − = −  =
∆t  10  10 14. Rate law is
= 0.01 mol dm min –3 –1
rate = k [A]2[B]
∴ When concentration of A is tripled by keeping B
1 d[C] constant,
8. Rate of reaction =
2 dt rate1 = k [3A]2[B]= k 9 [A]2[B]= 9 k [A]2[B]
1  rate1 = 9 rate
=  ×1.0  mol L–1 s–1
 2  ∴ Rate of reaction increases by 9 times.
= 0.5 mol L–1 s–1.
16. Order of a reaction = sum of the exponents of
d[N 2O5 ] the concentration terms
9. – = 0.03 M/s
dt 3 3 1
∴ Order of reaction = + (–1) = – 1 =
1 d[N 2O5 ] 1 d[NO 2 ] 2 2 2
rate = – =
2 dt 4 dt
d[NO 2 ]
∴ rate of formation of NO2 = the concentration terms
dt
1 1
 d[N 2O5 ]  ∴ Order of reaction = + +1
= 2 × − 2 3
 dt 
3+ 2+6 11
= 2 × (0.03 M/s) = =
6 6
= 0.06 M/s
18. Since the order of reaction with respect to X is 1,
10. Rate constant is independent of concentration of rate = k [X]
reactants. Rate 7.5 × 10−4
∴ k= = = 1.5 × 10−3 min–1
11. rate = k[A] [B]2 X
  0.5
Rate = 0.125 M/s; [A] = 2.0 M, [B] = 0.4 M
Substituting the values in the equation: 19. Rate = k[N2O5] = 6.2 × 10–1 × 1.25 = 0.775
rate = k[A] [B]2 = 7.75 × 10–1 mol L−1 s–1
42

Chapter 06: Chemical Kinetics

20. Rate1 = k[A]x 2.303  1 
Rate2 = k[8A]x 34. k= log10  
t1/ 4 3/ 4
Rate2 = 2 Rate1
2.303 4 0.29
k[8A]x = 2k[A]x t1/4 = log10   =
k8x [A]x = 2k[A]x k 3 k
23x = 2
36. Reactions in which rate is independent of the
1
∴ x= reactant concentration are zeroth order reaction.
3
37. For a zero order reaction,
21. Molecularity of an elementary reaction is
defined as the number of reactant molecules [A]0 − [A]t
k=
taking part in the reaction, hence it can only t
have integral values. [A]0 – [A]t = kt
[A]t = –kt + [A]0
22. Molecularity = 2 + 1 = 3.
40. Hydrolysis of methyl acetate can be represented
24. The slowest intermediate step is also known as
as,
the rate determining step and it governs the
overall rate of reaction. CH3COOCH3(aq) + H2O(l)  → CH3COOH(aq)
+ CH3OH(aq)
25. The rate determining step is the slowest one in a
The solvent (H2O) participates in the reaction,
reaction mechanism. This step determines the rate
and it is expected to have second order kinetics.
of the overall reaction and the order as well.
But it follows first order kinetics, as the
∴ rate = k[A2] presence of huge amount of water, keeps its
∴ order = 1 concentration unchanged.
27. Integrated rate law for the first order reaction is ∴ [H2O] = constant = k1
given by the equation, ∴ rate = k [CH3COOCH3] k1
2.303 [A]0
k= log10 41. Inversion of cane sugar is the reaction in which
t [A]t
sucrose (cane sugar) is hydrolysed to a mixture
The unit of k will be given by reciprocal of time
of glucose and fructose.
[A]0
as log10 is a unitless quantity. C12H22O11 + H2O →
H +
C6H12O6 + C6H12O6
[A]t
∴ k = time−1 Sucrose (excess) Glucose Fructose
2.303 0.8 2.303 This is pseudo first order reaction as water is in

28. k1 = log10 = log10 2
15 0.4 15 excess.
2.303 0.1 2.303
Similarly, k2 = × log10 = log10 4 44. (A) k is rate constant.
t 0.025 t (B) A is pre-exponential factor (Arrhenius
Now, k1 = k2 parameter).
2.303 2.303
∴ log10 2 = × 2 log10 2 (C) R is universal gas constant
15 t
or, t = 30 mins 45. In Arrhenius equation, k = Ae RT , the pre-
− Ea
30. For a first order reaction, exponential factor and rate constant has same unit
0.693 0.693 in case of first order reactions i.e., A has the unit
t1/2 = = = 0.347 min of s−1.
k 2
31. For a first order reaction, 48. The catalyst does react with the reactants to
0.693 0.693 form intermediate of low activation energy. The
t1/2 = = = 1 hour intermediate then decomposes to form the
k 0.693hr −1
product along with the regeneration of catalyst.
32. t1/2 = 1386 sec Thus, it reduces energy of activation and
0.693 provides alternate path for the reaction.
k= = 5 × 10–4 s–1 = 0.5 × 10–3 s–1
1386
33. Half life of a first order reaction is constant and Critical Thinking
is independent of the reactant concentration. So,
the time taken by 10 g of reactant to reduce its 1. Feasibility of a reaction is dealt by
half is 10 years. thermodynamics.
43


2. 2A + B → C + D 9. Let the rate of reaction depends on xth power of
1 d[A] d[B] d[C] d[D] [A]. Then
Rate = − =– = = r1 = k[A]x and r2 = k[2A]x
2 dt dt dt dt
1 r1 [A]x
Thus, rate of disappearance of A = rate of ∴ =
2 r2 [2A]x
disappearance of B. r1 1
= x
3. 2A + B → 3C + D r2 2
1 d[A] d[B] 1 d[C] d[D] 1 1
∴ Rate = − =– = = ∴ = ( r2 = 4 r1)
2 dt dt 3 dt dt 4 2x
d[C] ∴ x=2
is change in concentration of C per unit
dt Rate of reaction remains unaffected if
time. Since C is product, its concentration will concentration of ‘B’ is doubled. So the reaction
d[C] rate does not depend upon the concentration of
increase and hence term is positive. B. Hence, the correct rate law will be:
dt
rate = k[A]2[B]0 = k[A]2
5. 2SO2(g) + O2(g) → 2SO3(g)
Rate of the reaction is represented as: 10. Rate = k[A]2,
d[O 2 ] 1 d[SO 2 ] 1 d[SO3 ] (Rate)2 = k[2A]2 = k4[A]2 = 4k[A]2
– =– =
dt 2 dt 2 dt ∴ (Rate)2 = 4 × Rate
–4 1 d[SO 2 ] i.e., the rate of formation of B will increase by a
∴ 2.5 × 10 = – factor of 4.
2 dt
d[SO 2 ] 11. Let the initial concentration be C and rate be R.
∴ rate of disappearance of SO2 i.e., –
dt According to the given condition,
= 5.0 × 10–4 mol L–1 s–1 When C1 = 2C, R1 = 4R
When C2 = 3C, R2 = 9R
6. N2 + 3H2 
→ 2NH3
Let the order be x.
−∆ [ N 2 ] 1 ∆[H2 ] 1 ∆ [ NH 3 ]
Rate = = − = ∴ Rate ∝ [Reactant]x
∆t 3 ∆t 2 ∆t R1 = k (C1)x
∴ Rate of disappearance of N2 4R = k (2C)x ….(i)
−∆ [ N 2 ] 1 ∆ [ NH 3 ] R2 = k (C2)x
= = ×
∆t 2 ∆t 9R = k (3C)x ….(ii)
1 Dividing (i) by (ii), we get
= × 4.0 × 10−4 = 2 × 10−4 mol L−1 s−1
2 4R (2C) x
Rate of disappearance of H2 =
9R (3C) x
−∆ [ H 2 ] 3 ∆ [ NH 3 ]
= = × 4 2
x
∆t 2 ∆t = 
3 9 3
= × 4 × 10−4 = 6 × 10−4 mol L−1 s−1 ∴ x=2 ∴ Order = 2
2
7. N2(g) + 3H2(g) → 2NH3(g) 12. Let the rate of the given reaction be
∆[H2 ] rate, r = k[G]x[H]y ….(i)
Rate of disappearance of hydrogen =− According to 1st condition,
∆t
8r = k[2G]x[2H]y ….(ii)
6 × 10−2
= According to 2nd condition
10
2r = k[2G]x[H]y ….(iii)
∆[ N2 ] 1 ∆ [ H 2 ] 1 ∆ [ NH 3 ]
Rate = − = − = Dividing equation (ii) by (iii), we get
∆t 3 ∆t 2 ∆t
8r k[2G]x [2H]y
∆ [ NH 3 ] 2 ∆ [ H 2 ] 2 6 × 10−2 =
∴ = − = × 2r k[2G]x [H]y
∆t 3 ∆t 3 10
4 = 2y
∆ [ NH 3 ] –2
= 0.4 × 10 mole per minute ∴ y=2
∆t
–2 −2 –1 Substituting the value of y in equation (ii), we get
∆[NH3] = 0.4 × 10 × 10 = 4 × 10 mol L
8r = k[2G]x(2)2[H]2
[ ∆t = 10 minutes] 8r
In 10 minutes, amount of NH3 formed = k[2G]x[H]2
4
= 4 × 10–2 mol L–1 2r = k[2G]x[H]2 ….(iv)
44


Dividing equation (iv) by substituted equation (i) 21. [A]0 = 100, [A]t = 100 − 75 = 25
2r k[2G] [H] x 2
2.303 100 2.303
= ∴ k= × log10 = × log 4
r k[G]x [H]2 t 25 30
2 = 2x ∴ x=1 2.303× 2log10 2
∴ k= …(i)
∴ Overall order = x + y = 1 + 2 = 3 30
[A]t1 = 100 – 93.75 = 6.25
13. Rate = k [NO]2 [O2]
2.303 100
As volume is halved, concentration gets doubled k= log10
t1 6.25
∴ Rate1 = k [2NO]2 [2O2]
2.303 2.303
= k 4[NO]2 2[O2] = 8 k [NO]2 [O2] = 8 × Rate k= log10 16 = 4 log10 2 …(ii)
t1 t1
14. The order and molecularity of the reaction may Equating (i) and (ii)
or may not be the same always. 2.303× 2log10 2 2.303
= × 4 log10 2
30 t1
2.303 [A]
15. t = log10 0 ( k = constant)
k [A]t
2.303 0.5 2.303 t1 = 60 mins
= log10 = × log10 10
6 0.05 6 22. Given,
2.303 a = 100, x = 80, when t = 10 min.
= = 0.3838 s ≅ 0.384 s
6 Substituting these values in the first order
integrated rate law,
0.693 0.693
16. t1/2 = = = 600 s 2.303 a
k 1.155 × 10−3 k= log10 , we get
t a−x
0.693 0.693 2.303 100 2.303
17. t1/2 = = s = 40764.7 s k= log10 = log10 5
k 1.7 × 10−5 10 × 60 100 − 80 10 × 60
40764.7 2.303
= hr = 11.32 hr ≅ 11.3 hr. = × 0.6989
3600 600
k = 0.00268 s−1 ≈ 0.0027 s−1
18. Rate = k[Concentration]
23. 60% of a first order reaction was completed
0.693
Rate = [Concentration] ∴ If a = 100 then a − x = 40
t1/ 2
and time, t = 60 min
0.693[Concentration] 2.303 100
∴ t1/2 = ∴ k= log10
Rate 60 40
0.693× 0.2 2.303
t1/2= = 20 min = 1200 s = log10 2.5 = 0.0153 min
−1
0.69×10−2 60
19. t1/2 = 10 min Time taken for 50% of reaction to be completed
is equal to t1/2.
0.693 0.693
∴ k= = = 0.0693 0.693
t1/ 2 10 k=
t1/ 2
2.303 [A]
Again, t = log10 0 0.693
k [A]t t1/2 = = 45.29 ≈ 45 min
0.0153
2.303 0.08
= × log10 = 30 min 0.693
0.0693 0.01 24. t1/2 =
k
0.693 t (for completion of 99.9 %)
20. k= = 0.0231 min−1
30 99.9% complete means 0.1% remaining
[A]0 = 100, [A]t = 100 − 75 2.303 100
t = log10
2.303  100  k 0.1
t= log10  
k  100 − 75  t k 2.303
∴ = × log10[103]
2.303 2.303 t1/ 2 0.693 k
t= log10 4 = × 2 × log10 2
0.0231 0.0231 t 2.303 × 3 6.909
∴ = = = 9.969 ≈ 10.
= 60 minutes t1/ 2 0.693 0.693
45


25. Flask I: [A]0 = 1 M 32. Activation energy (Ea) = 60 kJ mol−1
1 = 60 × 103 J mol−1
[A]t = 0.25 M  
of originalconcentration 
4
th
 Temperature (T) = 300 K
∴ 2 t1/2 = 8 hrs f = e-Ea / RT
t1/2 = 4 hrs Substituting the given value above
-60 ´103 J mol-1
æç ö÷
Flask II: [A]0 = 0.6 M ; [A]t = 0.3 M çç
çç
÷÷÷
çè 8.314 J K -1 mol-1 ´ 300 K ø÷
÷
Time = t1/2 = 4 hrs f= e

-60 ´ 103
th
ln f =
3 1 8.314 ´ 300
26. At life, a − x =
4 4 -60 ´ 103
2.303 log10 f =
  8.314 ´ 300
2.303 1
k= log10   log10f =
-60 ´ 103
t3 1
  8.314 ´ 300 ´ 2.303
4 4
log10f = −10.445 ≈ −10.4
2.303
t3 = log10 4 f = 10(–10.4)
4 k
33. k = (2.5 × 1011 s−1) e−25000 K/T
27. For integrated rate equation, Comparing the given equation with Arrhenius
kt = ln[A]0 − ln[A]t equation, k = Ae− Ea / RT
ln[A]t = −kt + ln[A]0 Ea
∴ − = −25000 K
On comparing the above equation with, R
y = mx + c ∴ Ea = 25000 K × 8.314 J K−1 mol−1
Y = 207850 J mol−1
Slope = −k ∴ Ea = 207.85 kJ mol−1
Intercept = ln[A]0 35. Larger the value of Ea smaller is the rate
constant.
ln[A]t k′ = 2 k″ (given)
∴ k′ > k″
X ∴ E′a < E′′a
time (t)
− Ea
29. For zero order reaction, 36. k = Ae RT

[A]0 − [A]t For Ea = Zero
k= k = Ae0 = A
t
where [A]0 = Initial concentration of reactant 37. k1 = k2
[A]t = Concentration of reactant at time ‘t’ 1016.e−2000/T = 1015.e−1000/T
After completion, [A]t = 0 e −1000/ T 2000 1000
−
[A]0 − 0 10 = −2000/ T
= e T T
∴ t= e
k 10 = e1000/T
a 1000
t= ….[ initial concentration is a] ln 10 =
k T
1000
30. For 1st order reaction 2.303 log 10 =
T
0.693 0.693
k1 = = = 0.01732 s−1 1000 1000
t1/ 2 40 2.303 = ∴ T= K
T 2.303
For zero order reaction
[A]0 1.386 k2 Ea T − T 
k0 = = = 0.03465 mol dm−3 s−1 38. log10 = ×  2 1
2t1/ 2 2 × 20 k1 2.303× R  T2T1 
k1 0.01732  6.90×10−3  Ea 40
= = 0.5 mol−1 dm3 log10  −5 
= ×
k0 0.03465  3.45×10  2.303×8.314 300× 340
31. Half life of a reaction is defined as the time 2.303×8.314× 300× 340× log 200
∴ Ea =
needed for the reactant concentration to reduce 40
to one half of its initial value. = 112.3 kJ
46


39. Arrhenius equation is given as: d d d[N 2 ]
44. rate = – C6 H 5 N +2 Cl−  = [ C6 H 5Cl] =
k = Ae − Ea / RT dt  dt dt
Ea Rate of evolution of N2 becomes two times
log10 k = log10 A − faster than the initial, when concentration of salt
RT × 2.303
is doubled.
 Ea  1 Therefore, the reaction is first order.
∴ log10 k = −   + log10 A ….(i)
 2.303R  T
1
log10 k = −(2000) + 6.0 ….(ii) [Given] Competitive Thinking
T
Comparing equation (i) and (ii), 3. For the given reaction,
Ea
3A → 2B
= 2000 1 d[A] 1 d[B]
2.303R Rate = − =
3 dt 2 dt
∴ Ea = 2000 × 8.314 × 2.303
d[B] 2 d[A]
= 38294 J mol−1 = 38.29 kJ mol−1 ∴ = −
dt 3 dt
= 38.3 kJ mol−1
log10 A = 6.0 4.  2NH3(g)
N2(g) + 3H2(g) 
⸫ A = Antilog (6.0) d[ N2 ] 1 d [ H 2 ] 1 d [ NH3 ]
Rate = − =− =
A = 106 = 1.0 × 106 s−1 dt 3 dt 2 dt
d[ N2 ] 1 d [ NH 3 ]
40. 2A + B → Products ∴ − =
dt 2 dt
When concentration of B was doubled, there is
no change in the half life i.e., half life is 5. 2N2O5(g) → 4NO2(g) + O2(g)
independent of concentration of B. 1 d[N 2O5 ] 1 d[NO 2 ] d [ O 2 ]
∴ With respect to B, the reaction follows first order. Rate = − = =
2 dt 4 dt dt
When the concentration of A is doubled, the rate d[NO 2 ] 4  d[N 2O5 ]  4
increases two times. ∴ = −  = × 0.02 = 0.04 M/s
dt 2 dt  2
So, the reaction follows first order with respect
to A. −d[N 2O5 ]
∴ Overall order is 1 + 1 = 2 6. = 6.25 × 10–3
dt
∴ Rate = k[A][B] 1
Rate N2O5(g) → 2NO2(g) + O2(g)
k= 2
[A][B] d[N 2O5 ] 1 d[NO 2 ] d[O 2 ]
∴ Rate = − = =2 …
(mol / L)(s −1 ) dt 2 dt dt
∴ Unit of k =
(mol / L)(mol / L) d[NO 2 ] d[N 2O5 ]
∴ =2× −
Unit of k = L mol−1 s−1 dt dt
= 2 × 6.25 × 10–3
41. Molecularity of a reaction is the number of
= 1.25 × 10–2 mol L−1s−1
reactant molecules taking part in the reaction,
d[O 2 ] 1 d[N 2O5 ]
and hence cannot be a fraction. = × −
dt 2 dt
1 1
42. Rate ∝ = × 6.25 × 10–3
t 2
As temperature increases, rate increases = 3.125 × 10–3 mol L−1s−1
∴ As rate increases, t (or even t1/2) decreases
∴ As temperature increases, t1/2 decreases. ∆[Br − ]
7. − = 0.05 mol L−1 min−1
∆t
43. For the reaction, A → products For the given reaction,
1 Average rate of reaction
When the volume of vessel changes into of
3 1 ∆[Br − ] ∆[BrO3− ]
its initial value then concentration of reactant =− =
−
5 ∆t ∆t
increases three times its initial concentration.
The rate of reaction for first order reaction is ∆[BrO3− ] 1
∴ − = × 0.05
proportional to concentration. So, rate of ∆t 5
reaction will increase three times. = 0.01 mol L−1 min−1
47


8. Rate = k[A]2[B] 1
y
0.22 = k (1)2(0.25) ∴ 1 =   ∴ y=0

2
1
0.22 = k × Now dividing equation (i) by (iii)
4
k = 0.88 M–2 s–1 1.2 × 10−3 k[0.1]x [0.1]y
∴ =
2.4 × 10−3 k[0.2]x [0.1]y
9. The order of a reaction can be fractional, zero, 1 x
negative or positive integer. 1  1 
∴ 2 = 2 ∴ x=1
   
11. The overall order of the given reaction is 3 and the d[C]
order of the reaction with respect to X is 2. Hence, = k[A]1[B]0
dt
∴ Order of the reaction with respect to Y = 3 − 2
=1 d[C]
∴ = k [A]
∴ The differential rate equation is dt
d[X] 14. Let the rate law for the reaction be,
− k[X]2 [Y]
=
dt Rate = k [A]x [B]y
12. Rate of the given reaction is doubled when 0.045 = k [0.05]x [0.05]y …(i)
concentration of ‘Y’ is doubled and it increases 0.090 = k [0.10]x [0.05]y …(ii)
by 8 times when concentrations of ‘X’ and ‘Y’ 0.72 = k [0.20]x [0.10]y …(iii)
are doubled. Dividing equation (ii) by (i),
Let the rate, R = k[X]a[Y]b …(i) 0.090  0.10 
x
= 
∴ When concentration of Y is doubled, the new 0.045  0.05 
rate (R1) will be 21 = 2x
R1 = k[X]a[2Y]b …(ii) ∴ x=1
But R1 = 2R Dividing equation (iii) by (i),
∴ k[X]a2b[Y]b = 2k[X]a[Y]b 1 y
( 0.20 ) ( 0.10 ) =  0.2   0.10 
x y
0.72
∴ 2b = 2 and thus b = 1 =
0.045 ( 0.05 ) x ( 0.05 ) y  0.05   0.05 
Similarly, when concentration of both X and Y
is doubled, the new rate (R2) will be 16 = 4 × 2y
R2 = k[2X]a[2Y]b 2y = 4
But R2 = 8R 2y = 22
∴ k[2X]a[2Y]b = 8k[X]a[Y]b ∴ y=2
Thus, rate = k [A] [B]2
a
[ X ] 2b [ Y ] = [X] [Y]
a b a b
k2 8k
15. For reaction A → B
2a 2b = 8
The rate law is,
2a 2 = 8 (∵ b = 1)
Rate = k[A]x ….(i)
2a = 4 = 22 and thus a = 2
3Rate = k[9A]x …..(ii)
Substituting the values of a and b in (i) the
Dividing (ii) by (i),
rate expression for the given reaction is rate,
3 = 9x
R = k[X]2[Y].
∴ x = 1/2
13. 2A + B → C + D
16. 9 r = k (3.24 × 10−2)n ….(i)
−1 d[A] d[B] d[C] d[D]
Rate = = − = = r = k (1.2 × 10−3)n ….(ii)
2 dt dt dt dt
Dividing (i) by (ii),
Let rate of reaction = k[A]x[B]y
n
d[C]  3.24 × 10−2 
Or, = k[A]x[B]y 9=  −3 
or 9 = (27)n
dt  1.2 × 10 
Now from table, or (3)2 = (33)n = (3)3n.
1.2 × 10–3 = k[0.1]x[0.1]y ….(i) Hence, 3n = 2 or n = 2/3.
1.2 × 10–3 = k[0.1]x[0.2]y ….(ii) 17. Let the rate of given reaction be:
2.4 × 10–3 = k[0.2]x[0.1]y ….(iii) (rate)1 = k [A]x [B]y
Dividing equation (i) by (ii) Doubling the concentration of A increases the
1.2 × 10−3 k[0.1]x [0.1]y rate by 4.
∴ =
1.2 × 10−3 k[0.1]x [0.2]y ∴ (rate)2 = k [2A]x [B]y = 2x k [A]x [B]y
48


(rate)2 = 2x × (rate)1 20. NO is formed in step (i) and consumed in step
(rate) 2
(ii). Hence, it is a reaction intermediate.
= 2x
(rate)1 22. The rate law expression is written for the
4=2 x
slowest step in the reaction mechanism. So, the
rate of the given reaction is
∴ x=2
rate = k1 [ClO−]2.
Doubling the concentration of B doubles the
reaction rate. 23. t = 40 min, [A]0 = 0.1 M, [A]t = 0.025 M
(rate)3 = k [A]x [2B]y 2.303 [A]0
For first order reaction, k = log10
(rate)3 = 2y k [A]x [B]y t [A]t
(rate)3 = 2y (rate)1 2.303 0.1
(rate)3
∴ k= log10
= 2y t 0.025
(rate)1
2.303 2.303
= × log10 4 = × 2 log10 2
2 = 2y 40 40
∴ y=1 2.303× 2× 0.3010
= = 0.03467 min −1
∴ Overall order = x + y = 2 + 1 = 3 40
18. Rate of the given reaction is doubled when ∴ Rate = k [X] = (0.03467 × 0.01) M min −1
concentration of ‘A’ is doubled and it is = 3.467 × 10 −4 M min −1
quadrupled when concentration of ‘A’ and ‘B’ ≈ 3.47 × 10 −4 M min −1
is raised four times.
Let the rate (R) = k[A]x [B]y ....(i) 1
24. [A]0 = 100, [A]t = 100 × = 10
∴ When concentration of A is doubled, the new 10
rate1 (R1) will be For first order reaction, k =
2.303 [A]0
log
Rate1 (R1) = k[2A]x [B]y ....(ii) t [A]t
But rate1(R1) = 2 rate(R) 2.303 [A]0 2.303 100 
x y x y
∴ t = log = −2
log  
∴ k[2A] [B] = 2k[A] [B] ….[From (i) and (ii)] k [A]t 2.303×10  10 
∴ k 2x[A]x [B]y = 2k[A]x [B]y 1
= × log(1) = 102 = 100 seconds
∴ x
2 = 2 and thus x = 1 10−2
Similarly, when concentration of both A and B 25. k = 10–2 s–1

is quadrupled, the new rate2 (R2) will be
2.303 [ A ]0
Rate2 (R2) = k[4A]x [4B]y ….(iii) t= log10
k [ A ]t
But rate2 (R2) = 4 Rate(r)
∴ k[4A]x [4B]y = 4k[A]x [B]y 2.303  20 
t= log10  
 5 
−2
10
….[From (i) and (iii)]
= 138.65 s ≈ 138.6 s
k 4x [ A ]x 4 y [ B ]y = 4 k [ A ]x [ B ]y
∴ 4x.4y = 4 26. For 1st order reaction, ln
[ A ]0 = kt
[ A ]t
∴ 4.4y = 4 ( x = 1)
99% of the reaction is complete,
∴ 4y = 1 and thus y = 0 so if [A]0 = 100, then [A]t = 100 – 99 = 1
Substituting the values of x and y in (i)., the rate ∴ ln 100 = kt
expression for the given reaction is
rate (R) = k[A]1 [B]0 1
∴ t= × 2.303 log10 102
∴ rate(R) = k[A] k
Thus, the order of the given reaction with 1
∴ t= × 2.303 × 2 × log10 10
respect to: k
i. ‘A’ is 1 and ii. ‘B’ is 0. 4.606
∴ t=
The overall order of the given reaction is 1. k
49


29. The half life of first order reaction is given by 2.303 0.04 2.303
∴ k= log10 = × 0.1249
0.693 10 0.03 10
equation t1/2 =
k 0.693 0.693× 10
∴ t1/ 2 =
=
The equation implies that the half life of a first k 2.303× 0.1249
order reaction is constant and is independent of the = 24.09 s ≈ 24.1 s
reactant concentration. Since, in given reaction,
change in concentration does not affect its half 1
35. of initial concentration is obtained after two
life; it must be a first order reaction. 4
30. For a first order reaction, t1/2 is independent of half-life.
initial concentration of the reactant. Thus, the i.e., 2 × t1/2 = 20 min
unit of rate constant will be s–1. t1/2 = 10 min
1
31. Half life period of first order reaction is given as; of initial concentration is obtained after 4
16
0.693
t1/ 2 = 1 1 1 1 1
k half life. i.e., = × × ×
16 2 2 2 2
0.693 0.693
∴ k= = = 0.1 hr−1 ∴ time required = 4 × t1/2 = 4 × 10 = 40 min
t1/ 2 6.93hr
Thus, the value of rate constant for the given 36. t1/2 = 10 min
reaction is 0.1 hr−1. ∴ 20 min = 2 half lives
After two half lives, concentration of reactant
32. The rate constant for a first order reaction is 1
independent of concentration. reduces to th of initial concentration.
4
0.693
It is given as t1/2 = 1
k ∴ Concentration after 20 min = × 12 = 3 M
4
0.693
= = 990 s 0.693 0.693
7.0 × 10−4 k= =
t1/ 2 10
33. For the given first order reaction, the k = 0.0693 min−1
concentration of the reactant is reduced to For a first order reaction,
12.5% in 1 h. rate = k[concentration of reactant]
∴ If [A]0 = 100, then [A]t = 12.5 and
= 0.0693 × 3 M min−1
t = 1 h = 60 min
2.303 [A]0 1
th
k= log10 37. 0.5 M ⇒ 0.125 M .... concentration
t [A]t 4
2.303 100 ⇒ 2t1/2 = 50 min
= log10 = 0.03466 min−1
60 12.5 ∴ t1/2 = 25 min
0.693 0.693
k= ∴ Rate constant (k) =
t1/ 2 t1/ 2
0.693 0.693
∴ t1/2 = = 19.99 ≈ 20 min k= min−1
0.03466 25
∴ The reaction was half completed in 20 min. Rate of H2O2 decomposition = k[H2O2]
d[H 2O 2 ] 0.693
34. For a first order reaction, Rate = k[A] ∴ − = (0.05)
dt 25
Rate
∴ [A] = For decomposition: 2H2O2 → 2H2O + O2
k
d[O 2 ] 1 d[H 2O 2 ]
0.04molL−1s −1 ∴ = −
∴ At t = 10 s, [A]0 = dt 2 dt
k s −1
1 (0.693)
At t = 20 s, i.e., after 10 s, =+ (0.05)
2 25
0.03molL−1s −1 = 6.93 × 10–4 M min−1
[A]t =
k s −1
39. Integrated rate law for zero order reaction is,
2.303 [A]0
∴ k= log10 [A]0 − [A]t
t [A]t k=
t
0.04
2.303 [A]0 − [A]t 0.30 − 0.03
∴ k= log10 k t= =
10 0.03 k 3.0 × 10−3
k = 90 s
50


41. For a zero order reaction, Ea
46. log10 k = log10 A −
[A]0 2.303RT
t1/2 =
2k − Ea 1
log10 k = × + log10 A
2 2.303R T
∴ k= = 1 mol L−1 h−1
2 ×1 1
A plot of log10 k against is a straight line
[A]0 − [A]t T
k=
t − Ea
with a slope equal to and intercept
[A]0 − [A]t 0.50 − 0.25 2.303R
t= = = 0.25 h
k 1 equal to log10 A.
42. According to collision theory, successful
conversion of reactant(s) to product(s) takes Ea
place when, Slope = −
log10 k 2.303R
i. reactant molecules possess certain energy
which is equal to or greater than the
activation energy, and
ii. are properly oriented with respect to each 1/T
other at the time of collision.
47. k = Ae−Ea/RT
43. For an endothermic reaction, the energy of ∴ k1 = Ae− Ea1 / RT and k2 = Ae− Ea 2 / RT
products will be more than that of reactants.  Ea1 − Ea 2 
k2  
∴ = e RT 
k1
k2 E − Ea 2 10,000
ln = a1 = =4
k1 RT 8.314 × 300
Products
48. Activation energy (Ea) = 600 R;
Ea
T1 = 27 °C = 300 K
∆H T2 = 327 °C = 600 K
k2 E T − T 
ln = a  2 1
Reactants k1 R  T1 × T2 
600R  600 − 300 

=  
∴ Ea > ∆H R  300 × 600 
44. Arrhenius equation is given as,  300 

= 600   =1
k = A.e–Ea/RT  300 × 600 
A k2
= Ea RT ∴ = e1 = e
e k1
45. By Arrhenius equation
k2 Ea  T2 − T1 
k = Ae− Ea / RT 49. log10 =  
By taking logarithms on both sides, k1 2.303R  T1 × T2 
Ea Ea  310 − 300 
ln k = ln A − log10 2 =
RT 2.303×8.314  300× 310 
1 log10 2× 2.303×8.314× 300× 310
On plotting ln k vs ∴ Ea =
T 10
0.3010× 2.303×8.314× 300× 310
=
10
Slope = −Ea/R = 53,598 J = 53.59 kJ ≈ 54 kJ
ln k
50. Rate of reaction = k[concentration of reactants]
When a catalyst increases the rate of a chemical
reaction, there is no change in initial
1/T
concentration of reactants.
∴ By knowing slope, activation energy can be So, when rate of reaction increases, the rate
determined. constant also increases.
51


52. There are few reactions of third order and Taking antilog on both sides
reactions of higher order are unknown. The [H+] = Antilog 3 = 10−3 M
reason is that the collisions in which three or
more molecules all come together at the same Similarly when pH = 1, [H+] = 10−1 M
time are very unlikely. pH changes from 3 to 1
i.e., [H+] = 10−3 M changes to [H+]′ = 10−1 M
53. Rate r = k[H+]n
i.e., concentration increases 100 times.
New rate, r′ = 100 r
[H + ]′ 10−1
∴
r′
= 100 = = 100
[H + ] 10−3
r
pH = −log10[H+] ….(i) r′ k[H + ]′n
∴ =
∴ When pH = 3, equation (i) becomes r k[H + ]n
3 = − log10[H+]
n
r′  [H ]′ 
+
∴ =  +  or 100 = (100)n or n = 1
∴ log10[H+] = −3 r  [H ] 
1. For a first order reaction From 1st and 4th set of data
2.303 a (5.0 × 10–3) = k2[0.010]y ….(iii)
k= log10 –3 y
t (a − x) (1.25 × 10 ) = k2[0.005] ….(iv)
2.303 100 Dividing equation (iv) by (iii),
t = log10 y
k (100 − 90) 1.25 × 10−3  0.005 
= 
2.303× t1/ 2 100 0.693 5.0 × 10−3  0.010 
= × log10 [ t1/2 = ] y
0.693 10 k  1.25   0.5 
 = 
= 3.3 × t1/2 × log10 10 = 3.32 t1/2 ≈ 3.3 t1/2  5   1 
y
2.303  0.25   0.5 
[A]  = 
2. k= × log10 0  1   1 
t [A]t
y=2
2.303 M / 10
= log10 ∴ Rate = k [A]2[B]1[C]0
500 M / 100
2.303 2.303 6. Given rate of the reaction (~7.3 × 10–2) is
= × log10 10 = = 0.004606
500 500 constant i.e., the reaction follows zero order
= 4.606 ×10–3 s–1 kinetics.
5. From 1st and 2nd set of data it is found that 0.5

7. At half life, a = 0.5, a – x =
change in concentration of C does not affect the 2
rate. So, the order with respect to C is zero. 2.303  0.5 
k= log10  
Let, Rate ∝ [B]x ∴ Rate = k1[B]x t1/ 2  0.5 / 2 
In 1st and 3rd set of data 2.303 ln 2
t1/2 = log10 2 ∴ t1/2 =
5.0 × 10–3 = k1 (0.005)x ….(i) k k
1.0 × 10–2 = k1[0.01]x ….(ii)
−d [ N 2 ] −1 d [ H 2 ] 1 d [ NH 3 ]
Dividing equation (ii) by (i), 8. = =
x
dt 3 dt 2 dt
 1.0 × 10−2   0.01  Rate of conversion of H2
 −3 
= 
 5.0 × 10   0.005  −d [ H 2 ] 3 d [ NH 3 ]
x = =
 10   10  dt 2 dt
 =  3
 5  5 = × 0.001 = 0.0015 kg/hr
∴ x=1 2
Let, Rate ∝ [A]y 9. The unit of rate constant for zero order reaction
∴ Rate = k2[A]y is mol dm−3 sec−1.
52


10. rate = k[A]n[B]m
New rate, r′
[B]m
r′ = k[2A]n[B/2]m = k[2]n[A]n
[2]m
[2]n
=k [A]n[B]m = 2(n−m) k[A]n[B]m
[2]m
= 2(n−m) rate
∴ The ratio of new rate (r′) to earlier rate of
r′
reaction i.e., = 2(n − m)
rate
12. Increase in concentration of B = 5×10–3mol L–1;
Time = 10 s
Increaseof [B]
Rate of appearance of B =
Time taken
5×10−3 mol L−1
=
10 s
= 5 × 10–4 mol L–1 s−1
13. rate = k[A]x
New rate, r′
r′ = k[8A]x = k 8x [A]x … (i)
r′ = 2 × rate
= 2 × k[A]x … (ii)
Equating (i) and (ii),
2 × k[A]x = k 8x [A]x
2 = 8x
1
x=
3
15. If the reaction is taken as A → Products.
Rate = k [A]
= 3 × 10–6 s–1 × 0.10 M = 3 × 10–7 M s–1
16. The unit of rate constant for 1st order reaction is
time−1.
17. t1/2 = 6.93 min
If a = 100, a − x = 100 – 99 = 1
0.693 0.693
k= = = 0.1 min−1
t1/ 2 6.93
2.303 a
k= log10
t a−x
2.303 a 2.303 100
t = log10 = log10
k a−x 0.1 1
2.303
= × 2 = 46.06 min
0.1
the concentration terms
3  1 2
∴ Order of the reaction = + −  = = 1.
2  2 2
53

07 Elements of Groups 16, 17 and 18
Hints
increases, ionization enthalpy

Classical Thinking decreases.
1
4. Copper pyrites formula: CuFeS2 Ionisation enthalpy ∝
atomic radius
(Sulfide ion S2–) 22. The size of F atom is smaller than Cl atom. As a
Gypsum formula: result, there are strong inter electronic
CaSO4.2H2O repulsions in the relatively small 2p orbitals of
fluorine and therefore, the incoming electron
Epsom salt formula: (Sulfate ion SO 24 − ) does not experience much attraction. Thus,
MgSO4.7H2O fluorine has less negative electron gain enthalpy
Baryte formula: than chlorine. Therefore, the correct decreasing
BaSO4 order of magnitude of electron gain enthalpy is
given as, Cl > F > Br > I.
5. Galena (PbS); Zinc blende (ZnS)
23. The ionisation enthalpy of chlorine is greater
7. Halogens are very reactive due to high than iodine as ionisation enthalpy decreases
electronegativities. down the group due to increase in the atomic
size.
9. Radon is a decay product of radium (226Ra).
24. The ionisation enthalpy decreases down the
12. 18Ar: [Ne] 3s2 3p6 ; 16S:[Ne] 3s2 3p4 group due to increase in the atomic size.
2 5 10 2 4
17Cl: [Ne] 3s 3p ; 34Se: [Ar] 3d 4s 4p
25. Argon is a group 18 element (noble gas). It has
13. Across a period, atomic and ionic radii decrease no tendency to accept electrons because of the
because atomic number increases with stable electronic configuration and thus have
consequent increase in effective nuclear charge large positive electron gain enthalpy.
(Zeff).
27. Metallic character increases down the group
15. i. The atomic radius increases down the thus, polonium is a metal whereas, sulfur is a
group, as a result of increase in the nonmetal and selenium, tellurium are
number of quantum shells. metalloids.
ii. The ionisation enthalpy decreases down 28. Fluorine and chlorine are gases whereas iodine
the group due to increase in the atomic is a solid at room temperature.
size.
iii. The electronegativity decreases down the 32. Oxygen shows –2, –1, and +2 oxidation states
group. while other elements show –2, +2, +4, +6
oxidation states.
17. The ionisation enthalpy decreases down the 36. Hydrogen fluoride is a liquid (b.p. 293 K) due to
group due to increase in the atomic size. strong hydrogen bonding while other hydrogen
20. On moving down the group, atomic size halides are gases.
increases. Larger the size of an atom, 37.
lesser is the attraction between the Example Oxidation state of oxygen
nucleus and outermost electron. Hence H2O –2
it is easier to remove electron from OF2 +2
it. Therefore, as atomic size Na2O2 –1
H2O2 –1
54


39. Arrhenius equation is given as: d d d[N 2 ]
44. rate = – C6 H 5 N +2 Cl−  = [ C6 H 5Cl] =
k = Ae − Ea / RT dt  dt dt
Ea Rate of evolution of N2 becomes two times
log10 k = log10 A − faster than the initial, when concentration of salt
RT × 2.303
is doubled.
 Ea  1 Therefore, the reaction is first order.
∴ log10 k = −   + log10 A ….(i)
 2.303R  T
1
log10 k = −(2000) + 6.0 ….(ii) [Given] Competitive Thinking
T
Comparing equation (i) and (ii), 3. For the given reaction,
Ea
3A → 2B
= 2000 1 d[A] 1 d[B]
2.303R Rate = − =
3 dt 2 dt
∴ Ea = 2000 × 8.314 × 2.303
d[B] 2 d[A]
= 38294 J mol−1 = 38.29 kJ mol−1 ∴ = −
dt 3 dt
= 38.3 kJ mol−1
log10 A = 6.0 4.  2NH3(g)
N2(g) + 3H2(g) 
⸫ A = Antilog (6.0) d[ N2 ] 1 d [ H 2 ] 1 d [ NH3 ]
Rate = − =− =
A = 106 = 1.0 × 106 s−1 dt 3 dt 2 dt
d[ N2 ] 1 d [ NH 3 ]
40. 2A + B → Products ∴ − =
dt 2 dt
When concentration of B was doubled, there is
no change in the half life i.e., half life is 5. 2N2O5(g) → 4NO2(g) + O2(g)
independent of concentration of B. 1 d[N 2O5 ] 1 d[NO 2 ] d [ O 2 ]
∴ With respect to B, the reaction follows first order. Rate = − = =
2 dt 4 dt dt
When the concentration of A is doubled, the rate d[NO 2 ] 4  d[N 2O5 ]  4
increases two times. ∴ = −  = × 0.02 = 0.04 M/s
dt 2 dt  2
So, the reaction follows first order with respect
to A. −d[N 2O5 ]
∴ Overall order is 1 + 1 = 2 6. = 6.25 × 10–3
dt
∴ Rate = k[A][B] 1
Rate N2O5(g) → 2NO2(g) + O2(g)
k= 2
[A][B] d[N 2O5 ] 1 d[NO 2 ] d[O 2 ]
∴ Rate = − = =2 …
(mol / L)(s −1 ) dt 2 dt dt
∴ Unit of k =
(mol / L)(mol / L) d[NO 2 ] d[N 2O5 ]
∴ =2× −
Unit of k = L mol−1 s−1 dt dt
= 2 × 6.25 × 10–3
41. Molecularity of a reaction is the number of
= 1.25 × 10–2 mol L−1s−1
reactant molecules taking part in the reaction,
d[O 2 ] 1 d[N 2O5 ]
and hence cannot be a fraction. = × −
dt 2 dt
1 1
42. Rate ∝ = × 6.25 × 10–3
t 2
As temperature increases, rate increases = 3.125 × 10–3 mol L−1s−1
∴ As rate increases, t (or even t1/2) decreases
∴ As temperature increases, t1/2 decreases. ∆[Br − ]
7. − = 0.05 mol L−1 min−1
∆t
43. For the reaction, A → products For the given reaction,
1 Average rate of reaction
When the volume of vessel changes into of
3 1 ∆[Br − ] ∆[BrO3− ]
its initial value then concentration of reactant =− =
−
5 ∆t ∆t
increases three times its initial concentration.
The rate of reaction for first order reaction is ∆[BrO3− ] 1
∴ − = × 0.05
proportional to concentration. So, rate of ∆t 5
reaction will increase three times. = 0.01 mol L−1 min−1
47


102. For filling balloons, a mixture of helium (85%)
2Fe3+ + SO2 + 2H2O and hydrogen (15 %) is used.
Ferric Sulfur
ion dioxide
Critical Thinking
→ 2Fe2+ + SO 24 − + 4H+
Ferrous Sulfate Hydrogen 2. CuFeS2: Copper pyrites
ion ion ion Na3AlF6: Cryolite
79. Sulphuric acid is a strong oxidising agent. 3Ca3(PO4)2.CaF2: Fluorapatite
83. Chlorine is 2-5 times heavier than air. CaSO4.2H2O: Gypsum
84. Excess of chlorine reacts with ammonia to give 3. (II) Sea weeds contain upto 0.5 % iodine.
nitrogen trichloride (explosive). (IV) Halogens are not found in free state in
nature.
NH3 + 3Cl2 → NCl3 + 3HCl 10 2 6
Ammonia Chlorine Nitrogen Hydrogen 4. 36Kr: [Ar] 3d 4s 4p
10 2 6
(excess) trichloride chloride 54Xe: [Kr] 4d 5s 5p
85. 2Ca(OH)2 + 2Cl2 5. The atomic radii increase down the group
Dry slaked lime Chlorine
whereas ionisation enthalpy decreases down the
group.
→ Ca(OCl)2 + CaCl2 + 2H2O
Bleaching powder Calcium chloride 6. The ionic radii increase down the group as a
result of increase in the number of quantum
86. Chlorine requires the presence of moisture for shells.
its bleaching action. Chlorine is not used to
bleach delicate materials such as silk, wool, etc. 7. Fluorine has highest ionisation enthalpy among
as it is a strong bleaching and oxidising agent. halogens. Chlorine has highest negative electron
This dual action will damage the base material. gain enthalpy among halogens.
88. Interhalogens have general formula XX′n. The 8. Group 18 elements have large positive electron
number of X′ atoms is always odd. gain enthalpy as they have no tendency to
accept electrons. This is because of their stable
89. Interhalogen compounds have even number of
atoms 2, 4, 6, 8. For example, ClF3 has 4 atoms. electronic configuration (ns2 np6).
90. BrF3: Yellow green liquid 9. Effective nuclear charge increases across a
IF3: Yellow powder period and decreases down the group. Thus,
IBr: Black solid ionisation enthalpy increases across a period and
ICl3: Orange solid decreases down the group.
+3 Element Cl O F He
91. I2 + 3Cl2 → 2 I Cl3
(excess) Ionisation 1256 1314 1680 2372
enthalpy
93. I2 + KClO3 
∆
→ ICl + KIO3 (kJ/mol)
95. Interhalogens of type XX′3 have sp3d 12.
hybridization. They have two lone pairs of
Compound Oxidation state of xenon
electrons on central atom X.
XeOF4 +6
99. Partial hydrolysis of XeF4 yields xenon XeO3 +6
monooxydifluoride (XeOF2). XeF6 +6
XeF4 + H2O 
80 ° C
→ XeOF2 + 2HF XeF4 +4
Xenon Water Xenon Hydrogen
XeF2 +2
tetrafluoride monooxydifluoride fluoride
13. The acidic character of the hydrides increases,
while thermal stability decreases from H2O to
101. XeF4: Square planar ; H2Te.
XeF6: Distorted octahedral
XeO3: Trigonal pyramidal ; 14. The acidic character of the hydrides increases
XeOF4: Square pyramidal from H2O to H2Te because the bond
56

Chapter 07: Elements of Groups 16, 17 and 18

dissociation enthalpy of the H–E bond decreases Thiosulfuric acid, H2S2O3
down the group. (where, E = O, S, Se, Te)
S
Thus, H2Te is most acidic among the given
hydrides and will have lowest value of pKa. S
HO
Hydride H2O H2S H2Se H2Te O
OH
pKa values 14.0 7.0 3.8 2.6
15. Peroxydisulfuric acid, H2S2O8
Hydrides H2O H2S H2Se H2Te O O
b.p. (K) 373 213 232 269
16. Dipole moment depends upon the S S
electronegativity of the atoms in the molecule. O O–O O
Oxygen is the second most electronegative OH OH
23. Hypochlorous acid, HOCl
element and the electronegativity decreases
down the group. So, the increasing order of O
dipole moment will be H Cl
H2Te < H2Se < H2S < H2O. Chlorous acid, HOClO or HClO2
17. The acidic character of hydrides increases down O
the group i.e., from HF to HI. HF is least acidic O
hence will have the highest pKa value. H Cl
18. Bond dissociation enthalpies of halogen Chloric acid, HClO3
molecules follow the order: O
Cl – Cl > Br – Br > F – F > I – I. O
H Cl
19. The tetrahalides of group 16 elements undergo O
sp3d hybridisation and possess trigonal Perchloric acid, HClO4
bipyramidal geometry with one equatorial
O
position occupied by a lone pair of electrons. O
H Cl O
F
F O
Se
F 24. Out of several oxoacids of halogens, only 4
F have been isolated in pure form. These are HOF,
HClO4, HIO3 and H2IO6. All others are stable
20. (I) S2 molecule has two unpaired electrons in only in aqueous solutions or in the form of their
the antibonding π* orbitals. salts.
(IV) Grey selenium allotrope is a
photoconductor used in photocells. 25. 4HCl + O2 
CuCl
Δ
→ 2Cl2 + 2H2O
2
21. Sulfurous acid, H2SO3 26. NO, N2O and CO are examples of neutral
oxides.
28. (I) Ozone is thermodynamically less stable
than dioxygen.
S (IV) Ozone acts as a good bleaching agent due
HO to its oxidising nature.
HO O
29. 2NaOH + SO2 → Na2SO3 + H2O
Disulfuric acid or pyrosulfuric acid, H2S2O7 (X)
Na2SO3 + H2O + SO2 → NaHSO3
O O (Y)
S S 30. In SO2, O – S – O bond angle is 119.5°.
O O O
OH HO 31. SO3 + H2SO4 → H2S2O7
Sulfur Oleum
trioxide
57


32. Concentrated sulphuric acid is a powerful 37. XeF4: Square planar
dehydrating agent due to its strong affinity for
water. It removes water from a large number of F F
organic and inorganic compounds.
conc. H SO Xe
C12H22O11 
2 4→ 12C + 11H2O
Sucrose Carbon Water
F F
33. 2HBr + H2SO4 → Br2 + SO2 + H2O
Hydrobromic Sulphuric Bromine Sulphur Water
acid acid dioxide 38. XeF6 + H2O → XeOF4 + 2HF
(P)
34. CaF2 + H2SO4 → CaSO4 + 2HF Square pyramidal
(Conc.)
35. I2 + 5Cl2 + 6H2O → 2HIO3 + 10HCl XeF6 + 3H2O → XeO3 + 6HF
(Q)
Oxidation state of Cl in HCl = –1 Trigonal pyramidal
Oxidation state of I in HIO3 = +5 39. 2XeOF4 + SiO2 → 2XeO2F2 + SiF4
Xenon
36. (A) Structure of XeF6: dioxydifluoride
F 40. Mixture of 85 % Ar and 15 % N2 is filled in

F electric bulb to increase life of filament.
F
Xe
Competitive Thinking
F F
2. The abundance of noble gases in dry air is ∼ 1%
F (by volume) with argon as the major constituent.
(B) Structure of XeO3: 3. Due to smaller size of fluorine, it shows inter
electronic repulsion among its electrons. Hence,
electron gain enthalpy of F is less negative than
Cl. The value of electron gain enthalpy becomes
Xe
less negative going down the group from Cl.
O O Thus, chlorine has the highest value of negative
O
electron gain enthalpy.
4.
(C) Structure of XeOF4:
Electron gain F Cl Br I
O enthalpy –333 –349 –325 –296
F F (kJ mol−1)
Xe
The order of the electron gain enthalpies of
F F halogens is Cl > F > Br > I.
Fluorine has unexpectedly low negative value of
electron gain enthalpy due to its small atomic
(D) Structure of XeF2:
size.
F
5. The order of the electron gain enthalpies of
halogens is Cl > F > Br > I.
Xe
7. Argon is a monoatomic gas.
F 8. Boiling point (in K) of inert gases:
He Ne Ar Kr Xe Rn
4.2 27.1 87.2 119.7 165.0 211
58


10. Thermal stability decreases from H2O to H2Po.
23. Chlorine reacts with water to form HCl and
11. All hydrides except H2O possess reducing HOCl. HOCl gives nascent oxygen which
property as H2O is very stable molecule. results in bleaching action.
∆Hdiss(O – H) = 463 kJ mol–1. Therefore, it does OCl– → [O] + Cl–
not act as a reducing agent. Hence, the reactive species in chlorine bleach is
OCl–.
13. Among halogens, only chlorine forms the
halous acid like chlorous acid wherein the 26. Aqua regia dissolves gold,
chlorine atom is in tripositive oxidation state. +5
Au + 4H+ + NO3− + 4Cl−
O Gold Nitrate Chloride
O ion ion
H Cl +2
→ AuCl−4 + NO + 2H2O
Chlorous acid Tetrachlorido- Nitric Water
(Oxidation state of Cl: +3) aurate(III) oxide
14. The acid strength of the halogen oxoacids
27. Interhalogen compounds are more reactive than
increases with the increasing oxidation state of
halogen. halogens. This is because X−X′ bonds present in
Also, the increasing order of charge them are weaker than X−X or X′−X′ bonds.
delocalization in the anions of oxoacids of ∆
28. MnO2 + 4HCl → MnCl2 + Cl2 + H2O
chlorine is, ClO− < ClO 2− < ClO3− < ClO −4 . Manganese Chlorine
Manganese Hydrochloric Water
With increase in charge delocalisation, the dioxide acid
dichloride (A)
stability of the ion increases and the basicity of
the anion decreases. Thus, ClO− is the strongest 573 K
base and ClO −4 is the weakest base. A weak base Cl2 + 3F2 → 2ClF3
Chlorine Fluorine Chlorine trifluoride
has strong conjugate acid and vice versa. Hence, (A) (excess) (colourless gas)
HClO (conjugate acid of ClO−) is the weakest (B)
acid and HClO4 (conjugate acid of ClO −4 ) is the
3ClF3(l) + U(s) → UF6(g) + 3ClF(g)
strongest acid. Hence, the correct increasing Chlorine Uranium Chlorine
order of acid strength is: Uranium
trifluoride hexafluoride monofluoride
HClO < HClO2 < HClO3 < HClO4. (B) (C) (D)
15. SO2, CO2 → Acidic oxide In the given series of reactions, the gases A, B,
BaO → Basic oxide C and D are Cl2, ClF3, UF6 and ClF
N2O → Neutral oxide respectively.
17. Ozone, on reaction with potassium iodide (KI) 30. The structure of BrF5:
solution, oxidises iodide ions to iodine (I2).
2KI(aq) + H2O(l) + O3(g) → 2KOH(aq) + I2(s) + O2(g)
Potassium Ozone Potassium Iodine Oxygen F F
iodide hydroxide Br
F F
18. Ozone molecule is angular with O − O − O bond F
angle as 116.8° (≈ 117°). Both O − O bonds are
identical having bond length 128 pm (i.e., 1.28 Å) 32. 1 mol of H2O = 18 g of H2O
[Since, 1 Å = 10−10 m and 1 pm = 10−12 m]. ∴ 0.1 mol of H2O = 1.8 g of H2O
19. Sulphur dioxide is not a dehydrating agent. Molar ratio of XeF6 : H2O = 1 : 1
0.1 mole of XeF6 reacts with 0.1 mole of H2O
22. Chlorine reacts with cold and dilute alkali to (i.e., 1.8 g) to form 0.1 mole of XeOF4.
produce a mixture of chloride and hypochlorite.
2NaOH + Cl2 → NaCl + NaOCl 36. Rhombic sulphur and monoclinic sulphur are
Sodium hydroxide Chlorine Sodium Sodium polymorphic forms of sulphur, i.e, arrangement
(Cold and dilute) chloride hypochlorite
59


of molecules is different. However, both the N2O5 is an acidic oxide.
crystals are made up of S8 molecules. MgO is a basic oxide.
40.
37. The valence shell electronic configuration of Element Nature of oxide
p-block elements is ns2np1−6, except helium, Calcium Basic
which has 1s2 configuration. Helium contains Zinc Amphoteric
completed duplet and hence, one molecule of Carbon Acidic
He consists of only one atom (i.e., it is a Sulphur Acidic
monoatomic element).
38. Generally, acidic oxides are the binary 42.

compounds of oxygen with nonmetals whereas Element Type
basic oxides are the binary compounds of (A) Carbon Non-metal
oxygen with highly electropositive metals. (B) Neon Noble gas
(C) Sodium Alkali metal
39. ZnO and Al2O3 are amphoteric oxides. (D) Tellurium Metalloid

5.
Compound Oxidation state of xenon 9. Acidic oxides: Cl2O7
XeOF4 +6 Amphoteric oxides: Al2O3
XeO3 +6 Neutral oxides: CO, NO
XeF6 +6 10. SO2 is highly soluble in water and its solution in
XeF4 +4 water is called sulfurous acid (H2SO3).
XeF2 +2 11. Perchloric acid, HClO4
7. Acidic character of hydrides of group 17 Oxidation state of ‘Cl’ = +7
elements increases down the group. Thus, HF is
13. Let ‘x’ be the oxidation number of sulphur. S8 is
least acidic in nature.
the elemental form of sulphur. Hence, oxidation
8. Peroxydisulfuric acid, H2S2O8 state is zero.
In S2F2, 2x − 2 = 0
O O
∴ 2x = 2
S S x=1
O O–O O In H2S, 2 + x = 0
OH OH x=−2
Thiosulfuric acid, H2S2O3 14. The noble gas which forms maximum number
of compounds is Xe.
S e.g. XeF2 , XeOF2 . XeF4 , XeOF4 . XeF6 , XeO3 .
S 18. Most electronegative fluorine shows only –1
HO
O oxidation state. Chlorine, bromine and iodine
OH
show –1, +1, +3, +5 and +7 oxidation states.
Sulfurous acid, H2SO3 Chlorine and bromine also exhibit +4 and +6
oxidation states.
S
HO
HO O
Disulfuric acid or pyrosulfuric acid, H2S2O7

O O
S S
O O O
OH HO
60

Chapter 08: Transition and Inner
Transition Elements
08 Transition and Inner Transition Elements
Hints
28. Oxidation of I− from aqueous solution of KI by

Classical Thinking acidified K2Cr2O7 gives I2. Potassium
dichromate is reduced to chromic sulphate.
8. Fe, Cu and Ni show variable oxidation states Liberated I2 turns the solution brown.
whereas Zn shows only +2 due to completely K2Cr2O7 + 6KI + 7H2SO4 → 4K2SO4
filled stable 3d10 electronic configuration. + Cr2(SO4)3 + 7H2O + 3I2
10. For the same oxidation state, the ionic radii
32. x + 4 (−2) = 0
generally decrease with increase in nuclear
charge. Therefore, the decreasing order of ionic x−8=0
radii of given ions will be: x = +8
Sc3+ > Ti3+ > Mn3+ > Co3+ 33. Noble metals like gold, platinum, etc., being
73 pm 67 pm 65 pm 61 pm
unreactive, are found in free state.
So, Sc3+ has the largest ionic radius.
11. In transition series, the first ionization enthalpy 43. In the zone of combustion, the temperature is
slightly increases from left to right, due to around 2000 K.
decrease in size of the atom from left to right. 44. Reaction (A) and (C) occur in the zone of slag
However, the ionization enthalpy of the last formation.
element (i.e., Zn) is high due to extra stability Reaction (B) occurs in the zone of reduction.
gained because of completely filled d-orbitals.
Reaction (D) occurs in the zone of combustion.
14. Fe3+ ion is [Ar] 3d5 4s0. It has 5 unpaired
electrons. 48. Lanthanoids (14 elements) and actinoids
(14 elements) together form the inner transition
∴ Spin-only magnetic moment, µ = n(n + 2) BM
elements.
= 5(5+ 2) = 35 BM
56. Electronic configuration of Gadolinium is:
15. A single unpaired electron has magnetic [Xe] 4f7 5d1 6s2
moment µ = 1.73 BM.
Outer electronic configuration of Ti3+ and Cu2+ 57. The colour of ions having nf electrons is about
ions is 3d1 and 3d9 respectively possessing the same as those having (14 – n)f electrons.
single unpaired electron. (where n is an integer 1-13).
17. Ni2+ and Cr3+ are coloured due to the presence 71. Nichrome, an alloy of nickel and chromium in
of 2 and 3 unpaired electrons respectively. But the ratio 80 : 20 has been developed specifically
Zn2+ is colourless because of absence of for gas turbine engines.
unpaired electrons. Bronze, an alloy of copper and tin is used for
making statues, medals and trophies.
20. Co-Th alloy is used in Fischer Tropsch process
in the synthesis of gasoline.
Mo/Fe is used as a catalyst in the manufacture Critical Thinking
of ammonia by Haber’s process.
1. Zr, Cd and Ag are 4d transition series elements.
26. In acidic medium,
5S2– + 2MnO −4 + 16H+ → 2Mn2+ + 5S + 8H2O 3. 3d series begins with Sc and ends with Zn.
Oxidation state of S in the product is 0. 4. Electronic configuration of Co2+ ion: [Ar] 3d7
27. In neutral medium, KMnO4 oxidises Mn2+ salt ↑ ↑ ↑
↑↓ ↑↓
to Mn4+.
2MnO −4 + 3Mn2+ + 2H2O → 5MnO2 + 4H+ ⸫ No. of unpaired e– = 3
61


5. Cr2+ : [Ar] 3d4 14. If d-orbital contains 7-electrons, it has
Co3+ : [Ar] 3d6 3 unpaired electrons.
Mn3+ : [Ar] 3d4 ∴ Spin-only magnetic moment (µ)
Fe3+ : [Ar] 3d5 = n(n + 2) BM
6. Electronic configuration of Cu+ ion: = 3(3 + 2) = 3×5 = 15 = 3.87 BM
1s2 2s2 2p6 3s2 3p6 3d10
Number of s electrons = 2 + 2 + 2 = 6 15. [Co(H2O)6]2+ + 4Cl– → [CoCl4]2– + 6H2O
pink deep blue
8. Ti : [Ar] 3d2 4s2 ⇒ Ti+ : [Ar] 3d2 4s1
V : [Ar] 3d3 4s2 ⇒ V+ : [Ar] 3d3 4s1 18. 3MnO2 + 6KOH + KClO3  ∆
→
Cr : [Ar] 3d5 4s1 ⇒ Cr+ [Ar] 3d5 4s0 3K2MnO4 + KCl + 3H2O
Mn : [Ar] 3d5 4s2 ⇒ Mn+ [Ar] 3d5 4s1 Compound (X) is potassium manganate
In Cr, for second ionization, the electron needs (K2MnO4). It is dark green coloured. Oxidation
to be removed from stable half-filled orbital and state of Mn in X is +6.
hence requires more energy. +
19. 2MnO−4 + 5H2C2O4 + 6H →
Therefore, the order of decreasing second
ionization enthalpy is Cr > Mn > V > Ti. 2Mn2+ + 10CO2 + 8H2O
9. Third ionization enthalpy involves removal of 21. Na2Cr2O7 + 2KCl → K2Cr2O7 + 2NaCl
third outermost electron. (X)
The electronic configurations are
K2Cr2O7 + 4H2SO4 + 3H2S → K2SO4
Ni = [Ar] 3d8 4s2
+ Cr2(SO4)3 + 7H2O + 3S
Co = [Ar] 3d7 4s2
(Y)
Mn = [Ar] 3d5 4s2
Fe = [Ar] 3d6 4s2 22. Siderite (FeCO3) and calamine (ZnCO3) are
On removing the third electron, Fe will attain carbonate ores of iron and zinc respectively.
half filled stability. Hence, among the given
24. Conversion of ferrous oxide (FeO) to ferric
elements, the third ionization enthalpy is
oxide (Fe2O3) occurs during roasting and not
minimum for Fe.
during extraction of iron in blast furnace.
10. Among elements of first transition series, zinc
has the highest first ionization enthalpy. This is 25. Wrought iron is very soft while cast iron is hard
due to its completely filled 3d and 4s orbitals. and brittle.
11. Cu2+ : [Ar] 3d9 4s0 → 1 unpaired e− 26. Lanthanoids react with water to give the metal
Ni2+ : [Ar] 3d8 4s0 → 2 unpaired e− hydroxide and hydrogen gas. Their hydroxides
are ionic and basic.
Ti4+ : [Ar] 3d0 4s0 → 0 unpaired e−
Mn2+ : [Ar] 3d5 4s0 → 5 unpaired e− 28. The third ionization enthalpy involves removal
Hence, Ti4+ is diamagnetic as it does not have of third outermost electron.
unpaired electrons. Yb = [Xe]4f14 6s2
La = [Xe]4f0 5d1 6s2
12. Magnetic moment = n(n + 2) BM
Lu = [Xe]4f14 5d1 6s2
(where n = number of unpaired electrons) Ce = [Xe]4f1 5d1 6s2
Paramagnetic behaviour is directly proportional On removing the third electron, Yb will lose its
to the number of unpaired electrons. completely filled stability. Hence, among the
Outer electronic No. of unpaired given elements, the third ionization enthalpy is
Ion highest for Yb.
configuration electrons
Mn2+ 3d5 5 29.
Cu2+ 3d9 1 Outer No. of
Sc2+ 3d1 1 Ion electronic unpaired
Cr2+ 3d4 4 configuration electrons
Therefore, among the given ions, Mn2+ has Lu3+ (Z = 71) [Xe] 4f14 0
maximum paramagnetic behaviour. Pr3+ (Z = 59) [Xe] 4f2 2
La3+ (Z = 57) [Xe] 4f0 0
13. Magnetic moment will be equal if the ions have
Yb2+ (Z = 70) [Xe] 4f14 0
same number of unpaired electrons.
Cr2+ and Fe2+ The colour is due to electronic transitions
Cr2+ : [Ar]3d4 ∴ 4 unpaired electrons among the f orbitals. If there are no unpaired
Fe2+ : [Ar]3d6 ∴ 4 unpaired electrons electrons, such ions are colourless.
62

Transition Elements
30. Yb3+ (Z = 70) < Pm3+ (Z = 61) < Ce3+ (Z = 58) 41. (A) The last element of actinoid series is
< La3+ (Z = 57). lawrencium.
Atomic number decreases from Yb to La. (C) The last element of 5d transition series is
Hence, ionic radii increase from Yb3+ to La3+. mercury.
(D) The first element of lanthanoid series is
31. As we move along the lanthanoids series, lanthanum.
atomic and ionic radii gradually decrease with
increase in atomic number.
Therefore, ionic radius of Lu3+ (86 pm) is less
than the ionic radius of Ce3+ (102 pm). 1. Since Zn, Cd and Hg have completely filled
(n – 1) d orbitals in their ground states as well as
32. Ce → [Xe]4f1 5d1 6s2 ; Ce4+ → [Xe] in the form of ions, they are excluded from
Yb → [Xe]4f14 6s2 ; Yb2+ → [Xe]4f14 transition series. Hence, among the given
Lu → [Xe]4f14 5d1 6s2 ; Lu3+ → [Xe]4f14 options, only Au is a transition element.
Eu → [Xe]4f7 6s2 ; Eu2+ → [Xe]4f7 2. Observed electronic configuration of titanium
2+
Eu has 7 unpaired electrons. Hence, it is is:
paramagnetic. 1s2 2s2 2p6 3s2 3p6 4s2 3d2
The 4s orbital is lower in energy as compared to
33. Actinium is the first element of 6d transition the 3d orbital.
series. So, in ground state, it will have 1 electron
in its 6d orbital. Hence, correct answer is (A). 3. Electronic configuration of Ni = [Ar] 3d8 4s2
34. Electronic configuration of uranium is: ↑↓ ↑↓ ↑↓ ↑ ↑ ↑↓

[Rn] 5f3 6d1 7s2
No. of unpaired electrons = 2
The formation of +6 oxidation state corresponds
to an electronic configuration of [Rn]. 4. Electronic configuration of X3+ : [Ar] 3d5
Electronic configuration of X : [Ar] 3d6 4s2
35. Electronic configuration of nobelium (No) is: Atomic number of X = 18 + 6 + 2 = 26
[Rn] 5f14 6d0 7s2.
7. Sc3+ → [Ar]3d0
After losing 2 electrons No forms No2+ ion, Due to absence of unpaired electrons, it is
which is stable due to completely filled diamagnetic.
5f-orbitals. Such extra stability due to
completely filled orbital is not acquired by any 8. Magnetic moment = n(n + 2) BM (where
other actinoid in their +2 oxidation state. n = number of unpaired electrons)
Hence, nobelium is the only actinoid with Therefore, magnetic moment is directly
+2 oxidation state. proportional to the number of unpaired electrons.
36. UO3(s) + H2SO4(aq) → UO2SO4(aq) + H2O(l) Calculated
Outer No. of
Uranyl sulphate value of
Ion electronic unpaired
magnetic
37. Among lanthanoids, only promethium is moment
radioactive. In actinoid series, all elements are Fe3+ 3d5 5 5.92 BM
radioactive. Cr3+ 3d3 3 3.87 BM
Ti3+ 3d1 1 1.73 BM
38. Pre-transition metals do not exhibit ligand field Co3+ 3d6 4 4.90 BM
effects.
39. (B) Lanthanoids do not form oxocations while (where n = number of unpaired electrons)
actinoids form oxocations.
Therefore, magnetic moment is directly
(C) Lanthanoids show a maximum oxidation proportional to the number of unpaired electrons.
of +4 while actinoids show a maximum
oxidation state of +7. Calculated
Outer No. of
value of
(D) Lanthanoids show flexibility in geometry Ion electronic unpaired
magnetic
while transition metals show fixed configuration electrons
moment
geometries (ligand field effects).
Cr3+ 3d3 3 3.87 BM
40. Pr is f-block element, As is p-Block element Co3+ 3d6 4 4.90 BM
(representative element), Rb is an alkali metal Ti3+ 3d1 1 1.73 BM
and Mo is a transition element. V3+ 3d2 2 2.83 BM
63


10. The condensed electronic configuration for 18. Sc → [Ar] 3d1 4s2
Ni2+ (Z = 28) will be Sc3+ → [Ar] 3d0
3d 4s Due to absence of unpaired electrons,
compounds of Sc3+ are colourless.
[Ar]
19. x −1
CrCl3 : x + 3(−1) = 0 ⇒ x = 3
There are 2 unpaired electrons, so n = 2.
Cr : [Ar] 3d5 4s1
∴ µ= n(n + 2) BM = 2( 2 + 2) Cr3+ : [Ar] 3d3 4s0
= 2.83 BM ≈ 2.84 BM Cr3+ contains three unpaired electrons. Hence,
CrCl3 will be coloured.
11.
20. Intense purple colour of KMnO4 results from the
Ion Outer electronic Number of momentary transfer of an electron from oxygen
configuration unpaired electrons (ligand L) to Mn (metal M).
Ni2+ 3d8 2
22. In Fischer-Tropsch process (for the synthesis of
Ti3+ 3d1 1 gasoline), Co-Th alloy is used as a catalyst.
Cr2+ 3d4 4
Co2+ 3d7 3 23. Transition metallic carbides are chemically inert.
24. In neutral or faintly alkaline KMnO4 solution,
The magnetic moment µ = n(n + 2) BM,
iodide ion is converted into iodate.
Where n = number of unpaired electrons. − −
2MnO 4− + H2O + I → 2MnO2 + 2OH + IO3−
When n = 2; µ = 2(2 + 2) = 8 = 2.84 BM
∴ Magnetic moment 2.84 BM is given by Ni2+. 25. In acidic medium:
+ – 2+
MnO −4 + 8H + 5e → Mn + 4H2O
12. Magnetic moment (µ) = n ( n + 2 ) BM (i) FeC2O4 ⇒ 1 mol oxalate ion and 1 mol
ferrous ion:
Number Calculated Oxalate ion:
Outer
of value of +
2MnO 4− + 5C2O 24 − + 16H → 2Mn
2+
Ion electronic
unpaired Magnetic
configuration + 8H2O + 10CO2
electrons moment
∴ 2
1 mol C2O4 ≡ mol MnO−4
Co3+ 3d6
2−
4 24 BM 5
Cr3+ 3d3 3 15 BM Ferrous ion:
2+ + 2+
Fe3+ 3d5 5 35 BM 2MnO −4 + 10Fe + 16H → 2Mn
Ni2+ 3d8 2 + 10Fe3+ + 8H2O
8 BM
3+ 2+
∴ 1 mol Fe2+ ≡ 1 mol MnO−4
13. Fe and Mn will have similar magnetic 5
moment as they have same number of unpaired (ii) Fe2(C2O4)3 ⇒ 3 mol oxalate ions and 2
electrons. mol ferric ions:
Fe3+ (3d5) : 5 unpaired electrons ∴ 1 mol C2O24 − ≡ 2 mol MnO−4
Mn2+ (3d5) : 5 unpaired electrons 5
Now, 1 mol Fe2(C2O4)3 ≡ 3 mol C2O42 −
14. CuSO4 will be absorbing orange-red colour and 6
emits out blue colour. ∴ 3 mol C2O24 − ≡ mol MnO−4
5
15. The colour of light in the wavelength region (iii) FeSO4 ⇒ 1 mol ferrous ion and 1 mol
490-500 nm is green. Its complementary colour sulphate ion:
is red. ∴ 1 mol Fe2+ ≡ 1 mol MnO−4
5
4+ 0 + 10
16. Ti (3d ) and Cu (3d ) ions are colourless due (iv) Fe2(SO4)3 ⇒ 2 mol ferric ions and 3 mol
to absence of unpaired electrons. sulphate ions:
No oxidation reaction.
17. Sc3+ → [Ar] 3d0
Thus, total moles of KMnO4 required
Fe2+ → [Ar] 3d6 2 1 6 1
Ti3+ → [Ar] 3d1 = + + +
5 5 5 5
Mn2+ → [Ar] 3d5 = 10
Due to absence of unpaired electrons, Sc3+ ion 5
will be colourless. = 2 mol
64

Transition Elements
26. Chromite ore is FeCr2O4 (or FeO.Cr2O3). 40. Due to poor shielding of 4f electrons (i.e.,
negligible screening effect of ‘f’ orbitals),
27. Sodium chromate is converted to sodium
increased effective nuclear charge is
dichromate by treatment with concentrated
experienced and the valence shell is pulled
sulphuric acid.
slightly towards nucleus thereby resulting in the
2Na2CrO4 + H2SO4 (Conc.) → Na2Cr2O7
lanthanoid contraction.
+ Na2SO4.H2O
41. Since the ionic size decreases from La3+ to Lu3+,
28. In acidic medium, Cr(VI) of potassium the basicity of hydroxides decreases in the
dichromate gains 3 electrons and is reduced to following order:
Cr(III) of chromium sulphate. Thus, potassium La(OH)3 > Pr(OH)3 > Sm(OH)3 > Ho(OH)3
dichromate is a good oxidizing agent.
+ − 3+
Cr2O72 − + 14H + 6e → 2Cr + 7H2O 42. Lu3+ → [Xe]4f14 5d0 6s0
Thus, oxidation state of chromium changes by Ce3+ → [Xe]4f1 5d0 6s0
(+6) − (+3) = 3 Eu3+ → [Xe]4f6 5d0 6s0
Yb3+ → [Xe]4f13 5d0 6s0
29. Siderite (FeCO3) is a carbonate ore of iron while Lu3+ does not have any unpaired electrons and
magnetite (Fe3O4), haematite (Fe2O3) are oxide hence, it is not paramagnetic.
ores and iron pyrites (FeS2) is a sulphide ore.
43. Yb2+ has an electronic configuration of 4f14. Since
36. The observed electronic configuration of Ce is there is absence of unpaired electron, it is
[Xe] 4f1 5d1 6s2. Therefore, the electronic diamagnetic in nature.
configuration of Ce3+ ion is [Xe] 4f1.
45. The atomic radii of 4d (Ag) and 5d (Au) series
38. elements belonging to the same group are
Outer electronic Oxidation almost similar.
Element
configuration states
63
Eu 4f7 5d0 6s2 +2, +3 46. Magnesite (MgCO3) is a mineral of magnesium
65
Tb 4f9 5d0 6s2 +3, +4 while others are minerals of iron.
5. When H2S gas is passed through acidified 10. In this reaction

2+ + 2+ 3+
K2Cr2O7 solution, it is oxidized to sulphur. MnO −4 + 5Fe + 8H → Mn + 5Fe 4H2O
Colour of the solution changes from orange to 1 mol 5 mol
green due to formation of Cr2(SO4)3. 1 mol MnO −4 = 5 mol Fe2+
K2Cr2O7 + 3H2S + 4H2SO4 → K2SO4 + Since concentration of the solutions is the same,
Cr2(SO4)3 + 7H2O + 3S volume of FesO4 will be 5 times, i.e., 50 mL.
7. Cu : [Ar] 3d10 4s1 13. Electronic configuration of cobalt:

Cu2+ : [Ar] 3d9 4s0 [Ar] 3d7 4s2
⸫ No. of d-electrons = 7
∴ 1 unpaired electron
V : [Ar] 3d3 4s2 14. (B) Nitrates and sulphates of lanthanoids and
actinoids are soluble.
V2+ : [Ar] 3d3 4s0
(C) The electronegativity of lanthanoid and
∴ 3 unpaired electrons actinoid elements are low.
Cr : [Ar] 3d5 4s1 (D) Actinoids show greater tendency to form
Cr2+ : [Ar] 3d4 complexes as compared to lanthanoids.
∴ 4 unpaired electrons 15. The element in + 3 oxidation state has the
Mn : [Ar] 3d5 4s2 electronic configuration [Ar] 3d3. Hence, the
Mn2+ : [Ar] 3d5 electronic configuration in elemental form is
∴ 5 unpaired electrons [Ar] 3d6. So, the atomic number is sum of
Greater the number of unpaired electrons, atomic number of Ar and 6 electrons in 3d
greater will be its paramagnetic property. Hence subshell i.e., 18 + 6 = 24.
the order of increase in the paramagnetic 20. Among the given transition elements, tungsten
property is Cu2+ < V2+ < Cr2+ < Mn2+. (W) has the highest melting point.
65


102. For filling balloons, a mixture of helium (85%)
2Fe3+ + SO2 + 2H2O and hydrogen (15 %) is used.
Ferric Sulfur
ion dioxide
Critical Thinking
→ 2Fe2+ + SO 24 − + 4H+
Ferrous Sulfate Hydrogen 2. CuFeS2: Copper pyrites
ion ion ion Na3AlF6: Cryolite
79. Sulphuric acid is a strong oxidising agent. 3Ca3(PO4)2.CaF2: Fluorapatite
83. Chlorine is 2-5 times heavier than air. CaSO4.2H2O: Gypsum
84. Excess of chlorine reacts with ammonia to give 3. (II) Sea weeds contain upto 0.5 % iodine.
nitrogen trichloride (explosive). (IV) Halogens are not found in free state in
nature.
NH3 + 3Cl2 → NCl3 + 3HCl 10 2 6
Ammonia Chlorine Nitrogen Hydrogen 4. 36Kr: [Ar] 3d 4s 4p
10 2 6
(excess) trichloride chloride 54Xe: [Kr] 4d 5s 5p
85. 2Ca(OH)2 + 2Cl2 5. The atomic radii increase down the group
Dry slaked lime Chlorine
whereas ionisation enthalpy decreases down the
group.
→ Ca(OCl)2 + CaCl2 + 2H2O
Bleaching powder Calcium chloride 6. The ionic radii increase down the group as a
result of increase in the number of quantum
86. Chlorine requires the presence of moisture for shells.
its bleaching action. Chlorine is not used to
bleach delicate materials such as silk, wool, etc. 7. Fluorine has highest ionisation enthalpy among
as it is a strong bleaching and oxidising agent. halogens. Chlorine has highest negative electron
This dual action will damage the base material. gain enthalpy among halogens.
88. Interhalogens have general formula XX′n. The 8. Group 18 elements have large positive electron
number of X′ atoms is always odd. gain enthalpy as they have no tendency to
accept electrons. This is because of their stable
89. Interhalogen compounds have even number of
atoms 2, 4, 6, 8. For example, ClF3 has 4 atoms. electronic configuration (ns2 np6).
90. BrF3: Yellow green liquid 9. Effective nuclear charge increases across a
IF3: Yellow powder period and decreases down the group. Thus,
IBr: Black solid ionisation enthalpy increases across a period and
ICl3: Orange solid decreases down the group.
+3 Element Cl O F He
91. I2 + 3Cl2 → 2 I Cl3
(excess) Ionisation 1256 1314 1680 2372
enthalpy
93. I2 + KClO3 
∆
→ ICl + KIO3 (kJ/mol)
95. Interhalogens of type XX′3 have sp3d 12.
hybridization. They have two lone pairs of
Compound Oxidation state of xenon
electrons on central atom X.
XeOF4 +6
99. Partial hydrolysis of XeF4 yields xenon XeO3 +6
monooxydifluoride (XeOF2). XeF6 +6
XeF4 + H2O 
80 ° C
→ XeOF2 + 2HF XeF4 +4
Xenon Water Xenon Hydrogen
XeF2 +2
tetrafluoride monooxydifluoride fluoride
13. The acidic character of the hydrides increases,
while thermal stability decreases from H2O to
101. XeF4: Square planar ; H2Te.
XeF6: Distorted octahedral
XeO3: Trigonal pyramidal ; 14. The acidic character of the hydrides increases
XeOF4: Square pyramidal from H2O to H2Te because the bond
56

Chapter 9: Coordination Compounds

25. NH3 (Ammonia) is a neutral ligand with zero charge and named “ammine”.
32. EAN = atomic number (Z) − oxidation number of metal ion + number of electrons donated by ligands.
86 = Z − (4) + (2 × 6)
86 = Z – 4 + 12
Z = 78
33. Oxidation state of Co is +3 and ligands donate 12 electrons.
Z = 27, X = 3, Y = 12
EAN of Co3+ = Z – X + Y
= 27 – 3 + 12
= 36
34. a b a a
M M
b a b b
Trans-isomer Cis-isomer
Ma2b2
35. Octahedral complexes of the types; [MA4B2], [MA2B4] exhibit geometrical isomerism.
36. Tetrahedral complexes do not exhibit geometrical isomerism.
37. In ionization isomerism, there is exchange of ions inside and outside the coordination sphere. They have the
same formula but produce different ions in solution.
38. Coordination isomerism is observed in the coordination compounds having both cationic and anionic
complex ions. The ligands are interchanged in both the cationic and anionic ions to form isomers.
40. SCN− ion can coordinate through the sulphur or nitrogen atom. Such possibilities give rise to linkage
isomerism in coordination compounds.
M ← SCN Thiocyanato or thiocyanato-S ; M ← NCS Isothiocyanato or thiocyanato-N
41. In coordination isomerism, there is an interchange of ligands between cationic and anionic spheres of
different metal ions.
42. Higher the value of stability constant, greater is the thermodynamic stability of the complex.
44. Higher the charge to size ratio, greater is the stability. For the metal ions having same change, smaller the
atomic radius, greater will be charge to size ration and hence, grewter will be the stability of complex.
48. The four metal ion orbitals for bonding with Cl– ligands are derived from the sp3 hybridization. The complex
is tetrahedral. Electronic configuration after complex formation would be
4s 4p
↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓
sp3
49. The central atom is surrounded by four chloride molecules (ligands) exhibiting tetrahedral configuration.
Electronic configuration after complex formation would be.
4s 4p
[VCl4]– 3d
↑ ↑ ↓↑ ↓↑ ↓↑ ↓↑
sp3
67


10. Thermal stability decreases from H2O to H2Po.
23. Chlorine reacts with water to form HCl and
11. All hydrides except H2O possess reducing HOCl. HOCl gives nascent oxygen which
property as H2O is very stable molecule. results in bleaching action.
∆Hdiss(O – H) = 463 kJ mol–1. Therefore, it does OCl– → [O] + Cl–
not act as a reducing agent. Hence, the reactive species in chlorine bleach is
OCl–.
13. Among halogens, only chlorine forms the
halous acid like chlorous acid wherein the 26. Aqua regia dissolves gold,
chlorine atom is in tripositive oxidation state. +5
Au + 4H+ + NO3− + 4Cl−
O Gold Nitrate Chloride
O ion ion
H Cl +2
→ AuCl−4 + NO + 2H2O
Chlorous acid Tetrachlorido- Nitric Water
(Oxidation state of Cl: +3) aurate(III) oxide
14. The acid strength of the halogen oxoacids
27. Interhalogen compounds are more reactive than
increases with the increasing oxidation state of
halogen. halogens. This is because X−X′ bonds present in
Also, the increasing order of charge them are weaker than X−X or X′−X′ bonds.
delocalization in the anions of oxoacids of ∆
28. MnO2 + 4HCl → MnCl2 + Cl2 + H2O
chlorine is, ClO− < ClO 2− < ClO3− < ClO −4 . Manganese Chlorine
Manganese Hydrochloric Water
With increase in charge delocalisation, the dioxide acid
dichloride (A)
stability of the ion increases and the basicity of
the anion decreases. Thus, ClO− is the strongest 573 K
base and ClO −4 is the weakest base. A weak base Cl2 + 3F2 → 2ClF3
Chlorine Fluorine Chlorine trifluoride
has strong conjugate acid and vice versa. Hence, (A) (excess) (colourless gas)
HClO (conjugate acid of ClO−) is the weakest (B)
acid and HClO4 (conjugate acid of ClO −4 ) is the
3ClF3(l) + U(s) → UF6(g) + 3ClF(g)
strongest acid. Hence, the correct increasing Chlorine Uranium Chlorine
order of acid strength is: Uranium
trifluoride hexafluoride monofluoride
HClO < HClO2 < HClO3 < HClO4. (B) (C) (D)
15. SO2, CO2 → Acidic oxide In the given series of reactions, the gases A, B,
BaO → Basic oxide C and D are Cl2, ClF3, UF6 and ClF
N2O → Neutral oxide respectively.
17. Ozone, on reaction with potassium iodide (KI) 30. The structure of BrF5:
solution, oxidises iodide ions to iodine (I2).
2KI(aq) + H2O(l) + O3(g) → 2KOH(aq) + I2(s) + O2(g)
Potassium Ozone Potassium Iodine Oxygen F F
iodide hydroxide Br
F F
18. Ozone molecule is angular with O − O − O bond F
angle as 116.8° (≈ 117°). Both O − O bonds are
identical having bond length 128 pm (i.e., 1.28 Å) 32. 1 mol of H2O = 18 g of H2O
[Since, 1 Å = 10−10 m and 1 pm = 10−12 m]. ∴ 0.1 mol of H2O = 1.8 g of H2O
19. Sulphur dioxide is not a dehydrating agent. Molar ratio of XeF6 : H2O = 1 : 1
0.1 mole of XeF6 reacts with 0.1 mole of H2O
22. Chlorine reacts with cold and dilute alkali to (i.e., 1.8 g) to form 0.1 mole of XeOF4.
produce a mixture of chloride and hypochlorite.
2NaOH + Cl2 → NaCl + NaOCl 36. Rhombic sulphur and monoclinic sulphur are
Sodium hydroxide Chlorine Sodium Sodium polymorphic forms of sulphur, i.e, arrangement
(Cold and dilute) chloride hypochlorite
59


of molecules is different. However, both the N2O5 is an acidic oxide.
crystals are made up of S8 molecules. MgO is a basic oxide.
40.
37. The valence shell electronic configuration of Element Nature of oxide
p-block elements is ns2np1−6, except helium, Calcium Basic
which has 1s2 configuration. Helium contains Zinc Amphoteric
completed duplet and hence, one molecule of Carbon Acidic
He consists of only one atom (i.e., it is a Sulphur Acidic
monoatomic element).
38. Generally, acidic oxides are the binary 42.

compounds of oxygen with nonmetals whereas Element Type
basic oxides are the binary compounds of (A) Carbon Non-metal
oxygen with highly electropositive metals. (B) Neon Noble gas
(C) Sodium Alkali metal
39. ZnO and Al2O3 are amphoteric oxides. (D) Tellurium Metalloid

5.
Compound Oxidation state of xenon 9. Acidic oxides: Cl2O7
XeOF4 +6 Amphoteric oxides: Al2O3
XeO3 +6 Neutral oxides: CO, NO
XeF6 +6 10. SO2 is highly soluble in water and its solution in
XeF4 +4 water is called sulfurous acid (H2SO3).
XeF2 +2 11. Perchloric acid, HClO4
7. Acidic character of hydrides of group 17 Oxidation state of ‘Cl’ = +7
elements increases down the group. Thus, HF is
13. Let ‘x’ be the oxidation number of sulphur. S8 is
least acidic in nature.
the elemental form of sulphur. Hence, oxidation
8. Peroxydisulfuric acid, H2S2O8 state is zero.
In S2F2, 2x − 2 = 0
O O
∴ 2x = 2
S S x=1
O O–O O In H2S, 2 + x = 0
OH OH x=−2
Thiosulfuric acid, H2S2O3 14. The noble gas which forms maximum number
of compounds is Xe.
S e.g. XeF2 , XeOF2 . XeF4 , XeOF4 . XeF6 , XeO3 .
S 18. Most electronegative fluorine shows only –1
HO
O oxidation state. Chlorine, bromine and iodine
OH
show –1, +1, +3, +5 and +7 oxidation states.
Sulfurous acid, H2SO3 Chlorine and bromine also exhibit +4 and +6
oxidation states.
S
HO
HO O
Disulfuric acid or pyrosulfuric acid, H2S2O7

O O
S S
O O O
OH HO
60

Transition Elements
08 Transition and Inner Transition Elements
Hints
28. Oxidation of I− from aqueous solution of KI by

Classical Thinking acidified K2Cr2O7 gives I2. Potassium
dichromate is reduced to chromic sulphate.
8. Fe, Cu and Ni show variable oxidation states Liberated I2 turns the solution brown.
whereas Zn shows only +2 due to completely K2Cr2O7 + 6KI + 7H2SO4 → 4K2SO4
filled stable 3d10 electronic configuration. + Cr2(SO4)3 + 7H2O + 3I2
10. For the same oxidation state, the ionic radii
32. x + 4 (−2) = 0
generally decrease with increase in nuclear
charge. Therefore, the decreasing order of ionic x−8=0
radii of given ions will be: x = +8
Sc3+ > Ti3+ > Mn3+ > Co3+ 33. Noble metals like gold, platinum, etc., being
73 pm 67 pm 65 pm 61 pm
unreactive, are found in free state.
So, Sc3+ has the largest ionic radius.
11. In transition series, the first ionization enthalpy 43. In the zone of combustion, the temperature is
slightly increases from left to right, due to around 2000 K.
decrease in size of the atom from left to right. 44. Reaction (A) and (C) occur in the zone of slag
However, the ionization enthalpy of the last formation.
element (i.e., Zn) is high due to extra stability Reaction (B) occurs in the zone of reduction.
gained because of completely filled d-orbitals.
Reaction (D) occurs in the zone of combustion.
14. Fe3+ ion is [Ar] 3d5 4s0. It has 5 unpaired
electrons. 48. Lanthanoids (14 elements) and actinoids
(14 elements) together form the inner transition
∴ Spin-only magnetic moment, µ = n(n + 2) BM
elements.
= 5(5+ 2) = 35 BM
56. Electronic configuration of Gadolinium is:
15. A single unpaired electron has magnetic [Xe] 4f7 5d1 6s2
moment µ = 1.73 BM.
Outer electronic configuration of Ti3+ and Cu2+ 57. The colour of ions having nf electrons is about
ions is 3d1 and 3d9 respectively possessing the same as those having (14 – n)f electrons.
single unpaired electron. (where n is an integer 1-13).
17. Ni2+ and Cr3+ are coloured due to the presence 71. Nichrome, an alloy of nickel and chromium in
of 2 and 3 unpaired electrons respectively. But the ratio 80 : 20 has been developed specifically
Zn2+ is colourless because of absence of for gas turbine engines.
unpaired electrons. Bronze, an alloy of copper and tin is used for
making statues, medals and trophies.
20. Co-Th alloy is used in Fischer Tropsch process
in the synthesis of gasoline.
Mo/Fe is used as a catalyst in the manufacture Critical Thinking
of ammonia by Haber’s process.
1. Zr, Cd and Ag are 4d transition series elements.
26. In acidic medium,
5S2– + 2MnO −4 + 16H+ → 2Mn2+ + 5S + 8H2O 3. 3d series begins with Sc and ends with Zn.
Oxidation state of S in the product is 0. 4. Electronic configuration of Co2+ ion: [Ar] 3d7
27. In neutral medium, KMnO4 oxidises Mn2+ salt ↑ ↑ ↑
↑↓ ↑↓
to Mn4+.
2MnO −4 + 3Mn2+ + 2H2O → 5MnO2 + 4H+ ⸫ No. of unpaired e– = 3
61


39. i. NO2 is an ambidentate ligand. It can show linkage isomerism.
ii. The complex can show ionization isomerism with the complex [Co(NH3)4Cl(NO2)]NO2
iii. The complex shows geometrical isomerism.
NO2 NH3
H3N NH3 H3N NO2
Co Co
H3N NH3 H3N NO2

NO2 NH3
Trans-isomer Cis-isomer
41. Higher the magnitude of charge and smaller the size of the ion, more is the charge density on the metal ion
and greater is the stability of the complex. The magnitude of positive charge on Cu2+ and Cd2+ is same;
however, the ionic radius of Cu2+ ion is less than that of Cd2+ ion. Hence, the charge density (Charge by size
ratio) on Cu2+ ion is greater than that of Cd2+ ion. Thus, the complexes formed by Cu2+ ion are more stable
than those formed by Cd2+ ion.
43. Cyanide ion has greater basicity than halide ion; hence it forms stronger complex with Cd.
3d 4s 4p 4d
3–
44. [CoF6] ↑↓ ↑ ↑ ↑ ↑ ×× ×× ×× ×× ××××
Valence electrons of
Co sp3d2 orbitals containing
electrons of ligands
45. Oxidation state of metal = +2

[Ni(NH3)6]2+
3d 4s 4p 4d
↑↓ ↑↓ ↑↓ ↑ ↑ ×× ×× ×× ×× ××××
sp3d2 (outer)
46. In [Ni(CN)4]2– ion, electronic configuration of central metal ion would be
3d 4s 4p
↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↓↑ ↓↑ ↓↑
47. Electronic configuration of central metal ion after formation of complex would be
3d 4s 4p 4d
↓↑ ↑ ↑ ↑ ↑ ↓↑ ↓↑ ↓↑ ↓↑ ↓↑ ↓↑
sp3d2
There are 4 unpaired electrons in 3d orbitals.
48. Outer electronic configuration of Pt is 5d9 6s1. Outer electronic configuration of Pt2+ is 5d8. As CN− is strong
field ligand, so pairing will take place.
Pt2+:
↑↓ ↑↓ ↑↓ ↑↓ × × × × × × × ×
5d 5p
6s
2
dsp hybridised orbitals containing
electrons of CN– ligands
There is no unpaired electron in 3d orbitals.
71


49. (I) [Fe(CN)6]3–
Configuration of central metal ion after complex formation:
3d 4s 4p
↑↓ ↑↓ ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓
d2sp3
3–
(III) [COF6]
Configuration of central metal ion after complex formation:
3d 4s 4p 4d
↑↓ ↑ ↑ ↑ ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓
sp3d2
There are one and four unpaired electrons in complexes I and III, respectively; hence, these complexes are
paramagnetic.
50. [Fe(H2O)6]2+ is paramagnetic while [Fe(CN)6]4− is diamagnetic.
51. In [NiX4]2–Ni has +2 oxidation state.
The eletronic configuration of [NiX4]2– would be
3d 4s 4p
↑↓ ↑↓ ↑↓ ↑ ↑ ↑↓ ↑↓ ↑↓ ↑↓
Hence, it has two unpaired electrons and is tetrahedral complex.
52. In octahedral complex, the ligands approach along the axes and hence, the dz2 and dx2−y2 orbitals experience
maximum electrostatic repulsion due to ligands. Hence, the energy of these orbitals increases.
53. The oxidation state of metal is same in all the cases, i.e., +3. CN– being the strongest ligand among the given,
[Co(CN)6]3− will have maximum crystal field stabalization energy.
54. Crystal field splitting energy for tetrahedral complex (∆t) = (4/9) Crystal field splitting energy for octahedral
complex.
55. Only Cr3+ in the complex has unpaired electrons in the d orbital, while Sc3+, Ti4+ and Zn2+ do not have d
electrons.
59. Since no precipitate of AgCl with AgNO3 is obtained, all the chloride ions are inside the coordination
sphere. Therefore, PtCl4.2NH3 gives zero ions in the solution. Hence, all the ligands are present inside the
coordination sphere. Thus, the structure is [Pt(NH3)2Cl4]. In PtCl4.2KCl gives 3 moles of ions in solution.
 2K+ + [PtCl6]−2 . Hence, the structure is K2[PtCl6].
K2[PtCl6] 
60. The complex is K 2 [ PtCl6 ] .
When the complex is dissolved in water, it ionises as:
K 2 [ Pt Cl6 ]  2K + + [ PtCl6 ]
2−
3 ions
Hence, each molecule will give 3 ions.
As Cl− ions are not present in the ionisation sphere, Cl− ions will not be formed and hence, AgCl will not be
precipitated.
4–
N≡ C≡
61. 4K+ N≡ Fe C≡
N≡ C≡
Bond between K+ and [Fe(CN)6]4– is ionic.
Bond between C and N in CN– ions is covalent.
Bond between CN– ions and Fe is coordinate covalent.
72


62. The formula of the complex is [M(H2O)4Cl2]Cl.
0.1 × V = 0.01 × 200
∴ V = 20 mL
−
1. x 
 AuCl4 
x + 4(–1) = –1
∴ x = +3
2. Charge on the ligand C 2 O 24 − is −2 and charge on the complex ion is −4.

Let the oxidation number of Ni be x.
∴ x + 3 × (−2) = −4
x = +2
Oxidation number of Ni in [Ni(C2O4)3]4– = +2
3. The complex is [Fe(CN)6]3–
x + 6 (–1) = –3
∴ x = +3
Since there are 6 CN– ligands attached to Fe, the coordination number of Fe is 6.
4. [M(en)2(C2O4)]Cl
The complex has two molecules of en and one C2O42− ion. Thus, the complex has three bidentate ligands in
all.
∴ Coordination number = 2 × number of bidentate ligands. = 2 × 3 = 6
Let the oxidation number of metal ‘M’ in the complex be ‘x’.
The charge on complex ion, en and C2O42− are +1, 0 and −2 respectively.
Hence, x + 0 − 2 = +1
x=3
∴ The sum of coordination number and oxidation number of the metal M = 6 + 3 = 9.
6. Mohr’s salt is FeSO4.(NH4)2SO4.6H2O.
When it is dissolved in excess of water, one molecule forms one Fe2+ ion, two NH4+ ions and two SO 24 − ions
(i.e., total five ions per molecule).
7.
Composition Formula of the complex No. of Cl− ions precipitated by AgNO3
CoCl3.3NH3 [CoCl3(NH3)3] 0
CoCl3.4NH3 [CoCl2(NH3)4]Cl 1
CoCl3.5NH3 [CoCl(NH3)5]Cl2 2
CoCl3.6NH3 [Co(NH3)6]Cl3 3
Therefore, CoCl3.3NH3 will not give test for chloride ions with silver nitrate.
8. CoCl3.6NH3 contains 3 Cl– ions in ionization sphere.
CoCl3.5NH3 contains 2 Cl– ions in ionization sphere.
CoCl3.4NH3 contains 1 Cl– ion in ionization sphere.
11. [Co(H2O)4(NH3)2]Cl3: Diamminetetraaquacobalt(III) chloride.
13. EAN = Atomic number – oxidation state + 2 × coordination number
Hence, EAN of Ni in Ni(CO)4 is equal to 28 − 0 + 2 × 4 = 36
14. Z − 3 + 12 = 33
Z = 24
73


15. EAN of [Pt(NH3)6]4+ = 78 – 4 + 12 = 86
EAN of [Fe(CN)6]4– = 26 – 2 + 12 = 36
EAN of [Zn(NH3)4]2+ = 30 – 2 + 8 = 36
EAN of [Cu(NH3)4]2+= 29 – 2 + 8 = 35
Hence, [Cu(NH3)4]2+ is an exception to EAN rule.
16. Cis isomer of [Co(en)2Cl2]+ is optically active whereas trans isomer contains a plane of symmetry and is
optically inactive.
+ +
Cl Cl
Cl Cl
en Pt Pt en
en en
d-form l-form
cis mirror
17. [Co(en)2Cl2]+ is optically active in cis isomer. Trans isomer contains a plane of symmetry and is therefore
optically inactive. The resolution of cis isomer in d and l-form is possible. Hence, total 3 sterioisomers are
possible for the complex.
+ + +
en en
Cl
Cl Cl
Co Co en Co en
Cl
Cl
en en Cl
d- form l-form Optically inactive

Mirror trans-form
Optically active
cis-forms
18. The ionisation isomer for the given compound will be obtained by exchanging ligand with counter ion as:
[Cr(H2O)4Cl2](NO2).
19. [Co(NH3)5SO4]Br and [Co(NH3)5Br]SO4 involves exchange of ligand in between the ionization
and coordination sphere.
22. Cu2+ has maximum charge density (Charge by radius ratio); hence, it forms most stable complex
with ammonia.
23. In [Ni(CN)4]2−, Ni has +2 oxidation state.
Ni2+ ⇒ [Ar] 3d8 4s0
[Ni(CN)4]2– = ↑↓ ↑↓ ↑↓ ↑↓ × × ×× ×× ××
dsp2 hybridization
24. Co2+ → 3d7 4s0
↑↓ ↑↓ ↑ ↑ ↑ ; having minimum number of unpaired electrons.
25. 3d 4s 4p
Ni = ↑↓ ↑↓ ↑↓ ↑ ↑ ×× ×× ×× ××
In [Ni(CO)4], Ni has 0 oxidation state
[Ni(CO)4] ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ×× ×× ×× ××
3
sp hybridization
74


In [Ni(CN)4]2–, Ni has +2 oxidation state
∴ Ni2+ − 1s2 2s2 2p6 3s2 3p6 3d8 4s0
3d 4s 4p
2–
[Ni(CN)4] = ↑↓ ↑↓ ↑↓ ↑↓ × × × × × × × ×
dsp2 hybridization
26. (A) Ni in [Ni(CO)4] (B) Co3+ in [Co(NH3)6]3+

↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ×× ×× ×× ×× ↑↓ ↑↓ ↑↓ ×× ×× ×× ×× ×× ××
3
(10 electrons of Nickel) sp hybrid orbitals (6 electrons of d2sp3 hybrid orbitals
(8 electrons of CO ligands) cobalt) (12 electrons of NH3 ligands)
(C) Ni2+ in [Ni(CN)4]2– (D) Ni2+ in [NiCl4]2–
↑↓ ↑↓ ↑↓ ↑↓ ×× ×× ×× ×× ↑↓ ↑↓ ↑↓ ↑ ↑ ×× ×× ×× ××
(8 electrons of Nickel) dsp2 hybrid orbitals (8 electrons of Nickel) sp3 hybrid orbitals
(8 electrons of CN− ligands) (8 electrons of Cl− ligands)
CO, NH3 and CN− are strong ligands, thus they induce pairing of electrons and their complexes are diamagnetic.
Cl− is a weak ligand, thus it does not induce the pairing of electrons and its complex is paramagnetic.
29. According to spectrochemical series, the strength of the ligands can be given as CN− > OH− > F− > Br−
31. Crystal field stabilization energy (CFSE)
= 4 Dq × (number of electrons in t2g orbital) − 6 Dq × (number of electrons in eg orbital)
Complex Outer electronic configuration CFSE
[Mn(H2O)6]3+ 4 3 1
3d (t 2g eg ) 4Dq(3) − 6Dq(1) = 6 Dq
[Fe(H2O)6]3+ 3d5 (t 32g eg2 ) 4Dq(3) − 6Dq(2) = 0 Dq
2+
[Co(H2O)6] 3d7 (t 52g eg2 ) 4Dq(5) − 6Dq(2) = 8 Dq
3+
[Co(H2O)6] 3d6 (t 42g eg2 ) 4Dq(4) − 6Dq(2) = 4 Dq
32. In [Co(CN)6]3–, Co has +3 oxidation state.

Co3+ → [Ar] 3d6
CN− being strong field ligand causes pairing up of d-electrons.
dx2− y2 dz2
Energy
↑↓ ↑ ↑ ↑ ↑ Large value of ∆o
Co3+ion
(3d6) ↑↓ ↑↓ ↑↓
dxy dyz dxz
[Co(CN)6]3−
Low spin complex
(Strong field ligand)
Thus, [Co(CN)6]3− has no unpaired electrons and will be in a low-spin configuration (i.e., it forms low spin
complex).
33. The magnetic moment of a substance increases with increase in the number of unpaired electrons.
For the complexes [Fe(CN)6]3− and [Fe(H2O)6]3+, the central metal ion is Fe3+ with outer electronic
configuration 3d5. CN− is a strong field ligand while H2O is a weak field ligand. Therefore, [Fe(CN)6]3− has
magnetic moment of a single unpaired electron while [Fe(H2O)6]3+ has magnetic moment of five unpaired
electrons.
75


5. Cr2+ : [Ar] 3d4 14. If d-orbital contains 7-electrons, it has
Co3+ : [Ar] 3d6 3 unpaired electrons.
Mn3+ : [Ar] 3d4 ∴ Spin-only magnetic moment (µ)
Fe3+ : [Ar] 3d5 = n(n + 2) BM
6. Electronic configuration of Cu+ ion: = 3(3 + 2) = 3×5 = 15 = 3.87 BM
1s2 2s2 2p6 3s2 3p6 3d10
Number of s electrons = 2 + 2 + 2 = 6 15. [Co(H2O)6]2+ + 4Cl– → [CoCl4]2– + 6H2O
pink deep blue
8. Ti : [Ar] 3d2 4s2 ⇒ Ti+ : [Ar] 3d2 4s1
V : [Ar] 3d3 4s2 ⇒ V+ : [Ar] 3d3 4s1 18. 3MnO2 + 6KOH + KClO3  ∆
→
Cr : [Ar] 3d5 4s1 ⇒ Cr+ [Ar] 3d5 4s0 3K2MnO4 + KCl + 3H2O
Mn : [Ar] 3d5 4s2 ⇒ Mn+ [Ar] 3d5 4s1 Compound (X) is potassium manganate
In Cr, for second ionization, the electron needs (K2MnO4). It is dark green coloured. Oxidation
to be removed from stable half-filled orbital and state of Mn in X is +6.
hence requires more energy. +
19. 2MnO−4 + 5H2C2O4 + 6H →
Therefore, the order of decreasing second
ionization enthalpy is Cr > Mn > V > Ti. 2Mn2+ + 10CO2 + 8H2O
9. Third ionization enthalpy involves removal of 21. Na2Cr2O7 + 2KCl → K2Cr2O7 + 2NaCl
third outermost electron. (X)
The electronic configurations are
K2Cr2O7 + 4H2SO4 + 3H2S → K2SO4
Ni = [Ar] 3d8 4s2
+ Cr2(SO4)3 + 7H2O + 3S
Co = [Ar] 3d7 4s2
(Y)
Mn = [Ar] 3d5 4s2
Fe = [Ar] 3d6 4s2 22. Siderite (FeCO3) and calamine (ZnCO3) are
On removing the third electron, Fe will attain carbonate ores of iron and zinc respectively.
half filled stability. Hence, among the given
24. Conversion of ferrous oxide (FeO) to ferric
elements, the third ionization enthalpy is
oxide (Fe2O3) occurs during roasting and not
minimum for Fe.
during extraction of iron in blast furnace.
10. Among elements of first transition series, zinc
has the highest first ionization enthalpy. This is 25. Wrought iron is very soft while cast iron is hard
due to its completely filled 3d and 4s orbitals. and brittle.
11. Cu2+ : [Ar] 3d9 4s0 → 1 unpaired e− 26. Lanthanoids react with water to give the metal
Ni2+ : [Ar] 3d8 4s0 → 2 unpaired e− hydroxide and hydrogen gas. Their hydroxides
are ionic and basic.
Ti4+ : [Ar] 3d0 4s0 → 0 unpaired e−
Mn2+ : [Ar] 3d5 4s0 → 5 unpaired e− 28. The third ionization enthalpy involves removal
Hence, Ti4+ is diamagnetic as it does not have of third outermost electron.
unpaired electrons. Yb = [Xe]4f14 6s2
La = [Xe]4f0 5d1 6s2
Lu = [Xe]4f14 5d1 6s2
(where n = number of unpaired electrons) Ce = [Xe]4f1 5d1 6s2
Paramagnetic behaviour is directly proportional On removing the third electron, Yb will lose its
to the number of unpaired electrons. completely filled stability. Hence, among the
Outer electronic No. of unpaired given elements, the third ionization enthalpy is
Ion highest for Yb.
Mn2+ 3d5 5 29.
Cu2+ 3d9 1 Outer No. of
Sc2+ 3d1 1 Ion electronic unpaired
Cr2+ 3d4 4 configuration electrons
Therefore, among the given ions, Mn2+ has Lu3+ (Z = 71) [Xe] 4f14 0
maximum paramagnetic behaviour. Pr3+ (Z = 59) [Xe] 4f2 2
La3+ (Z = 57) [Xe] 4f0 0
13. Magnetic moment will be equal if the ions have
Yb2+ (Z = 70) [Xe] 4f14 0
same number of unpaired electrons.
Cr2+ and Fe2+ The colour is due to electronic transitions
Cr2+ : [Ar]3d4 ∴ 4 unpaired electrons among the f orbitals. If there are no unpaired
Fe2+ : [Ar]3d6 ∴ 4 unpaired electrons electrons, such ions are colourless.
62

Transition Elements
30. Yb3+ (Z = 70) < Pm3+ (Z = 61) < Ce3+ (Z = 58) 41. (A) The last element of actinoid series is
< La3+ (Z = 57). lawrencium.
Atomic number decreases from Yb to La. (C) The last element of 5d transition series is
Hence, ionic radii increase from Yb3+ to La3+. mercury.
(D) The first element of lanthanoid series is
31. As we move along the lanthanoids series, lanthanum.
atomic and ionic radii gradually decrease with
increase in atomic number.
Therefore, ionic radius of Lu3+ (86 pm) is less
than the ionic radius of Ce3+ (102 pm). 1. Since Zn, Cd and Hg have completely filled
(n – 1) d orbitals in their ground states as well as
32. Ce → [Xe]4f1 5d1 6s2 ; Ce4+ → [Xe] in the form of ions, they are excluded from
Yb → [Xe]4f14 6s2 ; Yb2+ → [Xe]4f14 transition series. Hence, among the given
Lu → [Xe]4f14 5d1 6s2 ; Lu3+ → [Xe]4f14 options, only Au is a transition element.
Eu → [Xe]4f7 6s2 ; Eu2+ → [Xe]4f7 2. Observed electronic configuration of titanium
2+
Eu has 7 unpaired electrons. Hence, it is is:
paramagnetic. 1s2 2s2 2p6 3s2 3p6 4s2 3d2
The 4s orbital is lower in energy as compared to
33. Actinium is the first element of 6d transition the 3d orbital.
series. So, in ground state, it will have 1 electron
in its 6d orbital. Hence, correct answer is (A). 3. Electronic configuration of Ni = [Ar] 3d8 4s2
34. Electronic configuration of uranium is: ↑↓ ↑↓ ↑↓ ↑ ↑ ↑↓

[Rn] 5f3 6d1 7s2
No. of unpaired electrons = 2
The formation of +6 oxidation state corresponds
to an electronic configuration of [Rn]. 4. Electronic configuration of X3+ : [Ar] 3d5
Electronic configuration of X : [Ar] 3d6 4s2
35. Electronic configuration of nobelium (No) is: Atomic number of X = 18 + 6 + 2 = 26
[Rn] 5f14 6d0 7s2.
7. Sc3+ → [Ar]3d0
After losing 2 electrons No forms No2+ ion, Due to absence of unpaired electrons, it is
which is stable due to completely filled diamagnetic.
5f-orbitals. Such extra stability due to
completely filled orbital is not acquired by any 8. Magnetic moment = n(n + 2) BM (where
other actinoid in their +2 oxidation state. n = number of unpaired electrons)
Hence, nobelium is the only actinoid with Therefore, magnetic moment is directly
+2 oxidation state. proportional to the number of unpaired electrons.
36. UO3(s) + H2SO4(aq) → UO2SO4(aq) + H2O(l) Calculated
Outer No. of
Uranyl sulphate value of
Ion electronic unpaired
magnetic
37. Among lanthanoids, only promethium is moment
radioactive. In actinoid series, all elements are Fe3+ 3d5 5 5.92 BM
radioactive. Cr3+ 3d3 3 3.87 BM
Ti3+ 3d1 1 1.73 BM
38. Pre-transition metals do not exhibit ligand field Co3+ 3d6 4 4.90 BM
effects.
39. (B) Lanthanoids do not form oxocations while (where n = number of unpaired electrons)
actinoids form oxocations.
Therefore, magnetic moment is directly
(C) Lanthanoids show a maximum oxidation proportional to the number of unpaired electrons.
of +4 while actinoids show a maximum
oxidation state of +7. Calculated
Outer No. of
value of
(D) Lanthanoids show flexibility in geometry Ion electronic unpaired
magnetic
while transition metals show fixed configuration electrons
moment
geometries (ligand field effects).
Cr3+ 3d3 3 3.87 BM
40. Pr is f-block element, As is p-Block element Co3+ 3d6 4 4.90 BM
(representative element), Rb is an alkali metal Ti3+ 3d1 1 1.73 BM
and Mo is a transition element. V3+ 3d2 2 2.83 BM
63

10 Halogen Derivatives
Hints
Classical Thinking
1. Westrosol contains three chloro functional groups.
Cl − CH = CCl2
H H
4. H3C C C Cl
CH3 H
In this structure, the chlorine atom is attached to a primary carbon atom (a carbon atom which is further attached
to only one carbon atom). Hence, among the given options (CH3)2CHCH2Cl is the primary alkyl halide.
2°
5. Isopropyl chloride CH3 – CH – CH3
Cl
Chlorine atom is attached to 2° carbon atom. Hence, it is a 2° alkyl halide..
6. Compound I and III: Allylic halides
Compound II: Aryl halide
Compound IV: Vinylic halide
1 2 3
13. CH2 − CH − CH3
Cl CH3
(1-Chloro-2-methylpropane)
16. R – CH2 – OH + HCl →

anhydrous ZnCl2
R – CH2 – Cl + H2O
Primary alcohol Alkyl chloride
18. 2NaBr + H2SO4 

∆
→ Na2SO4 + 2HBr
Sodium (conc.) Hydrogen
bromide bromide
C2H5OH + HBr → C2H5Br + H2O
Ethanol Ethyl
bromide
19. Alkyl iodides are obtained by heating alcohols with sodium or potassium iodide in 95% H3PO4.
HI is generated in situ.
R – OH + HI  NaI/ H3 PO4
Δ
→ R – I + H2O
20. 3C2H5 − OH + PBr3 P + Br2

 → 3C2H5 − Br + H3PO3
Ethanol Phosphorus Ethyl Phosphorus
tribromide bromide acid
(Monohalogen
derivative)
78

Chapter 10: Halogen Derivatives

21. CH3CH2 − OH + PCl5 
∆
→ CH3CH2 − Cl + HCl + POCl3
Ethanol Ethyl Phosphorus
(X) chloride oxychloride
22. The reaction of alcohol with SOCl2 (thionyl chloride) is the best method for the preparation of alkyl halides
as in this method all the other products are gases and thus there is no need to put extra efforts for the
separation alkyl halide..
R – OH + SOCl2  ∆
→ R – Cl + HCl ↑+SO2↑
23. C3H8 + Cl2 Light

→ C3H7Cl + HCl
This is an example of substitution reaction. Hydrogen atom of alkane is replaced (substituted) by halogen
atom.
25. Iodination is a reversible reaction and hydroiodic acid formed during iodination is a strong reducing agent,
which reduces alkyl iodide back to alkane. Presence of strong oxidising agent (e.g. HgO, HIO3) decomposes
hydroiodic acid and prevents the backward reaction.
26. H3C – CH = CH – CH3 + HBr → CH3 – CH2 – CH(Br) − CH3 or CH3 − CH(Br) − CH2 − CH3
But-2-ene 2-Bromobutane 2-Bromobutane
(A) (B)
Since the alkene is symmetrical, only one product is possible. (A) and (B) both are same product.
28. The bromide ion does not get attached to the carbon atom, with lesser number of H-atoms, in the presence of
peroxide as predicted by Markovnikov’s rule. This phenomenon is also known as peroxide effect or anti-
Markovnikov’s rule or Kharasch effect.
CH3 – CH2 − CH = CH2 + HBr  Peroxide
→ CH3 – CH2 – CH2 – CH2Br
But-1-ene 1-Bromobutane
29. In presence of peroxide the addition of HBr to an asymmetrical alkene follows the anti-Markovnikov’s rule.
HCl and HI always add according to Markovnikov’s rule even in the presence of peroxide.
30. When alkene is heated with Cl2 at high temperature, hydrogen atom of allylic carbon is substituted with
chlorine atom giving allyl chloride.
CH2 = CH − CH3 + Cl2 
∆
→ CH2 = CH – CH2Cl + HCl
Propene 3-Chloroprop-1-ene
CH3 CH3 CH3

Cl
34. 2 + 2Cl2 
Fe
→ + + 2HCl
dark
Toluene o-Chlorotoluene
Cl
p-Chlorotoluene
+ −
N2Cl Cl
35. CuCl/HCl

→ + N2 ↑
Benzenediazonium Chlorobenzene
chloride
36. The electronegativity difference between the H-atoms and the halide atoms, results in polar covalent bond.
Therefore, alkyl halides are moderately polar compounds.
37. For a given alkyl group, alkyl iodides have the highest molecular weight and boiling point also. Because as
the molecular weight increases, boiling point increases for alkyl halides.
38. For alkyl chlorides, boiling point increases with increase in molecular weight.
39. Alkyl halides are insoluble in water but soluble in non-polar organic solvents.
40. The isomeric dihalobenzenes have nearly same boiling points, but show variation in melting points.
79


41. A chiral molecule and its mirror image are not identical.
45. A compound which rotates the plane of plane polarized light towards right is dextrorotatory in nature.
46. Enantiomers have identical physical properties like melting point, boiling points, densities, refractive index
except the sign of optical rotation. The magnitude of their optical rotation is equal.
47. CH3
H − C*− I
C2H5
sec-Butyl iodide has one asymmetric carbon atom (marked *) and is therefore capable of exhibiting
enantiomerism.
49. This is the laboratory test for haloalkanes.
R – X + OH–  ∆
→ R – OH + X– Ag (+aq ) + X (−aq ) → AgX↓
Alkyl Hydroxide Alcohol Halide ; Halide ion Silver halide
Halide ion ion
(X)
50. In alkyl halides, the C−X carbon is an electrophilic centre. Hence, it has a tendency to react with a
nucleophile. Alkyl halides react with a large number of nucleophilic reagents.
R – X + Nu– → R – Nu + X– (leaving group)
51. C2H5Cl + KOH(aq) 
∆
→ C2H5OH + KCl.
52. When alkyl halide react with sodium alkoxide corresponding ether is formed.
R–X + NaOR′  ∆
→ R – O – R′ + NaX
Ether
53. C2H5ONa + C2H5Br − NaBr

 → C2H5 − O − C2H5
Sodium salt Ethyl bromide Diethyl ether
of ethanol
54. CH3Br + CH3COOAg 

∆
→ CH3COOCH3 + AgBr
Methyl Silver Methyl acetate
bromide acetate
55. C2H5Br + NH3 (alc.) →∆

pressure
C2H5NH2 + HBr
Ethyl (Excess) Ethylamine
bromide
56. H3C – CH2 – CH2Cl + KCN 

Boil
→ H3C – CH2 – CH2 – CN + KCl
n-Propyl chloride (alc.) Butanenitrile or n-Propyl cyanide
57. → R−NC + AgX ↓

AgCN + R − X  ∆
Silver Alkyl Alkyl Silver

cyanide halide isocyanide halide
(Alc.) precipitate
59. In SN2 mechanism, the rate is proportional to concentration of the reactants; both substrate and reagent.
e.g. CH3Br + OH– → CH3OH + Br–
Rate = k[CH3Br] [OH–]
The reaction is said to follow second order kinetics, since rate is dependent on the concentration of two
substances.
62. The SN2 mechanism is found to proceed with inversion of configuration which is also known as Walden
inversion.
63. Example of SN1 mechanism:
(CH3)3C − Br 
NaOH ( aq )
hydrolysis
→ (CH3)3C+ + Br–
Planar Carbocation
80


64. In SN1 reaction, the incoming nucleophile can attack from the back and front sides because it is a 2 step
process; in 1st step carbocation is formed and in 2nd step nucleophile attacks, for which both sides are
available for attack. Hence, there is inversion as well as retention of configuration.
65. When an optically active alkyl halide follows SN1 mechanism, racemic mixture is formed.
R2 R2 R2
−
R1 − C − Cl 
CN
→ R1 − C − CN + NC − C − R1
R3 R3 R3
Racemised Products
3° halides are more susceptible to SN1 mechanism.

66. Primary alkyl halides readily undergo SN2 reaction.
67. Reactivity is directly related to the stability of carbocations. the stability of carbocation is
3° > 2° > 1° > CH3. Greater the number of alkyl groups, the more stable the carbocation. This is due to the
(+I) inductive effect of the alkyl group.
68. Conversion of bromomethane to methanol follows SN2 mechanism. It readily takes place in the presence of
strong nucleophile and aprotic solvents or solvents of low polarity.
69. SN1 reaction is most favoured in the presence of polar protic solvents. Also, it is favoured in the presence of
tertiary alkyl group and independent of the nature of nucleophile.
70. CH3CH2Br  alc.KOH
→ CH2 = CH2 + HBr
Dehydrohalogenation is a process in which both hydrogen and halogen are removed from a molecule of
alkyl halide.
71. CnH2n + 1X 
− HX
→ CnH2n + HX (Dehydrohalogenation)
Haloalkane Alkene
72. Dehydrohalogenation is the removal of hydrogen and halogen altogether from an alkyl halide, and the
reaction can be effectively carried out by alcoholic KOH.
73. CH3 − CH2 − CH2Br + KOH(alc.) 

∆
→ CH3 − CH = CH2 + KBr + H2O
n-Propyl bromide Propene
CH3
CH3 − C = CH − CH3
Br
2-Methylbut-2-ene (80 %)
alc. KOH
74. CH3 − C − CH2 − CH3
∆
CH3 CH2 = C − CH2 − CH3
2-Bromo-2-methylbutane
CH3
Br
CH3 − CH = CH − CH3
alc. KOH But-2-ene (major)
75. CH3 − CH − CH2 − CH3
sec-Butyl bromide ∆ H2C = CH − CH2 − CH3
But-1-ene (minor)
Since two different types of hydrogen atoms are present to the adjacent C atoms of secondary carbon
containing −Br group, two products are possible. However, according to Saytzeff’s rule, “In
dehydrohalogenation reaction, the preferred product is that alkene which has greater number of alkyl groups
attached to doubly bonded carbon atoms.” Hence, but-2-ene is the preferred product, and is formed as the
major product.
81


76. Alkyl iodides have the weakest C − X bond, hence can be broken easily.
77. The stability order of alkyl substituted alkenes with reference to dehydrohalogenation reaction is:
R2C = CR2 > R2C = CHR > R2C = CH2, RCH = CHR > RCH = CH2
78. In an organometallic compound, the metal is directly bonded to any one of the carbon atoms of the chain.
80. CH3 – CH2 – Br + Mg 

Dry ether
→ CH3CH2MgBr
Ethyl bromide Ethyl magnesium
bromide
This is the method for preparation of Grignard reagent.
81. C4H9MgBr 

HOH
→ C4H10 + MgBr(OH)
n-Butyl n-Butane
magnesium bromide
Grignard reagent is very sensitive to moisture. When it comes into contact with water, it is converted to the
corresponding alkane.
−δ +2δ −δ +δ −δ
R − Mg − X + H − OH → R − H + MgOH(X)
Grignard Alkane
reagent
83. Ethyl bromide and methyl bromide undergo Wurtz reaction with metallic sodium in dry ether.
CH3 – CH3
Ethane
Na
CH3Br + C2H5Br CH3 – CH2 – CH3
Methyl Ethyl dry ether Propane
bromide bromide CH3 – CH2 – CH2 – CH3
Butane
84. The above reaction is known as Wurtz-Fittig reaction.

85. The product is biphenyl, formed by Fittig reaction.
87. The presence of electron withdrawing groups at o- and p-positions with respect to halogen atom activates the
aryl halides towards nucleophilic substitution reactions. As the number of electron withdrawing groups at
o- and p-positions increases, the reactivity of aryl halides also increases.
88. Chlorobenzene when heated with nitrating mixture (conc. H2SO4 + conc. HNO3) yields both ortho and para
chloronitrobenzene, with para derivative as the major product.
Cl Cl Cl
SO3H
89. 2 + 2 H2SO4 
∆
→ + + H2O
Chlorobenzene (conc.) (Minor)

2-Chlorobenzene SO3H
sulphonic acid (Major)
4-Chlorobenzene
sulphonic acid
Cl Cl Cl
CH3
90. 2 + 2CH3Cl →
anhydrous AlCl3
+ + 2HCl
Chlorobenzene Methyl (Minor)

CH3
chloride 1-Chloro-2-methylbenzene
(Major)
1-Chloro-4-methylbenzene
82


94. Freons are chlorofluorocarbons (CFC's) which are commonly used as refrigerants.
95. They are position isomers as both have the same molecular formula and only differ by the position of the
halide group.
96. In geminal dihalides, both the halogen atoms are attached to the same carbon atom.
97. H2SO4 is an oxidising agent. It oxidises HI produced during the reaction to I2. This can be represented as,
2HI + H2SO4 → 2H2O + I2 + SO2↑
As a result, it prevents the reaction between an alcohol and HI to form an alkyl iodide. Therefore, in order to
overcome this difficulty, a non-oxidising acid such as H3PO4 is used instead of H2SO4.
98. Nucleophiles are electron rich groups capable of donating electrons to electron deficient centres. All the
mentioned groups are capable of donating lone pair of electrons.
Critical Thinking
2. C4H9Br can have the following structures

1°
(A) CH3 − CH2 − CH2 − CH2Br (1° Bromoalkane)
2°
(B) CH3 − CH2 − CH− CH3 (2° Bromoalkane)
|
Br
CH3
| 3°
(C) H3C − C − CH3 (3° Bromoalkane)
|
Br
3. The structure of (CH3)3C − Cl is,
CH3

CH3  C  CH3

Cl
The chlorine is attached to a 3° carbon atom. So, it is a tertiary alkyl halide. ‘A’ and ‘B’ are primary alkyl
halides while ‘D’ is a secondary alkyl halide.
1° 1°
CH3 CH3
1° 3° 4° 2° 1°
4. Cl–CH2 − CH − C − CH2 − CH3
1°
CH3
1-Chloro-2,3,3-trimethylpentane
10. The order of reactivity of alcohols towards a given haloacid is 3° > 2° > 1°.
11. The reactivity of alcohols with HBr is in the order 3° > 2° > 1°. 2-Methylpropan-2-ol is a tertiary alcohol.
CH3
i.e., CH3 – C – CH3
OH
Hence, it reacts fastest with HBr. Propan-1-ol and 2-Methylpropan-1-ol are primary alcohols. Propan-2-ol is
a secondary alcohol.
83


12. CH3CH2OH + SOCl2 
∆
→ C2H5Cl + HCl ↑ + SO2↑
Ethyl alcohol Thionyl Ethyl Sulphur
chloride chloride dioxide
13. Alcohols do not react with NaCl.

ROH + HCl 
Anhydrous ZnCl2
→ RCl + H2O
3ROH + PBr3 → 3RBr + H3PO3
ROH + SOCl2 
∆
→ RCl + SO2 + HCl
15. Addition occurs according to Markovnikov’s rule.

Cl
|
CH3− CH2 − CH2 − CH = CH2 + HCl 
Markovnikov's rule
→ CH3− CH2 − CH2 − CH − CH3
Pent-1-ene 2-Chloropentane
16. CH2 = CH − CCl3 + HBr → CH3 − CH(Br) − CCl3

17. Peroxide effect is shown by unsymmetrical alkenes like CH2 = CH − CH3.
18. In the presence of benzoyl peroxide, the reaction gives a product contrary to the Markovnikov’s rule.
CH3 CH3
| |
CH3 – C = CH2  HBr
Peroxide
→ CH 3 – CH – CH2Br
Isobutylene Isobutyl bromide
19. In presence of peroxide, Anti-Markovnikov’s product is the major product formed.

Ph–CH = CH2 + HBr  H 2 O2
Anti-Markovnikov’s rule
→ Ph(CH2)2–Br
Phenylethene 1-Bromo-2-phenylethane (X)
21. The reaction is addition reaction. Since only one molecule of HBr is added, ‘A’ contains one double bond.
∴ It is an alkene.
23. Fluoro compounds cannot be prepared by direct halogenation of benzene as fluorine is highly reactive.
Though the reaction with iodine is reversible, iodobenzene can be prepared in presence of HNO3/HIO4, which
prevents the reverse reaction
+ –
24. C6H5N2Cl 
CuBr / HBr
→ C6H5Br + N2↑
Benzene Bromobenzene
diazonium (Aryl halide)
chloride
26. The three dimensional structure of the given compounds along with the direction of dipole moment in each
of their bonds is given below:
Cl H Cl H Cl Cl Cl Cl
C C C C
H H Cl H Cl H Cl Cl
In CH2Cl2, the resultant of two C−Cl dipole moments is reinforced by resultant of two C−H dipoles.
Therefore, CH2Cl2 has a dipole moment higher than that in the other given options.
27. C–X bond enthalpy of halomethanes in kJ mol–1:
CH3F: 452 CH3Cl: 351
CH3Br: 293 CH3I: 234
C–X bond enthalpy of fluoromethane is highest amongst others.
28. With increased branching, surface area decreases, hence, van der Waal’s forces of attraction also decreases.
As a result, boiling point among the isomeric alkyl halides follows the order: 1° > 2° > 3°.
84


29. Physical properties depend upon the nature of alkyl chain if the halogen atom is same. For the same halogen,
boiling points of alkyl halides increase as the molecular weight increases. Hence, CH3Br has the lowest
boiling point.
30. Melting points of isomeric dichlorobenzenes are given below:
Cl Cl Cl
Cl
Cl
Cl
o-Dichlorobenzene m-Dichlorobenzene p-Dichlorobenzene
m.p./K 256 249 323
COOH
31. H − C*− OH
CH3
Lactic acid contains one asymmetric carbon atom (marked *).
32. Compound containing asymmetric carbon atom i.e., carbon atom attached to 4 different groups, shows
optical isomerism.
Cl
33. (A) H3C − C*− CH2Cl (* Asymmetric carbon, optically active)
H
Cl
(B) H3C − CH2 − C − Cl (No asymmetric carbon, optically inactive)
H
Cl
(C) H3C − C − CH3 (No asymmetric carbon, optically inactive)
Cl
Cl Cl
(D) H2C − CH2 − CH2( (No asymmetric carbon, optically inactive)
CH3 CH3
* *
34. C2H5 – C – H H – C – C2H5
COOH COOH
All the four groups attached to the carbon atom are different. Hence, it is asymmetric and it can exist in two
enantiomeric forms.
Addition
reaction
Not shown by alkyl halide as it is a
saturated compound
Dehydrohalogenation
R − CH = CH2 + HX
Alc. KOH
36. R − CH2 − CH2 − X ––– Alkene
Alkyl halide Elimination
R − CH = CH2 + HX
Alc. KOH
Alkene
aq. KOH
R − CH2 − CH2 − OH + HX
Substitution
Alcohol
85

37. C2H5OH 
Na
→ C2H5ONa ; C2H5OH 
PCl5
→ C2H5Cl
Ethanol Sodium Ethanol 1-Chloroethane
(X) ethoxide (X) (Z)
(Y)
C2H5ONa + C2H5Cl → C2H5 – O – C2H5 + NaCl

Sodium Chloroethane Diethyl ether
ethoxide (Z)
(Y)
O O
38. CH3CH2−Br + Ag – O – C – CH3 

∆
→ CH3 – C – O – CH2CH3 + AgBr
Bromoethane Silver acetate Ethyl acetate Silver bromide
39. C3H7Br + KCN →

boil
C3H7CN + KBr
Bromopropane (Alc.) Butanenitrile
40. (I) RX + alc. KCN  ∆

→ RCN
(II) RX + alc. AgCN  ∆
→ RNC
Alkyl halides when treated with alcoholic solution of KCN give alkyl cyanide whereas with AgCN they give
alkyl isocyanides.
41. Cyanide ion is capable of attacking through more than one site (atom).
– –
C ≡ N ↔ C=N
KCN is predominantly ionic and provides cyanide ions. Both carbon and nitrogen are capable of donating
electron pair. C-C Bond being stronger than C-N bond, attack occurs through carbon atom of cyanide group
forming alkyl cyanides as major product.
AgCN (Ag – C ≡ N) is mainly covalent compound and nitrogen is free to donate pair of electrons. Hence,
attack occurs through nitrogen resulting in formation of isocyanide.
43. The product formed from SN2 reaction of a dextro rotatory compound will be laevo rotatory as SN2
mechanism involves Walden inversion.
44. Alkaline hydrolysis of tertiary alkyl halide follows SN1 mechanism. It involves two steps (i) formation of
carbcation and (ii) attack of nucleophile resulting in the formation of the product.
45. Alkaline hydrolysis of tert-Butyl bromide follows SN1 mechanism.
∴ Rate of reaction ∝ [(CH3)3C – Br]
∴ Rate of reaction is doubled if the concentration of alkyl halide is doubled.
46. The hydrolysis of tertiary butyl bromide takes place by the SN1 mechanism. The rate of this reaction depends
only on the concentration of tert-butyl bromide and is independent of the concentration of alkali added.
47. A good ionizing solvent or polar protic solvents will favour SN1 mechanism.
Order of reactivity of alkyl halide is 3° > 2° > 1°.
SN1 reaction proceeds mainly with racemization (i.e., both retention and inversion of configuration).
48. Benzylic halides (1°, 2°, 3°) prefer to undergo SN1 mechanism. Option (D) is 3° benzylic halide which is
highly stabilised resonance structure. Thus, amongst given compound, PhC(CH3)(Ph)Cl is most reactive
towards SN1 reaction.
CH3
C6H5 − C − Cl
C6H5
49. Benzylic, allylic and tertiary alkyl halides undergo SN1 mechanism. Thus, compounds II, V, and VI will
readily undergo SN1 mechanism.
86


50. The rate of SN1 mechanism is independent of the nature of nucleophile. Nucleophile does not react in slow
step of SN1 mechanism (i.e., formation of carbocation). So, increase in concentration of nucleophilic reagent
will not affect the rate of reaction. Thus, rate depends only on the substrate.
51. SN1 reaction proceeds mainly with racemization (i.e., both retention and inversion of configuration).
52. CH3 – CH2 – CH2 – CH2Cl + KOH(alc) → CH3 – CH2 – CH = CH2 + KCl + H2O
n-Butyl chloride But-1-ene
This reaction involves 1,2-elimination (β-elimination).

53. Elimination takes place in accordance with Saytzeff’s rule.
CH3 CH3
| |
H3C – C – CH2 – CH3 + KOH(alc) → H3C – C = CH – CH3 + KCl + H2O
|
2-Methylbut-2-ene
Cl
2-Chloro-2-methylbutane
54. (A) Tertiary alkyl halides prefer to undergo elimination reaction.

(B) Substitution reaction is favoured by weak bases.
(C) Less polar solvent, high temperature favours elimination reaction.
55. 1.4 L = 1 g
22.4 L = 16 g.
Hence, gas is methane (CH4) and RMgX is CH3MgBr.
56. Wurtz reaction is,
2R − X + 2Na  dry ether
→ R − R + 2NaX
57. C2H5Cl + 2Na + ClC2H5 

Dry Ether
→ C2H5 − C2H5 + 2NaCl
Ethyl Ethyl n-Butane
chloride chloride
58. The reaction is known as Wurtz reaction.
C2H5Br + 2Na + C2H5Br  dry ether
→ CH3CH2CH2CH3 + 2NaBr.
Ethyl Ethyl n-Butane
bromide bromide
CH3 CH3
| |
C2H5Br + 2Na + BrCHCH3 
dry ether
→ CH3CH2CHCH3
Ethyl Isopropyl Isopentane
bromide bromide
H3C CH3 H3C CH3

CHBr + 2Na + Br CH dry ether
 → CH − CH
H3C CH3 H3C CH3
Isopropyl Isopropyl 2,3-Dimethylbutane
bromide bromide
But n-Hexane cannot be formed.
59. Chlorobenzene is less reactive than benzyl chloride.
CH2 – Cl Cl
Benzyl Chlorobenzene
chloride
In Chlorobenzene, the lone pairs present on Cl-atom get involved in resonance with π electrons of benzene
due to which C – Cl bond acquires double bond character. Hence, reactivity decreases.
87


Br Br Br
CH3
62. 2 + 2CH3I →
anhydrous AlCl3
+ + 2HI
Bromobenzene o-Bromotoluene CH3

p-Bromotoluene
Cl Cl Cl
COCH3
Anhydrous AlCl
63. 2 + 2CH3 − C − Cl 
3
→ + + 2HCl
Chlorobenzene O
2-Chloro COCH3
acetophenone
4-Chloroacetophenone
(Minor product) (Major product)
64. Triiodomethane is a yellow crystalline substance with disagreeable smell. Tetrachloromethane is a colourless
liquid with sweet smell.
67. DDT is not metabolised very rapidly by animals; instead, it is deposited and stored in the fatty tissues.
68. CH3Br →
Zn / HCl
CH4 + HBr
Methyl Methane
bromide
CH3Br + 2Na + BrCH3 

ether
→ CH3 − CH3 + 2NaBr
Methyl Methyl Ethane
bromide bromide
69. – C – Cl → – C+ + Cl−
Cation Anion
During heterolytic fission, asymmetrical breaking of covalent bond takes place where formation of positive
and negative ions occurs.
CH3 CH3
70. CH3 − C − Br + CH3ONa 

Elimination
→ CH3 − C = CH2 + CH3OH + NaBr
Sodium 2-Methylpropene
CH3 methoxide
tert-Butyl bromide
CH3ONa → CH3O− + Na+

Methoxide ion (CH3O−) is a strong base, therefore it abstracts proton from 3° alkyl halide and favours
elimination reaction.
1. In allylic halide, the halogen atom is attached to sp3 carbon atom next to a carbon-carbon double bond.
Br Br
CH2 – Cl CH – CH3
Cl
Benzyl chloride (1-Bromoethyl)benzene 1-Bromobenzene 3-Chlorocyclohex-1-ene
Among the given options, 3-chlorocyclohex-1-ene is an allylic halide.

88


2. 1,2-Dichloroethane (ethylene dichloride) is a vicinal halide as both the chlorine atoms are attached to
adjacent (vicinal) C-atoms.
H2C − CH2
Cl Cl
1,2-Dichloroethane
3. i. Primary and secondary alcohols react with concentrated HCl and anhydrous ZnCl2 to give the
corresponding alkyl chlorides.
e.g. a. CH3 − CH2 − OH + HCl 
Anhydrous ZnCl2
∆
→ CH3 − CH2 − Cl + H2O
Ethanol (conc.) Ethyl chloride
CH3 CH3
b. CH3 − C − OH + HCl 

Anhydrous ZnCl2
Room temperature
→ CH3 − C − Cl + H2O
(conc.)
H H
Propan-2-ol 2-Chloropropane
ii. Tertiary alcohols readily react (simply by shaking) with concentrated HCl even in the absence of
anhydrous ZnCl2.
e.g. CH3
CH3
CH3 − C − OH + HCl 
Room temperature
→ CH3 − C − Cl + H2O
(conc.)
CH3 CH3
2-Methylpropan-2-ol 2-Chloro-2-methylpropane
Therefore, among the given reactions, (I), (III) and (IV) can be used for the preparation of alkyl
halides.
4. Chlorination of ethane is carried out in the presence of ultraviolet light or diffused sunlight or at high
temperature.
CH3 CH3
5. CH3 − C − CH3 CH3 − C − CH2 − CH3 CH3CHCH3 CH3CHCH2CH3
CH3 CH3 CH3 CH3

Neopentane Neohexane Isobutane Isopentane
Neopentane has only one type of hydrogen atom and hence, gives only one derivative on monohalogenation.
Br
electrophilic addition of H +
→ CH3 − C = CH2  → CH3 − C − CH3
HBr
6. CH3 − C ≡ CH + HBr  ( from HBr )
Propyne Br Br
(Methyl acetylene) 2-Bromopropene 2,2-Dibromopropane
7. According to Markovnikov’s rule, when an unsymmetrical reagent (like HCl) adds to an unsymmetrical
alkene, the negative part of the reagent gets attached to that unsaturated carbon atom which carries lesser
number of hydrogen atoms.
CH2 CH3
H3C Cl H3C Cl
(A) HCl (B) HCl
  →   →
1-Chloro-1-methylcyclohexane 1-Chloro-1-methylcyclohexane
89


8. Both of the doubly bonded carbon atoms carry equal number of hydrogen atoms. However, benzyl
carbocation is more stable than 2° alkyl carbocation, hence option (A) is the correct answer.
C6H5CH = CHCH3 + HBr → C6H5 − CH − CH − CH3
1-Phenylprop-1-ene
Br H
1-Bromo-1-phenylpropane
9. The reaction of but-1-ene with HBr gives 2-bromobutane as the major product as the reaction proceeds
according to Markovnikov’s rule.
10. In Finkelstein reaction, alkyl chlorides or bromides are treated with sodium iodide in dry acetone to give
corresponding alkyl iodides.
CH3 – CH2 – Br + NaI 
Dry acetone
→ CH3 – CH2 – I + NaBr
Ethyl bromide Sodium Ethyl iodide
iodide
12. Preparation of alkyl fluorides by heating alkyl bromides or chlorides in the presence of metallic fluorides is
known as Swarts reaction. Hence, among the given options, (C) is Swarts reaction.
13. Alkyl fluorides can be prepared by the action of mercurous fluoride (Hg2F2), silver fluoride (AgF), arsenic
trifluoride (AsF3) or antimony trifluoride (SbF3) on alkyl chloride or bromide.
This reaction is known as “Swarts Reaction”.
e.g. 2CH3 − Cl + Hg2F2 → 2CH3 − F + Hg2Cl2
Methyl Mercurous Methyl
chloride fluoride fluoride
15. CH3F > CH3Cl > CH3Br > CH3I

The sp3 orbital of carbon cannot penetrate into larger p-orbitals (3rd, 4th, 5th orbitals) sufficiently to form
strong bonds. Hence, C−F bond will be the strongest and C−I the weakest.
16.
Halomethane C–X Bond Enthalpy (kJ/mol)
CH3 − F 452
CH3 − Cl 351
CH3 − Br 293
CH3 − I 234
Thus, the C–X bond energy (bond enthalpy) increases in the order:
CH3I < CH3Br < CH3Cl < CH3F
17. Cl
CH3 − C*− CH2 − CH3
H
2-Chlorobutane
2-Chlorobutane has one asymmetric carbon atom (marked *), hence it is an optically active compound.
Br
2 4
3 HBr
* *
1 5  →
21. H 2 O2
2-Bromo-3-methylpentane
3-Methylpent-2-ene (Anti Markownikov product)
Four stereoisomers are possible due to the presence of 2 chiral centres in the addition product.
22. (+) 2-Methylbutan-1-ol and (−) 2-methylbutan-1-ol are enantiomers. They differ only in their specific
rotations.
90


24. Br NH2
CH3 − C − CH3 

Alc.NH3 ,Δ
− HBr
→ CH3 − C − CH3
CH3 CH3
2-Bromo-2-methylpropane 2-Amino-2-methylpropane
(Y)
25. Reactivity of an alkyl halide in SN2 mechanism is in the following order:
CH3X > 1° alkyl halide > 2° alkyl halide > 3° alkyl halide
26. The reactivity of alkyl halides in SN2 mechanism decreases in the following order:
Primary alkyl halide > secondary alkyl halide > tertiary alkyl halide
∴ The correct order of reactivity of the given iodides in SN2 reaction is,
CH3CH2CH2CH2I > CH3CH2CHCH3 > (CH3)3CI
1° alkyl halide 3° alkyl halide
I
2° alkyl halide
27. In SN2 reaction, the rate is proportional to concentration of the reactants, i.e., substrate and nucleophilic
reagent.
28. (CH3)3C − Br + NaOH(aq) → (CH3)3C − OH + NaBr
Rate ∝ [(CH3)3C − Br]
∴ Rate = k [(CH3)3C − Br]
Hence, with respect to the nucleophile (OH−), the order of the reaction is zero.
29. 1-Bromo-1-phenylethane follows SN1 mechanism.

H H
C − Br 
KOH
→ *
H2 O C − OH + KBr
CH3 CH3
1-Bromo-1-phenylethane 1-Phenylethanol
Racemic mixture
30. For any SN1 reaction reactivity is decided by the ease of dissociation of alkyl halide,
 R+ + X−
R − X 
Higher the stability of R+ (carbocation), higher would be reactivity of SN1 reaction.
Stability of carbocation follows order,
⊕ ⊕ ⊕
CH3 − CH2 − CH2 < CH3 − CH − CH2 − CH3 < p − H3CO − C6H4 − CH2
Hence, the correct increasing order of reactivity of the given alkyl halides for SN1 reaction is II < I < III.
31. Benzylic halides (1°, 2°, 3°) undergo SN1 reaction mechanism. In SN1 reaction, the order of reactivity is:
3° > 2° > 1°. The compounds in (ii) and (iii) are secondary benzylic halides. But the carbocation
intermediate obtained from (ii) is more stable than that obtained from (iii) because it is stabilised by two
phenyl groups due to resonance. Hence, (ii) is more reactive than (iii) in SN1 reactions.
32. 2CH3 − CH − CH2 − CH3 

Alc.KOH
Δ
→ CH3 − CH = CH − CH3 + H2C = CH – CH2 – CH3 + 2KI + 2H2O
2-Iodobutane But-2-ene But-1-ene
(Major product) (Minor product)
91


33. Dehydrohalogenation of CH3CH2Cl gives ethene as the main product.
CH3CH2Cl + KOH 
∆
→ H2C = CH2 + KCl + H2O
Ethyl Ethene
(Alc.)
chloride
Molar mass of CH3CH2Cl = 64.5 g/mol and Molar mass of ethene (C2H4) = 28 g/mol
6.45g
∴ Number of moles of CH3CH2Cl = = 0.1 mol
64.5g/mol
0.1 mol of CH3CH2Cl will give 0.1 mol of ethene.
However, only 50% of the reagent is used. So, only 50% of product will be formed, i.e., 0.05 mol of ethene.
∴ Weight of main product (ethene) obtained = 0.05 mol × 28 g/mol = 1.4 g
34. When 1-bromopropane is heated with alcoholic KOH, propene is obtained.
CH3CH2CH2Br + KOH  ∆
→ CH3CH = CH2 + KBr + H2O
1-Bromopropane (Alc.) Propene
Molar mass of CH3CH2CH2Br = 123 g/mol and Molar mass of propene (CH3CH = CH2) = 42 g/mol
12.3 g
∴ Number of moles of CH3CH2CH2Br = = 0.1 mol
123 g/mol
0.1 mol of CH3CH2CH2Br will give 0.1 mol of propene.
∴ Mass of propene obtained will be 0.1 × 42 = 4.2 g However, yield obtained is 50%.
50
∴ Mass of propene obtained = 4.2 × = 2.1 g
100
35. CH3
CH3
CH3 − CH − CH2 − CH2 − Br 

Alc.KOH
Δ
→ CH3 − CH − CH = CH2
(A)
CH3 CH3
(i) Conc. H2SO4
CH3 − CH − CH − CH3 + CH3 − CH − CH2 − CH2 − OH
(ii) H2O, ∆
(C)
OH (Minor product)
(B)
(Major product)
CH3 CH3 CH3

CH3 − CH − CH − CH3 HI, Δ

− H2 O
→ CH3 − C − CH2 − CH3 + CH3 − CH − CH − CH3
(3°) (2°)
OH I I
(B) (D) (E)
Major product Minor product
36. Br + Mg 
Dry ether
→ MgBr 
H2 O
H+
→
Bromocyclohexane ‘A’ Cyclohexane

‘B’
The Grignard reagent (formed as product ‘A’) reacts with any source of proton to give corresponding
hydrocarbon.
37. Grignard reagent reacts with water to form corresponding alkane.
δ− 2δ+ δ−
H5C2 − Mg − Br + H − OH 
→ C2H6 + Mg(OH)Br
Ethyl magnesium Ethane
bromide
92


38. The reaction of alkyl halide with sodium metal in the presence of dry ether is known as Wurtz synthesis. In
this reaction, the product formed always contains more number of carbon atoms than reactants. Hence,
ethane cannot be formed.
40. Wurtz reaction:
Cl
+ 2Na + dry ether

−2NaCl
→ + +
Cl 1-Chloropropane 2-Methylpentane 2,3-Dimethylbutane n-Hexane
2-Chloropropane
42. As the number of electron withdrawing groups at o- and p-positions increases, the reactivity of aryl halides
increases.
Cl OH
44. + NaOH →

623 K
pressure
+ NaCl
(aq.)
Chlorobenzene Phenol
CH3 CH3
47. CH3 − CH2 − CH2 − CH − CH2 − CH3 →

Cl2
hv
CH3 − (CH2)2 − C − CH2 − CH3
(X) Cl
48. CH3 − CH2 − CH2 − Br + NaCN → CH3 − CH2 − CH2 − CN + NaBr
This is SN2 reaction for which aprotic solvent is suitable for faster rate of reaction. Among the given options,
DMF is an aprotic solvent, which is polar enough to dissolve the substrate and nucleophile but do not
participate in hydrogen bonding with the nucleophile. Hence, the reaction will be fastest in DMF.
CH3
H−C−N
O CH3
N,N-Dimethylformamide
49. Grignard’s reagent is an example for organometallic compound having sigma bond while ferrocene,
cobaltocene and ruthenocene are organometallic π complexes.
52. Aryl halides do not give substitution reactions easily because C – X bond possesses partial double bond
character due to resonance.
53. Due to resonance, in (A), (B) and (C), C – Cl bond length is less compared to (D).
1. CH3 – CH2 – CH2 – Br 

Alc.KOH
→ CH3 – CH = CH2 
HBr
→ CH3 – CH – CH3
1-Bromopropane Propene
(A)
Br
2-Bromopropane
(B)
aq.KOH
CH3 – CH – CH3
OH
Propan-2-ol
(C)
93


2. Due to resonance stabilisation in aryl halides, C – X bond acquires some double bond character.
Br2
5. CH3 – CH2 – CH2 – I 
Alc.KOH
→ CH3 – CH = CH2  → CH3 – CH – CH2
Propene
1-Iodopropane Br Br
(A)
1,2-Dibromopropane
(B)
NaNH2/NH3
CH3 – C ≡ CH
Propyne
(C)
6. Order of reactivity towards nucleophilic substitution reaction is:

Allyl halides > alkyl halides > haloarenes
8. H It undergoes SN1 mechanism and due to asymmetric carbon atom, it is optically active.
C
Br CH3
C6H5
1-Bromo-1-phenylethane
9. Presence of electron withdrawing group (NO2) facilitates the benzene ring towards nucleophilic substitution
reaction.
10. Iodoethane on reaction with sodium methoxide gives ethyl methyl ether.
C2H5I + Na − O − CH3  ∆
→ C2H5 − O − CH3 + NaI
Iodoethane Sodium Ethyl methyl
methoxide ether
11. CH2 − Cl CH2CN
+ NaCN 
C2 H5 − OH
→
Br Br
4-Bromobenzyl 4-Bromobenzyl
chloride cyanide
+ −
NH2 N2Cl Br
12. NaNO2 + HCl


280 K
→ CuBr / HBr

Sandmeyers
→ + N2
reaction
Aniline
diazonium
chloride
13. Peroxide effect is observed only in case of HBr. Thus, addition takes place in accordance with the
Markovnikov’s rule.
+ − + −
H I I
CH3 – CH = CH2 
peroxide
→ CH 3 − CH − CH 3 
peroxide
→ CH3 – CH – CH3
|
Propene
I
2-Iodopropane
O O
14. C2H5 – Br + CH3 – C – OAg 

∆
→ C2H5 – O – C – CH3
(Ester)
94


15. For a given alkyl group, boiling point increases with increase in atomic mass of halogen.
+
Br
16. C6H5CH2Br 
Mg, ether
→ C6H5CH2MgBr 
H3 O
→ C6H5CH3 + Mg
Benzyl Benzyl Toluene OH
bromide magnesium
bromide
C2H5 C2H5
17. 2CH3(CH2)2 − CH – CH2CH3 + 2Na 

Wurtz reaction
→ CH3(CH2)2 – CH − CH − (CH2)2CH3 + 2NaI
I 4,5-Diethyloctane
3-Iodohexane
CH2 H3C Br
18. + HBr →
The reaction follows Markownikov’s rule.
19. CH3I + KCN →

Alcohol
CH3CN + KI
Methyl Potassium Acetonitrile
iodide cyanide
20. Alkaline hydrolysis of tert-butyl bromide follows SN1 mechanism.

Rate = k [(CH3)3C – Br]
The presence of methyl groups restricts the entry of the nucleophile from the rear side. Hence, the alkyl
halide first undergoes heterolysis, which is a slow process. The heterolysis produces a carbocation, which is
immediately attacked by the new nucleophile. Hence, in the slowest step of the reaction only one molecule is
involved and therefore rate is dependent only on its concentration.
∆
→ C2H5Cl + HCl ↑ + SO2↑
22. Order of reactivity:
For given alkyl group: R − I > R − Br > R − Cl
For given halogen atom: 3° > 2° > 1°
23. CH3 − Br + KOH(aq) 

∆
→ CH3 − OH + KBr
Rate ∝ [CH3 − Br] [OH−]
∴ Rate = k [CH3 − Br] [OH−]
Hence, this reaction is a second order reaction.
−
25. C6H5 − CH2 − Cl → C6H5 − CH2
OH
 → C6H5 − CH2 − OH
Benzyl (stabilized by
chloride resonance)
In benzyl chloride, the carbocation formed during SN1 mechanism is resonance stabilised.
95

11 Alcohols, Phenols and Ethers

Classical Thinking
Hints
Classical Thinking
1. In alcohols (i.e., hydroxyl derivatives of hydrocarbons), one or more hydrogen atoms are replaced by
hydroxyl (− OH) group.
2. In phenols, hydroxyl group is directly attached to benzene ring whereas in aromatic alcohols, hydroxyl group
is attached to side chain of aromatic ring.
4. Ethers contain an oxygen atom bonded to two alkyl groups or two aryl groups or one alkyl and one aryl
group which are organic entities; hence, called organic oxides.
7. Epoxides are called cyclic ethers in which ethereal oxygen is a part of three membered ring.
e.g. CH2 – CH2
O
8. CH2 – CH – CH2 is glycerol, a trihydric alcohol as it contains three hydroxyl groups.
| | |
OH OH OH
9. In a primary alcohol (−CH2OH), the alcoholic group is attached to the sp3 hybridized primary carbon atom.
10. OH OH
(A) H3C − CH − CH3 (B) H2C − CH2 − CH2 − CH2 − CH3

Propan-2-ol Pentan-1-ol
(Secondary alcohol) (Primary alcohol)
OH OH CH3 CH3
(C) H3C − CH − CH2 − CH3 (D) H3C − CH2 − CH− CH − CH − CH3

Butan-2-ol 4,5-Dimethylhexan-3-ol
(Secondary alcohol) (Secondary alcohol)
11. Isopropyl alcohol has structural formula

CH3 − CH − OH. The C bearing − OH group is 2° because it is attached to two other carbon atoms.
CH3
OH
12. Cyclohexanol is a secondary alcohol because (− OH) group is linked to 2° carbon.
13. In case of tertiary alcohols, (−OH) group should be attached to tertiary carbon atom.
16. R− O− R′ Ethers If R = R′ , Simple ether If R ≠ R′ , Mixed ether

96

Chapter 11: Alcohols, Phenols and Ethers

4
21. CH3 − 3CH2 − 2CH − 1CH2 − OH OR (C2H5)2CHCH2OH
|
CH2CH3 2-Ethylbutan-1-ol
29. The general form of the IUPAC name of ether is alkoxyalkane where the alkyl with larger number of
carbons is considered as parent.
1 2 3
C2H5 − O − CH2 − CH2 − CH3
∴ 1-Ethoxypropane is the IUPAC name.
1
CH3
|
31. H3C – O – 2CH – 3CH3
2-Methoxypropane
34. An alkyl halide on hydrolysis with aqueous KOH gives an alcohol. A primary alkyl halide is converted to a
primary alcohol and a secondary alkyl halide is converted to a secondary alcohol.
OH
CH3CHICH3 + KOH(aq) → CH3 – CH – CH3 + KI

Isopropyl Isopropyl alcohol
iodide
35. CH2 = CH2 →

H 2SO4
CH3 – CH2 – HSO4 
Hydrolysis
→ CH3CH2 – OH + H2SO4
Ethene Ethanol
OH
36. CH3 − CH = CH2 

(i) Conc.H 2SO4
(ii) H 2 O
→ CH3 − CH − CH3
Propene Propan-2-ol
37. This process effectively results in the addition of a molecule of water across a double bond. Hence, it is a
hydration reaction.
CH2 = CHCH3 + HO−SO3H → H3C− CH − CH3 H2 O
 → H2SO4 + H3C − CH – CH3
Propene Sulfuric acid | |
OSO3H OH
Isopropyl hydrogen sulfate Isopropyl
alcohol
38. CH2 = CH2 + B2H6 → B(CH2CH3)3 
H 2 O2
OH −
→ 3CH3CH2OH
39. Hydroboration-oxidation of alkenes:

1
3CH3CH = CH2 + B2H6 
THF
→ (CH3CH2CH2)3B 
H 2 O2
OH −
→ 3CH3CH2CH2OH
2
40. LiAlH4 in dry ether acts as a reducing agent. It reduces C = O to CHOH, i.e., an aldehyde is reduced
to a primary alcohol and a ketone is reduced to a secondary alcohol.

() i LiAlH
CH3CHO + 2[H] + → CH3CH2OH
4
( ii ) H3O
Acetaldehyde Ethanol
(Ethanal)
41. LiAlH4 attacks only carbonyl group and reduces it into alcohol group. It does not reduce C = C double bond.
() i LiAlH
C6H5 – CH = CHCHO + → C6H5 – CH = CH – CH2OH
4
( ii ) H3O
Cinnamic aldehyde Cinnamic alcohol
42. Carboxylic acids are converted to primary alcohols by reaction with LiAIH4, followed by hydrolysis.
97


44. CH3CHO 
i. CH3 MgBr / ether
ii. H + / H O
→ CH3CHOHCH3
2
Ethanal Propan-2-ol
45. HCHO →

i. C2 H5 MgI
ii. H + / H O
CH3CH2CH2OH
2
R2 R2
R1 OH
46. C = O + R3Mg X 
→ dry ether
R1 – C – O – Mg – X → R1 – C – OH + Mg
dil.HCl
+H 2 O
R2 Grignard X
Ketone R3 R3
reagent
adduct
3° alcohol
50. Phenol is obtained from cumene (isopropylbenzene) by air oxidation in presence of Co-naphthenate,
followed by hydrolysis.
CH3 CH3
51. H3C – C – H H3C – C – O − O – H OH

O
Cobalt
dil.HCl
+ O2 → naphthenate →∆ + CH3 – C – CH3
423 K
Acetone
Cumene Cumene Phenol
(Isopropylbenzene) hydroperoxide
SO3Na OH
()
52. 
+ →
i NaOH
( ii ) H / H2O
Sodium benzene Phenol

sulphonate
55. With increase in molecular mass, boiling point of alcohol increases.
56. The correct order of boiling point for primary, secondary and tertiary alcohols is,
1° alcohol > 2° alcohol > 3° alcohol
59. o-nitrophenol forms strong intramolecular hydrogen bonding whereas p-nitrophenol forms strong
intermolecular hydrogen bonding with solvent water, making it more soluble in water.
60. Both phenols and alcohols have low acidic strength; hence, they do not show reaction with weak bases like
NaHCO3.
61. Phenol gives violet/purple/green colour with neutral FeCl3 solution, while alcohols do not give such colour.
62. 2C2H5 − OH + 2Na → 2C2H5 − ONa + H2 ↑
63. Order of reactivity of alcohols towards Lucas reagent (conc. HCl and ZnCl2) is 3° > 2° > 1°.
64. The conjugate base of alcohol is destabilized by the +I effect (Electron donating inductive effect) of the alkyl
group.
65. Phenols are more acidic than alcohols. Nitro group at para position is electron withdrawing group and
stabilizes the phenoxide ion, thereby increasing the acidic character of p-Nitrophenol.
66. Electron withdrawing groups increases the acidity of phenol, while electron releasing group decreases the
acidity of phenol.
68. When benzoic acid reacts with ethyl alcohol in the presence of sulphuric acid, ethyl benzoate is formed. This
is known as esterification.
C6H5COOH + C2H5OH → H 2SO4
C6H5COOC2H5
Benzoic acid Ethyl alcohol Ethyl benzoate
98


69. CH3 − OH + CH3COCl →
pyridine
CH3COOCH3 + HCl
Methyl alcohol Methyl acetate
72. The reaction proceeds by the protonation of the hydroxyl group followed by loss of water to give a
carbocation which then reacts with X− to form the alkyl halide. More the acid strength of the halogen acid,
greater is the protonating ability. Since the order of strength of halogen acids is HI > HBr > HCl, the order of
reactivity is also the same.
73. Alcohols are converted to alkyl chlorides by PCl5. Alcoholic KOH converts alkyl halides to alkenes
(dehydrohalogenation).
CH3CH2CH2OH + PCl5 → CH3CH2CH2Cl  alc.KOH
→ CH3CH = CH2
n-Propyl alcohol n-Propyl chloride Propene
(X) (Y)
74. According to Saytzeff rule, but-2-ene will be the major product (as it is more substituted alkene).
60% H 2SO 4 But-2-ene
CH3 − CH − CH2 − CH3 373 K (major product)
|
OH CH3 − CH2 − CH = CH2
Butan-2-ol But-1-ene
(minor product)
75. The order of ease of dehydration of alcohols is 3° > 2° > 1°.
76. H3C − CH2 − OH 

Al2 O3 , 623K
→ H2C = CH2 + H2O
Ethanol Ethylene
78. H3C – CH – CH – CH2OH 

PCC
→ CH3 – CH – CH – CHO
CH3 CH3 CH3 CH3

2,3-dimethylbutanal
79. CH3OH + [O] 

→ HCHO → [O]
HCOOH
Methanol Formaldehyde Formic acid
80. H3C – CH – CH3 + [O] CrO3

 → H3C – C – CH3
OH O
Propan-2-ol Propanone
81. 3° alcohols undergo oxidation under drastic conditions.
OH OH
Br Br
82. + 3Br2 
→ + 3HBr
Phenol (Bromine Br
water)
2,4,6-Tribromophenol
OH OH OH
Br
83. 2 + 2Br2 

273 K
CS2
→ + + 2HBr
Phenol o-Bromophenol Br
p-Bromophenol
99


21. CH3CH2 − OH + PCl5 
∆
→ CH3CH2 − Cl + HCl + POCl3
Ethanol Ethyl Phosphorus
(X) chloride oxychloride
22. The reaction of alcohol with SOCl2 (thionyl chloride) is the best method for the preparation of alkyl halides
as in this method all the other products are gases and thus there is no need to put extra efforts for the
separation alkyl halide..
R – OH + SOCl2  ∆
→ R – Cl + HCl ↑+SO2↑
23. C3H8 + Cl2 Light

→ C3H7Cl + HCl
This is an example of substitution reaction. Hydrogen atom of alkane is replaced (substituted) by halogen
atom.
25. Iodination is a reversible reaction and hydroiodic acid formed during iodination is a strong reducing agent,
which reduces alkyl iodide back to alkane. Presence of strong oxidising agent (e.g. HgO, HIO3) decomposes
hydroiodic acid and prevents the backward reaction.
26. H3C – CH = CH – CH3 + HBr → CH3 – CH2 – CH(Br) − CH3 or CH3 − CH(Br) − CH2 − CH3
But-2-ene 2-Bromobutane 2-Bromobutane
(A) (B)
Since the alkene is symmetrical, only one product is possible. (A) and (B) both are same product.
28. The bromide ion does not get attached to the carbon atom, with lesser number of H-atoms, in the presence of
peroxide as predicted by Markovnikov’s rule. This phenomenon is also known as peroxide effect or anti-
Markovnikov’s rule or Kharasch effect.
CH3 – CH2 − CH = CH2 + HBr  Peroxide
→ CH3 – CH2 – CH2 – CH2Br
But-1-ene 1-Bromobutane
29. In presence of peroxide the addition of HBr to an asymmetrical alkene follows the anti-Markovnikov’s rule.
HCl and HI always add according to Markovnikov’s rule even in the presence of peroxide.
30. When alkene is heated with Cl2 at high temperature, hydrogen atom of allylic carbon is substituted with
chlorine atom giving allyl chloride.
CH2 = CH − CH3 + Cl2 
∆
→ CH2 = CH – CH2Cl + HCl
Propene 3-Chloroprop-1-ene
CH3 CH3 CH3

Cl
34. 2 + 2Cl2 
Fe
→ + + 2HCl
dark
Toluene o-Chlorotoluene
Cl
p-Chlorotoluene
+ −
N2Cl Cl
35. CuCl/HCl

→ + N2 ↑
Benzenediazonium Chlorobenzene
chloride
36. The electronegativity difference between the H-atoms and the halide atoms, results in polar covalent bond.
Therefore, alkyl halides are moderately polar compounds.
37. For a given alkyl group, alkyl iodides have the highest molecular weight and boiling point also. Because as
the molecular weight increases, boiling point increases for alkyl halides.
38. For alkyl chlorides, boiling point increases with increase in molecular weight.
39. Alkyl halides are insoluble in water but soluble in non-polar organic solvents.
40. The isomeric dihalobenzenes have nearly same boiling points, but show variation in melting points.
79


41. A chiral molecule and its mirror image are not identical.
45. A compound which rotates the plane of plane polarized light towards right is dextrorotatory in nature.
46. Enantiomers have identical physical properties like melting point, boiling points, densities, refractive index
except the sign of optical rotation. The magnitude of their optical rotation is equal.
47. CH3
H − C*− I
C2H5
sec-Butyl iodide has one asymmetric carbon atom (marked *) and is therefore capable of exhibiting
enantiomerism.
49. This is the laboratory test for haloalkanes.
R – X + OH–  ∆
→ R – OH + X– Ag (+aq ) + X (−aq ) → AgX↓
Alkyl Hydroxide Alcohol Halide ; Halide ion Silver halide
Halide ion ion
(X)
50. In alkyl halides, the C−X carbon is an electrophilic centre. Hence, it has a tendency to react with a
nucleophile. Alkyl halides react with a large number of nucleophilic reagents.
R – X + Nu– → R – Nu + X– (leaving group)
51. C2H5Cl + KOH(aq) 
∆
→ C2H5OH + KCl.
52. When alkyl halide react with sodium alkoxide corresponding ether is formed.
R–X + NaOR′  ∆
→ R – O – R′ + NaX
Ether
53. C2H5ONa + C2H5Br − NaBr

 → C2H5 − O − C2H5
Sodium salt Ethyl bromide Diethyl ether
of ethanol
54. CH3Br + CH3COOAg 

∆
→ CH3COOCH3 + AgBr
Methyl Silver Methyl acetate
bromide acetate
55. C2H5Br + NH3 (alc.) →∆

pressure
C2H5NH2 + HBr
Ethyl (Excess) Ethylamine
bromide
56. H3C – CH2 – CH2Cl + KCN 

Boil
→ H3C – CH2 – CH2 – CN + KCl
n-Propyl chloride (alc.) Butanenitrile or n-Propyl cyanide
57. → R−NC + AgX ↓

AgCN + R − X  ∆
Silver Alkyl Alkyl Silver

cyanide halide isocyanide halide
(Alc.) precipitate
59. In SN2 mechanism, the rate is proportional to concentration of the reactants; both substrate and reagent.
e.g. CH3Br + OH– → CH3OH + Br–
Rate = k[CH3Br] [OH–]
The reaction is said to follow second order kinetics, since rate is dependent on the concentration of two
substances.
62. The SN2 mechanism is found to proceed with inversion of configuration which is also known as Walden
inversion.
63. Example of SN1 mechanism:
(CH3)3C − Br 
NaOH ( aq )
hydrolysis
→ (CH3)3C+ + Br–
Planar Carbocation
80


64. In SN1 reaction, the incoming nucleophile can attack from the back and front sides because it is a 2 step
process; in 1st step carbocation is formed and in 2nd step nucleophile attacks, for which both sides are
available for attack. Hence, there is inversion as well as retention of configuration.
65. When an optically active alkyl halide follows SN1 mechanism, racemic mixture is formed.
R2 R2 R2
−
R1 − C − Cl 
CN
→ R1 − C − CN + NC − C − R1
R3 R3 R3
Racemised Products
3° halides are more susceptible to SN1 mechanism.

66. Primary alkyl halides readily undergo SN2 reaction.
67. Reactivity is directly related to the stability of carbocations. the stability of carbocation is
3° > 2° > 1° > CH3. Greater the number of alkyl groups, the more stable the carbocation. This is due to the
(+I) inductive effect of the alkyl group.
68. Conversion of bromomethane to methanol follows SN2 mechanism. It readily takes place in the presence of
strong nucleophile and aprotic solvents or solvents of low polarity.
69. SN1 reaction is most favoured in the presence of polar protic solvents. Also, it is favoured in the presence of
tertiary alkyl group and independent of the nature of nucleophile.
70. CH3CH2Br  alc.KOH
→ CH2 = CH2 + HBr
Dehydrohalogenation is a process in which both hydrogen and halogen are removed from a molecule of
alkyl halide.
71. CnH2n + 1X 
− HX
→ CnH2n + HX (Dehydrohalogenation)
Haloalkane Alkene
72. Dehydrohalogenation is the removal of hydrogen and halogen altogether from an alkyl halide, and the
reaction can be effectively carried out by alcoholic KOH.
73. CH3 − CH2 − CH2Br + KOH(alc.) 

∆
→ CH3 − CH = CH2 + KBr + H2O
n-Propyl bromide Propene
CH3
CH3 − C = CH − CH3
Br
alc. KOH
74. CH3 − C − CH2 − CH3
∆
CH3 CH2 = C − CH2 − CH3
2-Bromo-2-methylbutane
CH3
Br
alc. KOH But-2-ene (major)
75. CH3 − CH − CH2 − CH3
sec-Butyl bromide ∆ H2C = CH − CH2 − CH3
But-1-ene (minor)
Since two different types of hydrogen atoms are present to the adjacent C atoms of secondary carbon
containing −Br group, two products are possible. However, according to Saytzeff’s rule, “In
dehydrohalogenation reaction, the preferred product is that alkene which has greater number of alkyl groups
attached to doubly bonded carbon atoms.” Hence, but-2-ene is the preferred product, and is formed as the
major product.
81


76. Alkyl iodides have the weakest C − X bond, hence can be broken easily.
77. The stability order of alkyl substituted alkenes with reference to dehydrohalogenation reaction is:
R2C = CR2 > R2C = CHR > R2C = CH2, RCH = CHR > RCH = CH2
78. In an organometallic compound, the metal is directly bonded to any one of the carbon atoms of the chain.
80. CH3 – CH2 – Br + Mg 

Dry ether
→ CH3CH2MgBr
Ethyl bromide Ethyl magnesium
bromide
This is the method for preparation of Grignard reagent.
81. C4H9MgBr 

HOH
→ C4H10 + MgBr(OH)
n-Butyl n-Butane
magnesium bromide
Grignard reagent is very sensitive to moisture. When it comes into contact with water, it is converted to the
corresponding alkane.
−δ +2δ −δ +δ −δ
R − Mg − X + H − OH → R − H + MgOH(X)
Grignard Alkane
reagent
83. Ethyl bromide and methyl bromide undergo Wurtz reaction with metallic sodium in dry ether.
CH3 – CH3
Ethane
Na
CH3Br + C2H5Br CH3 – CH2 – CH3
Methyl Ethyl dry ether Propane
bromide bromide CH3 – CH2 – CH2 – CH3
Butane
84. The above reaction is known as Wurtz-Fittig reaction.

85. The product is biphenyl, formed by Fittig reaction.
88. Chlorobenzene when heated with nitrating mixture (conc. H2SO4 + conc. HNO3) yields both ortho and para
chloronitrobenzene, with para derivative as the major product.
Cl Cl Cl
SO3H
89. 2 + 2 H2SO4 
∆
→ + + H2O
Chlorobenzene (conc.) (Minor)

2-Chlorobenzene SO3H
sulphonic acid (Major)
4-Chlorobenzene
sulphonic acid
Cl Cl Cl
CH3
90. 2 + 2CH3Cl →
anhydrous AlCl3
+ + 2HCl
Chlorobenzene Methyl (Minor)

CH3
chloride 1-Chloro-2-methylbenzene
(Major)
1-Chloro-4-methylbenzene
82


94. Freons are chlorofluorocarbons (CFC's) which are commonly used as refrigerants.
95. They are position isomers as both have the same molecular formula and only differ by the position of the
halide group.
96. In geminal dihalides, both the halogen atoms are attached to the same carbon atom.
97. H2SO4 is an oxidising agent. It oxidises HI produced during the reaction to I2. This can be represented as,
2HI + H2SO4 → 2H2O + I2 + SO2↑
As a result, it prevents the reaction between an alcohol and HI to form an alkyl iodide. Therefore, in order to
overcome this difficulty, a non-oxidising acid such as H3PO4 is used instead of H2SO4.
98. Nucleophiles are electron rich groups capable of donating electrons to electron deficient centres. All the
mentioned groups are capable of donating lone pair of electrons.
Critical Thinking
2. C4H9Br can have the following structures

1°
(A) CH3 − CH2 − CH2 − CH2Br (1° Bromoalkane)
2°
(B) CH3 − CH2 − CH− CH3 (2° Bromoalkane)
|
Br
CH3
| 3°
(C) H3C − C − CH3 (3° Bromoalkane)
|
Br
3. The structure of (CH3)3C − Cl is,
CH3

CH3  C  CH3

Cl
The chlorine is attached to a 3° carbon atom. So, it is a tertiary alkyl halide. ‘A’ and ‘B’ are primary alkyl
halides while ‘D’ is a secondary alkyl halide.
1° 1°
CH3 CH3
1° 3° 4° 2° 1°
4. Cl–CH2 − CH − C − CH2 − CH3
1°
CH3
1-Chloro-2,3,3-trimethylpentane
10. The order of reactivity of alcohols towards a given haloacid is 3° > 2° > 1°.
11. The reactivity of alcohols with HBr is in the order 3° > 2° > 1°. 2-Methylpropan-2-ol is a tertiary alcohol.
CH3
i.e., CH3 – C – CH3
OH
Hence, it reacts fastest with HBr. Propan-1-ol and 2-Methylpropan-1-ol are primary alcohols. Propan-2-ol is
a secondary alcohol.
83


∆
→ C2H5Cl + HCl ↑ + SO2↑
13. Alcohols do not react with NaCl.

ROH + HCl 
Anhydrous ZnCl2
→ RCl + H2O
3ROH + PBr3 → 3RBr + H3PO3
ROH + SOCl2 
∆
→ RCl + SO2 + HCl
15. Addition occurs according to Markovnikov’s rule.

Cl
|
CH3− CH2 − CH2 − CH = CH2 + HCl 
Markovnikov's rule
→ CH3− CH2 − CH2 − CH − CH3
Pent-1-ene 2-Chloropentane
16. CH2 = CH − CCl3 + HBr → CH3 − CH(Br) − CCl3

17. Peroxide effect is shown by unsymmetrical alkenes like CH2 = CH − CH3.
18. In the presence of benzoyl peroxide, the reaction gives a product contrary to the Markovnikov’s rule.
CH3 CH3
| |
CH3 – C = CH2  HBr
Peroxide
→ CH 3 – CH – CH2Br
Isobutylene Isobutyl bromide
19. In presence of peroxide, Anti-Markovnikov’s product is the major product formed.

Ph–CH = CH2 + HBr  H 2 O2
Anti-Markovnikov’s rule
→ Ph(CH2)2–Br
Phenylethene 1-Bromo-2-phenylethane (X)
21. The reaction is addition reaction. Since only one molecule of HBr is added, ‘A’ contains one double bond.
∴ It is an alkene.
23. Fluoro compounds cannot be prepared by direct halogenation of benzene as fluorine is highly reactive.
Though the reaction with iodine is reversible, iodobenzene can be prepared in presence of HNO3/HIO4, which
prevents the reverse reaction
+ –
24. C6H5N2Cl 
CuBr / HBr
→ C6H5Br + N2↑
diazonium (Aryl halide)
chloride
26. The three dimensional structure of the given compounds along with the direction of dipole moment in each
of their bonds is given below:
Cl H Cl H Cl Cl Cl Cl
C C C C
H H Cl H Cl H Cl Cl
In CH2Cl2, the resultant of two C−Cl dipole moments is reinforced by resultant of two C−H dipoles.
Therefore, CH2Cl2 has a dipole moment higher than that in the other given options.
27. C–X bond enthalpy of halomethanes in kJ mol–1:
CH3F: 452 CH3Cl: 351
CH3Br: 293 CH3I: 234
C–X bond enthalpy of fluoromethane is highest amongst others.
28. With increased branching, surface area decreases, hence, van der Waal’s forces of attraction also decreases.
As a result, boiling point among the isomeric alkyl halides follows the order: 1° > 2° > 3°.
84


53. Primary alcohol 
Cu
→ Aldehyde + H2↑ Secondary alcohol 
Cu
→ Ketone + H2↑
300 ° C 300 ° C
Tertiary alcohol → Olefin + H2O

Cu
300 ° C
Primary and secondary alcohols on passing over hot reduced copper undergo dehydrogenation to give
carbonyl compounds. Tertiary alcohols undergo dehydration to give olefins.
OH OH
Br Br
54. + 3Br2 
→ + 3HBr
Phenol (Bromine
water) Br
SO3H OH OH
Br Br
→H 2 SO 4 i.Alkali fusion Br2
56. 350 K

→ii. dil. HCl →
H2 O
(A) (B)
Br
(C)
57. For the conversion of carbolic acid (phenol) to picric acid, the reagents used are conc. HNO3 in the presence
of conc. H2SO4.The nitrating mixture produces a large concentration of electrophile NO +2 .
 NO +2 + H3O+ + 2HSO −4
HONO2 + 2H2SO4 
OH OH
O2N NO2
+ 3HO − NO2 
→ ∆
conc.H 2SO4
+ 3H2O
Phenol (conc.)
NO2
Picric acid
(2,4,6–Trinitrophenol)
OH
58. ∆ + ZnO
+ Zn 
→
Phenol Benzene
59. Ethyl alcohol is dehydrated to ethylene by conc. H2SO4 at 443 K.

C2H5OH H 2SO4 /443 K
− H2 O
→ CH2 = CH2
Two molecules of ethyl alcohol are dehydrated to ethoxyethane by conc. H2SO4 at 413 K.
2C2H5OH 
H 2SO4 /413 K
− H2 O
→ C2H5 – O – C2H5
Ethanol Ethoxyethane
60. CH3 – I + NaOCH(CH3)2 → CH3 – O – CH(CH3)2 + NaI

Methyl Sodium Isopropyl methyl
iodide isopropoxide ether
106

CH3 CH3
| |
61. CH3− C − O − Na + Cl − CH3 ∆
 → CH − C − O −CH +NaCl
3 3
| |
CH3 CH3
2,2-Dimethyl sodium Methyl tert-butyl
ethoxide ether
62. C2H5OH + Na →C2H5ONa

Ethanol Sodium ethoxide
(A) (B)
C2H5OH 
Conc.H 2SO4
→ C2H5 – O – C2H5
Ethanol Diethyl ether
(A)
63. X 
Na
→ Y ; X 
PCl5
→ Z ; Y + Z → C2H5OC2H5.
C2H5OH + Na → C2H5ONa
Ethyl alcohol Sodium ethoxide
(X) (Y)
C2H5OH + PCl5 → C2H5Cl + POCl3 + HCl

Ethyl alcohol Ethyl chloride
(X) (Z)
C2H5ONa + C2H5Cl ∆
 → C2H5 − O − C2H5 + NaI
Sodium ethoxide Ethyl chloride Diethyl ether
(Y) (Z)
65. Since, the last step is the Williamson’s ether synthesis, hence alkanes cannot be obtained.
CH2 = CH2 

HBr
→ CH3 – CH2Br 
NaOH(aq)
→ CH3 – CH2 – OH 
Na
→ CH3 – CH2 – ONa
(P) (Q) (R)
CH3I
CH3 – CH2 – O – CH3

Ethyl methyl ether
(S)
CH3 CH3
66. CH3−CH – O–Na+ + Br – CH2CH3 

− NaBr
→ H3C – CH − O − CH2 − CH3
sec-Alkyl halides undergo elimination reaction with sodium alkoxides (strong bases) easily.
(CH3)2CHBr  RONa
→ H3CCH = CH2 + ROH + NaBr. This will be the product in option ‘B’. 2° alcohols in
presence of H2SO4 will give the alkene rather than the ether. An alkyl halide and an alcohol do not react to
give ether.
67. CH3− CH − CH3 + KOH → CH3− CH = CH2 + KBr + H2O
(alcoholic) (A)
Br
CH3− CH = CH2 + HBr 
Peroxide
→ CH3 − CH2 − CH2 − Br
(A) 1-Bromopropane
(B)
CH3− CH2−CH2− Br + CH3− O − Na → CH3− CH2−CH2− O – CH3 + NaBr

(B) Methyl n-propyl ether
(C)
107


68. With increase in molecular mass, boiling point increases.
70. Ethers do not react with active metals such as sodium.
71. Ethers dissolve in cold conc. H2SO4 due to formation of oxonium salts.
72. OC2H5 OH
∆
+ conc.HBr  → + C2H5Br
Ethyl phenyl Phenol Ethyl bromide

ether
73. Methoxymethane gives only methanol. Ethoxyethane gives only ethanol. Methoxyethane gives methanol
and ethanol, which are successive members of homologous series. 2-Methoxypropane gives methanol and
propan-2-ol, but they are not successive members of homologous series.
CH3 CH3 OH
dil.H 2SO4
74. H3C − CH − O − CH − CH3 + H2O  ∆
→ 2CH3− CH − CH3
2-Isopropoxypropane Propan-2-ol
OCH3 OCH3
Br2 in CH3COOH
75.  →
Anisole
Br
p-Bromoanisole
(Major product)
OH O CH3
77. CH3− CH − CH3 
K 2 Cr2 O7
dil.H 2SO4
→ CH3− C − CH3 
CH3 MgI
H2 O
→ CH3− C − CH3
Isopropyl alcohol Acetone OH

(A) (B) Tertiary butyl alcohol
78. (I) Dehydration of alcohols to form ether is an SN2 reaction.

(III) The reaction of an ether having one 3° alkyl group with hot HI follows SN1 mechanism.
H3 O +
80. CH3Br 
alc.KCN
→ CH3CN  → CH3COOH →
LiAlH 4
CH3CH2OH
81. CH3CH2CH2OH 

conc.H 2SO4
160 −180 ° C
→ CH3CH = CH2 →
Br2
CH3 – CH – CH2 
Alc. KOH
→ CH3 – C ≡ CH
(X) Propyne
Br Br
(Z)
(Y)
OH OH OH
COONa COOH OCOCH3
H+ / H2 O
82. i. NaOH
ii. CO2 /398 K
→ 
→ Ac2 O
 →
Salicylic
COOH
Phenol
Intermediate acid Aspirin
83. The CORRECT statements are:

(A) Phenol is a weak acid; hence, it does not react with NaHCO3.
(B) Monohydric alcohols are those, which contain one –OH group and which can be on primary,
secondary or tertiary carbon atoms.
(C) Boiling points of alcohols are higher than those of ethers because of hydrogen bonding between two
alcohol molecules.
(D) Ethers are prepared by Williamson’s synthesis.
108

1. H OH H OH OH H H OH
H3C – C – C – CH3 H3C – C – C – CH3 H3C – C – CH3 H3C – C – C – C – CH3
CH3 H H H CH3 H H H
3-Methylbutan-2-ol Butan-2-ol 2-Methylpropan-2-ol Pentan-2-ol
(2° alcohol) (2° alcohol) (3° alcohol) (2° alcohol)
4. This reaction follows Markownikoff’s rule.

OH
+
H
H3C − C = CH2 + H2O → H3C – C – CH3
CH3 CH3
2-Methylpropene 2-Methylpropan-2-ol
CH3O CH3OMgBr
5. H
OR H3C − C − C− H + CH3MgBr 
Dry ether
→ H3C − C − C − H
O H H CH3
2-Methylpropanal
Complex
(A)
H + / H 2O or H 3O +
CH3 OH
Br
H3C − C − C− H + Mg
OH
H CH3
3-Methylbutan-2-ol
(B)
H H
− +
6. H − C = O + C2H5MgBr 
dry ether
→ H − C − O Mg Br →H2 O
( Hydrolysis ) CH3− CH2 – CH2− OH + Mg(OH)Br
Methanal Propan-1-ol
(Formaldehyde) C2H5
(1º alcohol)
Addition compound
7. Aldehydes (other than formaldehyde) react with Grignard reagent, followed by acid hydrolysis, to form
secondary alcohols. Therefore, among the given options, acetaldehyde will give a secondary alcohol upon
treatment with methyl magnesium bromide followed by acid hydrolysis.
OH
(i) CH3MgBr /dry ether
CH3CHO 
(ii) H+ / H O
→ CH3− CH − CH3
2
Acetaldehyde Propan-2-ol
(2° alcohol)
109


8. H3C CH3 H3C CH3
CH C–O–O–H OH
H3C CH3
O2 H+
→ 
→ H2 O +
O
Cumene Cumenehydroperoxide Phenol
(A)
10. Boiling points of alcohols increases with increase in molecular mass while it decreases with increase in
branching. Since Butan-1-ol has high molecular mass and no branching, it has highest boiling point.
11. Boiling point decreases with an increase in branching. Amongst all the isomers of butyl alcohol, tert-Butyl
alcohol has the maximum branching and hence, it has the lowest boiling point.
12. Very weak acidic character of alcohol is revealed in the reaction with active metal.
2C2H5OH + 2Na → 2C2H5ONa + H2↑
The evolution of hydrogen gas indicates the acidic property of ethanol.
Alcohols are neutral to litmus test. They do not react with NaHCO3 and Na2CO3.
14. 2C2H5OH(l) + 2Na(s) → 2C2H5ONa(l) + H2(g)↑
2 mol of sodium liberate 22.4 dm3 of gas at NTP.
1 mol of sodium liberate 11.2 dm3 of gas at NTP.
i.e., 23 g of sodium liberate 11.2 dm3 of gas at NTP.
15. Tertiary alcohols react immediately with Lucas reagent and give turbidity.
16. Tertiary alcohols give immediate turbidity on shaking with HCl at room temperature.
17. Phenols are more acidic than alcohols. Further, phenols with electron-withdrawing substituents (like − NO2
group) are more acidic than phenols with electron-donating substituents (like −CH3 group).
OH
Hence, among the given options, the strongest acid is
NO2
18. Presence of electron releasing group like −NH2 decreases the acidic strength of phenol. Therefore, phenol is
more acidic than p-aminophenol. Presence of electron withdrawing group increases the acidic strength of the
phenol. When electron withdrawing group like −NO2 is present at p-position, then it exerts both −I and −R
effect whereas when it is present at m-position, it exerts only −I effect. Hence, p-nitrophenol is a stronger
acid than m-nitrophenol. Therefore, the most acidic phenolic compound is p-nitrophenol.
19. The order of acidity for the given compounds follows the order,
OH OH OH OH
O2N NO2
> > >
NO2 NO2 CH3

More −I, −M effect, more acidic is the compound.
CO2H
CO2H
( CH
3 CO ) O
20.  2
Conc.H 2SO4
→ + CH3COOH
(Catalyst )
HO
4-Hydroxybenzoic acid OCOCH3

4-Acetoxybenzoic acid [Q]
22. PCC being a mild oxidising agent, oxidises primary alcohols to corresponding aldehydes without further
oxidation to carboxylic acids.
110


R R
23. R – CH – OH 
Cu
573 K
→ R – C = O + H2 ↑
2° Alcohol Ketone
OH OH OH
NO2
Room temperature
24. 2 + 2HNO3 
→ + + 2H2O
(dil)
Phenol o-Nitrophenol
NO2
p-Nitrophenol
26. On treating phenol with chloroform in the presence of sodium hydroxide, a −CHO group is introduced at
ortho position of benzene ring. This reaction is known as Reimer-Tiemann reaction.
− + − +
OH ONa ONa OH
CHCl2 CHO CHO
NaOH H+
CHCl3 + aq. NaOH

→ → →
Phenol Salicylaldehyde
Intermediate
29. At high temperature, the ether is completely cleaved by concentrated HI to give the corresponding alkyl
iodide.
C2H5 – O – C2H5 + 2HI ∆
 → 2CH3CH2I + H2O
Diethyl ether (conc.) Ethyl iodide
+ + -
H
30. C6H5− O − CH3 → C6H5− O − CH3 
I
SN 2
→ C6H5 − OH + I − CH3
Methyl phenyl Phenol Methyl
ether H iodide
31. In case of 3-methoxystyrene, protonation gives corresponding oxonium ion.

The bond between O−CH3 is weaker than the bond between O−C6H4 – CH = CH2 because the carbon atom
of phenyl group is sp2 hybridised and there is a partial double bond character. Hence, the attack by Br– ion
results into the cleavage of O−CH3 bond to yield CH3Br. 3-Vinyl phenol do not react further with HBr
because the sp2 hybridised carbon (of aromatic ring) of 3-vinyl phenol cannot undergo nucleophilic
substitution reaction. Instead addition reaction occurs at C = C double of the side chain.
⊕
OCH3 O – CH3 OH OH
→ Conc. HBr →
CH3 BR
HBR
( Excess )
Δ
H 
→
CH = CH2 CH = CH2 CH = CH2 (Br)CH – CH3

3-Methoxystyrene 3-Vinyl phenol 3-(1-Bromoethyl)phenol
32. Br
+ HBr → OH
O
1-methylethylene 2-Bromopropanol
oxide
Br Br
Br
OH + HBr (excess) →
1,2-Dibromopropane
111


34. The given hydrocarbon is isopentane.
1 2 3 4
H3C − CH − CH2− CH3
CH3
H-atom attached to C-1, C-2, C-3 or C-4 can get replaced by hydroxy group. Thus, there are 4 different
monohydroxy derivatives possible for the given hydrocarbon.
35. Alcohols have higher boiling points than corresponding alkanes, alkyl halides, aldehydes, ketones and ethers
of nearly same molecular mass. This is due to intermolecular hydrogen bonding in alcohols.
H 2 O2
36. CH3−CH2−CH = CH2 + HBr 
Anti − Markownikoff 's
→ CH3CH2CH2CH2Br 
C2 H5 ONa
→ CH3(CH2)3−O−CH2CH3
rule
But-1-ene 1-Bromobutane (Y) 1-Ethoxybutane (Z)
37. The reaction is as follows

– +
2Na + 2C2H5OH → 2C2H5O Na + H2
∴ 2 mol Na = 1 mol H2
46 g Na ≡ 2 mol Na
∴ 46 g Na = 2 g H2 = 2 × 10–3 kg H2
39. i. OCH3
Cl
− +
H3C− C − CH2 −CH2 − CH3 + CH3− O N a Methanol/ Δ
→
Williamson H3C – C – CH2 – CH2 – CH3 + NaCl
synthesis
CH3 Sodium CH3

methoxide
2-Chloro-2-methyl 2-Methoxy-2-methylpentane (a)
pentane
ii. In case of secondary or tertiary alkyl halides, Williamson synthesis is sterically difficult (crowding
effect). Hence, β-elimination is predominant in the presence of stronger bases like alkoxides resulting
in the formation of corresponding alkene. In 2-chloro-2-methylpentane, two different products are
formed due to elimination of β-hydrogen from −CH3 and −CH2– groups respectively as given below:
H Cl
− + β α
H3C− O N a + H2C  C – CH2 – CH2 – CH3 
β− elimination
∆
→ H2C = C – CH2 – CH2 – CH3 + CH3OH + NaCl
Sodium
methoxide CH3 CH3
2-Chloro-2-methylpentane 2-Methylpent-1-ene
(b)
H Cl CH3
− + β α
H3C− O N a + H − C  C – (CH3)2 
β− elimination
∆
→ H − C = C – CH3 + CH3OH + NaCl
Sodium
methoxide CH2− CH3 CH2− CH3
2-Chloro-2-methylpentane 2-Methylpent-2-ene
(c)
OH O
40. CH3− CH = CH2 →

H 2SO4
CH3− CH − CH3 
H2 O
→ CH3− CH − CH3 K 2 Cr2 O7
 → CH3− C − CH3
Propylene Propan-2-ol Propanone
OSO3H (B) (C)
Isopropyl hydrogen
sulphate
(A)
112

1. In the carbinol system, monohydric alcohols are named as derivatives of methyl alcohol, CH3OH (which is
known as carbinol).
3. Tertiary alcohols undergo oxidation under drastic conditions.
4. Aspirin is prepared by acetylation of salicylic acid using acetic anhydride.
COOH COOH O
OH O O –O– C – CH3 + CH3COOH
+
H
+ CH3–C–O–C–CH3 → Acetic acid
Salicylic acid Aspirin
(Acetyl salicyclic acid)
OH O
Na 2 Cr2 O7
5. 
H 2SO4
→
Phenol
O
p-Benzoquinone
6. The boiling point of monohydric alcohols increases with increase in their molecular mass due to increase in
weak van der Waals forces; hence pentanol will have a higher boiling point than ethanol.
7. CH3−O−C2H5 + PCl5 → CH3–Cl + C2H5–Cl + H2O
Methoxyethane
+
8. (a) CH2 = CH – CH3 + H2O  H
acid catalysed
→ CH3 – CH – CH3
hydration
OH
Propan-2-ol
OH
(b) ( i ) CH3 MgI
CH3CHO → CH3 – CH – CH3 + Mg I
( ii ) H 2 O
Propan-2-ol OH
I
(c) ( i ) C2 H5 MgI
CH2O  ( ii ) H 2 O →
CH3CH2CH2OH + Mg
Propan-1-ol
OH
( i ) LiAlH 4
(d) CH3 – C – OH 
ii H O+
→ CH3CH2OH
( ) 3
Ethanol
O
10. Alcohols which form the most stable carbocation undergo dehydration more readily. Tertiary-butyl alcohol
forms the most stable tert-butyl carbocation among the given alcohols.
OCH3 OCH3 OCH3

COCH3
11. + CH3COCl 
Anhydrous
AlCl3
→ +
Anisole 2-Methoxy
COCH3 acetophenone
4-Methoxy (Minor)
acetophenone
(Major)
113


12. Higher the number of electron withdrawing substitituents, higher is the acidity of phenol. An electron
releasing substituent such as methyl group decreases the acidity of phenol.
13. Reactivity of alkyl halides having same halide group but with different alkyl groups is tertiary > secondary >
primary.
H3C H 3C OSO3H H3C OH

14. C = CH2 + H2SO4 → C ∆ , H2 O

− H 2SO4
→ C
H3C (cold and CH3 H3C CH3
conc.) H3C
Isobutylene
tert-Butyl hydrogen tert-Butyl alcohol
sulphate
CH3 CH3
15. CH3 − O − C − CH3 + HI 

cold
→ CH3− OH + I − C − CH3
Methanol
CH3 CH3
2-Methoxy-2-methylpropane tert-butyl iodide
OH O−Na+ O − CH3
CH3 − I
17. + NaOH → ∆
→
Phenol Sodium Anisole

phenoxide
19. −COOH group is reduced to –CH2OH group by LiAlH4, followed by hydrolysis.
O O O
H+
20. R – OH + R′ – C – O – C – R′ → R – C – OR′ + R′COOH
Alcohol Anhydride Ester Carboxylic
acid
114
 Chapter 12: Aldehydes, Ketones and
Carboxylic Acids
12 Aldehydes, Ketones and Carboxylic Acids
Hints
Classical Thinking
2. Aldehydic carbonyl group is also called as formyl group.
O O
3. Carboxyl (− C − OH) group is a combination of carbonyl (− C −) and hydroxyl (− OH) group.
4. Compounds given in options (A), (B) and (C) contain –CHO group (formyl group) attached directly to sp3
hybridized carbon atom. Thus, can be categorised as aliphatic aldehydes. However, in (D), –CHO group is
attached directly to an aromatic ring and hence, it is an aromatic aldehyde.
6. The ketones in which two alkyl/aryl groups bonded to carbonyl carbon are different, are called mixed
ketones or unsymmetrical ketones.
7. Camphor contains ketonic group.
8. The aromatic compounds in which the –COOH group is not attached directly to the ring are called side-
chain aromatic acids.
COOH OCOCH3 COOH
CH2 – COOH
COOH COOH COOH
Phenyl acetic acid Phthalic acid Acetyl salicylic acid Oxalic acid
CH3
3 2 1 O
12. CH3 C C
H
H
2-Methylpropanal
α
13. CH3CH2CH CHO
CH3
2-Methylbutanal
or
α-Methyl butyraldehyde
14. Oxaldehyde (Glyoxal): CHO – CHO

IUPAC name: Ethanedial
15. Benzene-1,2-dicarbaldehyde: Phthalaldehyde;
CHO
CHO
2-Methylbenzaldehyde: o-Tolualdehyde
CHO
CH3
115


H
16. H3C C COOH
CH3
2-Methylpropanoic acid
(Isobutyric acid)
17. Acrylic acid i.e., CH2 = CH – COOH

∴ IUPAC name is Prop-2-enoic acid.
18. H3C CH2 CH COOH
NH2
Principal functional group is carboxyl (−COOH). By IUPAC nomenclature, the name of the compound is
2-aminobutanoic acid.
5 4 3 2 1
19. H3C CH CH CH2 COOH
CH3 CH3
3,4-Dimethylpentanoic acid
22. CH3 CH2 C CH3

4 3 2 1
Butanone
23. Diethyl ketone is CH3CH2COCH2CH3 i.e.,

O
1 2 3 4 5
CH3 CH2 C CH2 CH3
Pentan-3-one
24. Methyl n-propyl ketone is CH3COCH2CH2CH3 i.e.,

O
1 2 3 4 5
CH3 C CH2 CH2 CH3
Pentan-2-one
25. (CH3)2CHOH 

Mild oxidation
[O]
→ (CH3)2C = O
Isopropyl alcohol Dimethyl ketone /Acetone
H3C CH3 H3C O CH3 CH3

26. C=C O3
 → C C H 2 O / Zn
 → 2 C=O
H3C CH3 H3C CH3 CH3
O O Acetone
2,3-Dimethylbut-2-ene
27. Ozonolysis of 2-methylbut-1-ene:
CH3
→ CH3 − CH2 − C = O + H − CHO

i. O3
CH3 − CH2 − C = CH2 
ii. Zn / H 2 O
Butanone Methanal
CH3
2-Methylbut-l-ene
40% H 2SO4
28. HC ≡ CH + H2O 
1% HgSO4
→ CH3CHO
Acetylene Acetaldehyde
116
Carboxylic Acids
O
40% H 2SO4
29. H3C – C ≡ CH + H2O 
1% HgSO4
→ H3C – C – CH3
Propyne Acetone
31. Rosenmund reduction of benzoyl chloride:

O
C CHO
Cl  H2
→
Pd − BaSO4 + HCl
Benzoyl chloride Benzaldehyde
32. (A) CH2 = CH − CH2 − CH = CH2  i) O3

ii) Zn,H 2 O
→ 2HCHO + OHC − CH2 − CHO
Penta-1,4-diene Formaldehyde Propanedial
(B) CH3CH  i) O3

ii) Zn,H 2 O
→ CH3CHO + O
Acetaldehyde Cyclopentanone
(C) HC ≡ CH + H2O 
40% H 2SO4
1% HgSO4
→ CH3CHO
Acetaldehyde
(D) CH3COCl + H2 

Pd-BaSO4
→ CH3CHO
Acetaldehyde
33. (C2H5)2Cd + 2CH3COCl → 2CH3COC2H5 + CdCl2

Diethylcadmium Acetyl chloride Ethyl methyl Cadmium
ketone chloride
35. This is an example of Stephen reaction.

+
H3C – C ≡ N + 2[H] 
SnCl2
dil.HCl
→ CH3CH = NH.HCl 
H3 O
→ CH3CHO + NH4Cl
Methyl cyanide Aldimine hydrochloride Acetaldehyde
AlH ( i − Bu )
36. H3C – CH = CH – CH2 – C ≡ N 
H O+
2
→ H3C – CH = CH – CH2 – CHO
3
Pent-3-enenitrile Pent-3-enal
Nitriles when reduced by AlH(i-Bu)2 to imines followed by acid hydrolysis to aldehydes, double or triple
bond present in the nitrile does not undergo reduction.
39. Aliphatic or aromatic esters are reduced to aldehydes by using diisobutylaluminium hydride [i.e., (DIBAl-H)
or AlH(i-Bu)2].
i) AlH(i − Bu)2
CH3 – CH2 – COOCH3  ii) H O+
→ CH3 – CH2 – CHO
3
Methyl propionate Propanal
OH O O
+
40. R – C ≡ N + H – OH → R – C = NH → R – C – NH2 →
H
R – C – OH + NH3
Alkyl cyanide Carboxylic acid
41. CH3CONH2 

H2 O
→ CH3COOH + NH3
42. Ph – COOC2H5 + H2O 

dil.H 2SO4
→ Ph – COOH + C2H5OH
Ethyl benzoate Benzoic acid Ethyl alcohol
+
43. CH3CH2CH2COOC2H5 
NaOH

− C2 H5 OH
 CH3CH2CH2COONa 
 H3 O
→ CH3CH2CH2COOH
Ethyl butanoate Sodium butanoate Butanoic acid
117


44. tert-Butylbenzene [i.e., PhC(Me)3] does not contain any benzylic H-atom. Thus, it will not undergo
oxidation reaction.
45.
(A) (B)
CH = CH2 COOH KMnO4 / dil.H 2SO4 COOH
→ ∆
KMnO4 / dil.H 2SO4
→ ∆
COOH
Phenylethene Cyclohexene Adipic acid
Benzoic acid (Hexane-1,6-dioic acid)
(C) CH3 COOH (D) CH3 COOH
CH3 COOH
KMnO4 / dil.H 2SO4
→ ∆ 
+
K 2 Cr2 O7 , H, ∆
→
o-Xylene Phthalic acid
CH3 COOH
p-Xylene Terephthalic acid
O O
46. C
(i) Dry ether
O + CH3MgBr 
(ii) hydrolysis
→ CH3 − C − OH + HO − Mg − Br
Solid Methyl Acetic acid
carbon magnesium
dioxide bromide
MgBr O COOH
O
47. C=O + dry ether

 →
C − OMgBr H3 O +
+ Mg(OH)Br
 →
Dry ice
(Solid carbon
dioxide) Phenyl Benzoic acid
magnesium
bromide
Adduct
49. Water solubility decreases with increase in molecular mass as the proportion of hydrocarbon part of the
molecule increases which cannot form hydrogen bonds with water.
51. Boiling point of aldehydes increases in the homologous series as the number of C-atoms increases.
Therefore, the increasing order of boiling point is: Ethanal < Propanal < Butanal < Pentanal
55. Carboxylic acids have higher boiling points than those of alkanes, ethers, alcohols aldehydes and ketones of
comparable mass.
56. Carboxylic acids have higher boiling points than those of alcohols, aldehydes and ketones of comparable
mass.
58. The carbonyl carbon has positive polarity. Therefore, it is electron deficient and electrophilic (electron
loving) in nature.
59. The general order of the reactivity of aldehydes and ketones towards nucleophile can be given as,
Formaldehyde > Other aldehydes > Ketones (This is due to inductive and steric effects).
60. Ketones are less reactive than aldehydes. Both acetone and benzophenone are less reactive than acetaldehyde
and benzaldehyde. But, benzophenone is least reactive due to presence of two bulky aryl groups (i.e., steric
hindrance).
63. Ketones (i.e., acetone) do not get oxidized by mild oxidizing agents like Schiff’s reagent, as they have no
hydrogen atom directly attached to the carbonyl carbon atom.
64. Only aldehydes get oxidized by Tollens’ reagent while ketones do not get oxidized by Tollens’ reagent.
118
Carboxylic Acids
65. Reaction of ethanal with ammonical silver nitrate (i.e.,Tollens’ reagent):
CH3CHO + 2[Ag(NH3)2]+ + 3OH– → CH3COO− + 2Ag ↓ + 4NH3 + 2H2O
Ethanal Tollens’ reagent Ethanoate Silver
ion metal
H O−
66. CH3 − C = O + 2Cu2+ + 5OH− 

→ CH3 − C = O + Cu2O↓ + 3H2O
Acetaldehyde Cuprous
oxide
67. Change in oxidation number of copper is from +2 to +1.

CH3CH2CHO + 2Cu2+ + 5OH− → CH3CH2COO– + Cu2O ↓ + 3H2O
Propanoate Cuprous oxide
Propanal ion
Fehling solution (Red ppt)
68. Acetone reacts with sodium nitroprusside [Fe(CN)5NO]2–, forming red coloured solution.
CH3 – CO – CH3 + OH– → CH3 – CO – CH −2 + H2O
Acetone
[Fe(CN)5NO]2– + CH3 – CO – CH −2 → [Fe (CN)5NO(CH3 – CO – CH2)]3–
Nitroprusside ion Red colouration
R′/H R′/H
69. R – C = O + HCN → R – C – OH
Aldehyde
or CN
ketone Cyanohydrin
CH3
H3C
70. C = O + NaHSO3 → H3C – C – OH
H3C
SO3Na
Acetone Acetone sodium
bisulfite adduct
O CH3
dry HCl
72. → CH3  C  O
CH3 − C − CH3 + HO − CH2 ←
+ H
CH2
Acetone CH2 O
CH2
HO − CH2 CH2
Propylene glycol Cyclic ketal
H H H
δ−
H − Cδ+ = O + CH3 – MgCl dry
ether
→ H − C −OMgCl 
 H − C − OH + Mg(OH)Cl
+
H
73. HOH
→
Formaldehyde Methyl
(X) magnesium chloride CH3 CH3
Adduct Ethyl alcohol
74. CH3CHO + H2N−NH−C6H5 → CH3CH = N − NH−C6H5

Acetaldehyde Phenylhydrazine Acetaldehyde phenylhydrazone
119


75. X is semicarbazide (NH2 – NH – CONH2).
O + H2N – NH – CONH2 

− H2 O
→ N − NH – CONH2
Cyclohexanone Semicarbazide Semicarbazone
76. Haloform reaction is given by acetaldehyde, all methyl ketones (CH3–CO–R) and all alcohols containing
CH3(CHOH)– group.
77. Among ethanal and propanal, only ethanal will react with I2 in presence of base, because haloform reactions
give positive test to only methyl ketone containing compounds i.e., H3C – C – group
O
O O
–+
H – C – CH3 + 3NaOI 
NaOH / I2
∆
→ H – C – ONa + CHI3 + 2NaOH
Ethanal Sodium formate Iodoform
78. Aldol condensation is shown by aldehydes and ketones having α-H atoms. The nucleophile formed by the
removal of a proton from the α-C attacks the carbonyl carbon of the second molecule, to form a β-hydroxy
aldehyde or ketone.
2CH3 – C – H 
dil NaOH
→ H3C – CH – CH2 – C – H
O OH O
Acetaldehyde Aldol product
(2 molecules)
H
α β α β α
79. H – C – C – H + H – CH2 – C – H dil.NaOH
 → H3C – CH – CH – CHO ∆
− H2 O
→ H3C – CH = CH – CHO
H O O OH H
Ethanal Ethanal 3-Hydroxybutanal But-2-enal
(an Aldol)
O O
α
10% NaOH
80. CH + CH2 − C − CH3  → CH − CH2 − C − CH3
O H OH
α
Benzaldehyde Acetone 4-Hydroxy-4-phenylbutan-2-one
O
− (H 2 O)
∆
→ CH = CH − C − CH3
4-Phenylbut-3-en-2-one
81. Cannizzaro reaction takes place for only those aldehydes which do not contain α-hydrogen atoms.
82. Cannizzaro reaction is given by aldehydes which do not have α-hydrogen atom.
83. p-Methoxybenzaldehyde undergoes Cannizzaro reaction as it lacks α-H atom.
CHO COOK CH2OH
2 + KOH 
Warm
→ +
(50%)
OCH3 OCH3 OCH3
Sodium
p-Methoxybenzaldehyde p-methoxybenzoate p-Methoxybenzyl alcohol
120
Carboxylic Acids
H O
C C CH2 – OH
84. 2 O O– K+
KOH in MeOH

→ ∆
+
Benzaldehyde Potassium benzoate Phenylmethanol /benzyl alcohol
H
O O
C CH2 – OH
H–C–H + O + H – C – OH
85. i. conc.NaOH
 →
ii.H O+
3
Formaldehyde Benzaldehyde Benzyl alcohol Formic acid
86. Aldehydes and ketones both get oxidized by acidified dichromate, the only difference is aldehydes oxidise to
carboxylic acids containing same number of carbon atoms while ketones give a mixture of carboxylic acids
with less number of carbon atoms than the starting ketone, as the oxidation of ketones is accompanied by
breaking C – C bond.
88. The conversion of aldehydes/ketones to the corresponding hydrocarbon is achieved by Clemmensen

reduction.
O
CH3 − C − H 
Zn -Hg + conc. HCl
4[H]
→ CH3 − CH3 + H2O
Ethanal Ethane
89. H3C H3C H3C

C = O →
H 2 N − NH 2
− H2 O
C = N – NH2 →
KOH / ethylene glycol
∆
CH2 + N2
H5C2 H5C2 H5C2
n-Butane
Ethyl methyl Hydrazone
ketone
90. Benzaldehyde undergoes electrophilic substitution to give m-nitrobenzaldehyde.
CHO CHO
conc. H 2SO4
+ HO − NO2  → + H2O
(Conc.HNO3)
Benzaldehyde
NO2
m-Nitrbobenzaldehyde
91. The negatively charged acetate ion (i.e., conjugate base of acetic acid) gets destabilized by +I effect of –CH3
group. In formate ion, there is no such destabilization effect. Higher the stability of the conjugate base,
stronger is the acid. Thus, formic acid is stronger than acetic acid.
92. More the number of electron withdrawing substituents, higher is the acid strength.
93. Electron withdrawing groups like –COOH, –NO2 increase the acidity of substituted benzoic acids while
electron donating groups like –CH3, –OCH3 decrease the acidity of substituted benzoic acids.
95. (B) Both carboxylic acid and phenol can be distinguished by sodium bicarbonate test. Sodium bicarbonate
test is answered by only carboxylic acids. Phenols does not evolve CO2(g) with sodium bicarbonate.
(C) Ester test of carboxylic acids gives fruity smell of ester formed.
(D) Water insoluble carboxylic acids react with NaHCO3 solution and give precipitate on acidification
with conc. HCl. This indicates the presence of –COOH group.
121


O O
+
H
96. R – C – OH + H – O – R′ 
 R – C – O – R′ + H2O
Acid Alcohol Ester
∆
97. CH3COOH + PCl5  → CH3COCl + POCl3 + HCl↑
Acetic acid Acetyl chloride
– +
98. R – C – OH + NH3 
 R – C – O NH 4 

 ∆
→ R – C – NH2 + H2O
O O O
Carboxylic Ammonium salt Amide
acid of acid
O O
P2 O5 , ∆
99. 2CH3COOH → CH3 – C – O – C – CH3 + H2O
Acetic acid Acetic anhydride
100. CH3CH2 – COONa + NaOH 

CaO
∆
→ CH3 – CH3 + Na2CO3
Ethane
101. RCOOH LiAlH 4

→ RCH2OH
Carboxylic acid Primary alcohol
β α
105. H3C – CH2 – CHO
Propionaldehyde contains two α-H atoms.
O O
106. R – C – OH 
R' − OH
H+
→ R – C – OR′
Carboxylic acid Ester
Critical Thinking
O O
2. (A) (B)
CH3 C CH3 C
Acetone
Benzophenone
(Simple ketone)
(Simple ketone)
O O
(C) C2H5 C C 2H 5 (D) C3H7 − C − C2H5

Diethyl ketone Ethyl n-propyl ketone
(Simple ketone) (Mixed ketone)
3. Citric acid is a tricarboxylic acid.
HOOC − COOH CH2 − COOH COOH CH2 − COOH

Oxalic acid
(Dicarboxylic acid) HO − C − COOH COOH COOH
Malonic acid
Phthalic acid
CH2 − COOH (Dicarboxylic acid)
(Dicarboxylic acid)
Citric acid
(Tricarboxylic acid)
122
Carboxylic Acids
4. 2 3 4 5
H5C2 CH CH CH2 CH3
1
CHO CH3
2-Ethyl-3-methylpentanal
5. Crotonaldehyde is an α,β−unsaturated aldehyde represented as follows:

CH3 − CH = CH − CHO
But-2-enal
(Crotonaldehyde)
7. (CH3)2CH–COOH
Common name: α-Methylpropionic acid IUPAC name: 2-Methylpropanoic acid
8. Carboxylic acid group is always given first preference.
Br
4 3 2 1
H3C CH CH COOH
CH3
3-Bromo-2-methylbutanoic acid
10. Cl – CH2 – CH2 – COOH

3 2 1
3-Chloropropanoic acid
CHO
11.
COOH
(2-Formylbenzoic acid)
13. Ethyl isopropyl ketone is,

O CH3
CH3 CH2 C CH CH3

5 4 3 2 1
2-Methylpentan-3-one
1 2 3 4 5 6
15. CH3 CH CO CH CH2CH3
CH3 CH3
2,4-Dimethylhexan-3-one
CH3
5 4 3 2 1
16. H3C – C – CH2 – C – CH3
OH O
4-Hydroxy-4-methylpentan-2-one
5 7
CH3 4 6
COCH3
20. ozonolysis
 → CHO
3
1
2
6-Oxoheptanal
123


22. Hydration of alkynes takes place in accordance with the Markovnikov’s rule.
CH3 − CH2 − C ≡ C − H + H − OH 
40% H 2SO4
→ Tautomerism
u
CH3 − CH2 − C = CH3  CH3 − CH2 − C − CH3
i. 1% HgSO4
But-1-yne
OH O
But-l-en-2-ol Butanone
ii. CH3 − C ≡ C − CH3 + H − OH 

40% H 2SO4
1% HgSO4
→ CH3 − CH = C − CH3 Tautomerism
u
 CH3 − CH2 − C − CH3
But-1-yne
OH O
But-2-en-2-ol Butanone
iii. 3-Methylbut-1-yne into 3-methylbutan-2-one:

CH3 CH3 CH3
40% H 2SO4
CH3 − CH − C ≡ C − H + H − OH 
1% HgSO4
→ CH3 − CH − C = CH2 Tautomerism
u
 CH3 − CH − C − CH3
3-Methylbut-1-yne
OH O
3-Methylbutan-2-one
iv. Hex-3-yne to hexan-3-one:
40% H 2SO4
CH3 − CH2 − C ≡ C − CH2 − CH3 + H−OH 
1% HgSO4
→ CH3 − CH2 − CH = C − CH2 − CH3
Hex-3-yne
OH
Hex-3-en-3-ol
Tautomerism
u
 CH3 − CH2 − CH2 − C − CH2 − CH3
O
Hexan-3-one
23. Acyl chloride can be converted to ketones by using dialkyl cadmium.

O
2CH3CH2COCl + (CH3)2Cd 

dry
ether
→ 2CH3CH2 – C – CH3 + CdCl2
N – Mg – I O
+
OH
25. CH3 – C ≡ N + CH3MgI Dry ether
 → CH3 – C – CH3 
H3 O
→ CH3 – C – CH3 + Mg
Acetonitrile Methyl magnesium Imine complex Acetone I
iodide
26.
(I) 2C6H5 – COCl + (CH3)2Cd → 2C6H5 – CO – CH3 + CdCl2
Benzoyl chloride Dimethyl Acetophenone
cadmium
+
(II) H5C6 – C ≡ N + 2[H] 
( reduction ) → C6H5 – HC = NH.HCl 
SnCl2 , HCl H3 O
→ C6H5 – CHO + NH4Cl
Benzonitrile Benzanimine hydrochloride Benzaldehyde
dry ether +
(III) C6H5 – C ≡ N + C6H5 – MgBr  → C6H5 – C = NMgBr  → C6H5 – CO – C6H5 + NH3 + Mg(Br)OH
H3 O
Benzonitrile C6H5 Benzophenone
O
(IV) Anhyd..AlCl3
+ C6H5COCl  → C + HCl
Benzoyl chloride
Benzene Benzophenone
124
Carboxylic Acids
O O
28. CH3 − C ≡ N + H2O 

Hydrolysis
→ CH3 − C − NH2 
H2 O
Hydrolysis
→ CH3 − C − OH + NH3
Acetonitrile Acetamide Acetic acid
(D)
29. Toluene is oxidised to benzoic acid with dilute HNO3 or alkaline / acidic KMnO4 or chromic acid.
30. Terephthalic acid is a para-dicarboxylic acid. Thus, p-xylene on oxidation will give terephthalic acid.
CH3 COOH
KMnO4 / dil.H 2SO4
→ ∆
H3C HOOC
p-Xylene
Terephthalic acid
O O
X
31. R − Mg − X 
CO2
dry ether
→ R − C − OMgX H2 O
→
Dil.HCl
R − C − OH + Mg
Grignard Carboxylic acid OH
reagent
O
ether
32. C O + CH3CH(CH3) CH(CH3) MgBr  → CH3 CH CH C OMgBr
Dry Grignard reagent
ice CH3 CH3 O
Unstable
H+ H2O
OH
CH3 CH CH C OH + Mg
CH3 CH3 O Br
2,3-Dimethylbutanoic acid
(i) Dry CO2 /dry ether

33. C6H5MgBr  → C6H5COOH
(ii) H + / H 2 O
34. Addition of Grignard reagent increases the number of carbon atom by one. Methanoic acid (HCOOH) has
only one carbon atom. Hence, it cannot be prepared using Grignard reagent and carbon dioxide.
35. Aldehydes and ketones being highly polar compounds have higher boiling points than non-polar
hydrocarbons of comparable molecular masses. This is due to the weak molecular association in aldehydes
and ketones arising because of dipole-dipole interactions.
36. The increasing order of boiling points: n-Butane < ethyl methyl ether < n-propyl alcohol < acetic acid
37. In liquid phase, acetic acid forms dimer in which two molecules are held by two hydrogen bonds.
O
O H O
2CH3 C OH  Dimerization
→ CH 3 C C CH3
O H O
Acetic acid
Dimer of acetic acid
38. (A) Trioxane use in chemical reactions as source of formaldehyde.
(B) Solid trimer of acetaldehyde is called as paraldehyde.
(D) Aqueous solution of formaldehyde gas is called formalin.
40. Generally in nucleophilic addition reactions, aldehydes are more reactive than ketones due to both steric and
electronic reasons.
125


41. The decreasing order of the reactivity towards nucleophilic addition reactions is,
acetaldehyde > acetone > methyl tert-butyl ketone > di-tert-butyl ketone or
CH3CHO > (CH3)2C=O > (CH3)3C–CO–CH3 > (CH3)3C–CO–C(CH3)3
42. Simple hydrocarbons, ethers, ketones and alcohols do not get oxidized by Tollens' reagent.
44. Sodium nitroprusside test is a laboratory test for ketonic group. Reaction given in option (A) will form a
ketone.
Thus, the product obtained by hydration of 3-methylbut-1-yne will give positive sodium nitroprusside test
CH3 CH3 CH3
40% H 2SO4
CH3 − CH − C ≡ C − H + H − OH  → CH3 − CH − C = CH2 Tautomerism
u
 CH3 − CH − C − CH3
1% HgSO 4
3-Methylbut-1-yne
OH O
3-Methylbutan-2-one
CH3 O CH3 OH CH3 OH
45. CH3 – C – C – H 

HCN
→ CH3 – C – C – CN 
HCl
→ CH3 – C – C – COOH
CH3 CH3 H CH3 H

2,2-Dimethylpropanal 2-Hydroxy-3,3- 2-Hydroxy-3,3-dimethyl
(A) dimethylbutanenitrile butanoic acid
(B)
O OCH3
46. (A) CH3 − C − CH3 + 2CH3OH dry HCl


 
 CH3 − C − CH3 + H2O
Propanone Methanol OCH3
(Ketal)
2,2-Dimethoxypropane
O O CH2CH3
(B) CH3 − C − H + 2 CH3CH2OH 

dry HCl
  CH3 − C − O CH2CH3 + H2O

Acetaldehyde Ethanol
H
(Acetal)
1,1-Diethoxyethane
O H
(C) CH3−C − H + HO − CH2 
dry HCl
  CH3  C  O

Ethanal HO − CH2 O CH2

Ethylene glycol CH2
Cyclic acetal
(D) Cyclohexanone reacts with ethyl alcohol to give ketal and not cyclic ketal.
Cyclic ketals are obtained when ketones react with 1,2- or 1,3- diols like ethylene glycol.
O
OC2H5
+ 2C2H5 − OH 
dry HCl
 
 + H2O
OC2H5
Cyclohexanone Ethyl alcohol
(Ketal)
1,1-Diethoxycyclohexane
47. (A) Fehling B is prepared by dissolving sodium potassium tartarate in sodium hydroxide solution.
Fehling A is prepared by dissolving crystals of copper sulfate in concentrated sulfuric acid.
126
Carboxylic Acids
48. CH3COCH3 
(i) CH3 MgI
+
→ (CH3)3COH
(ii) H3O
Acetone tert-Butyl alcohol

49. Ethanal with CH3MgBr gives propan-2-ol (after hydrolysis) and with C2H5OH, it gives acetal.
OMgBr OH
H+
i. CH3CHO + CH3MgBr → CH3CH → CH 3CH
H2 O
Ethanal CH3 CH3
(Acetaldehyde) Propan-2-ol
OC2H5
ii. CH3CHO + 2C2H5OH 

dry HCl

stepwise
→ H3C – C – H
addition
Ethanal
OC2H5
1,1-Diethoxyethane
OH O
[O] NH 2 OH
50. CH3 – CH – CH3 → CH3 – C – CH3  → (CH3)2C = NOH
Isopropyl alcohol Acetone Acetoxime
(A) (B)
CH3 CH3
51. C6H5NHNH2 + O = C → C6H5NHN = C
CH3 CH3
Phenylhydrazine Acetone Phenylhydrazone
52. Pentan-2-one (CH3 – CO – CH2 – CH2 – CH3) is a methyl ketone, thus gives positive iodoform test.
Pentan-3-one (CH3 – CH2 – CO – CH2 – CH3) is not a methyl ketone, thus does not give positive iodoform
test.
+ −
53. CH3 – CH – CH2 – CH3 + 3NaOI 
NaOH / I2
∆
→ CHI3 + NaO − C − CH2 − CH3 + 2NaOH
Iodoform
OH (Yellow ppt) O
Butan-2-ol Sodium propionate
54. This is an example of haloform reaction.

CH3 – C – CH2 – CH3  NaOH, I2
→ CHI3 + NaO – C – CH2 – CH3
Iodoform
O O
Butanone Sodium propionate
Sodium propionate on acid hydrolysis gives propanoic acid.

55. An aldehyde having α-H atoms in presence of dilute alkali undergoes aldol condensation to give a
β-hydroxyaldehyde.
H CH3 CH3
CH3 − CH2 − C = O + H − CH − CHO 

dil. NaOH
→ CH3 − CH2 − CH − CH − CHO
Propionaldehyde
OH
(2 molecules) 3-Hydroxy-2-methylpentanal
H H H H H
dil.NaOH
56. CH3 – C = O + CH3 – C = O  → CH3 – C – C – C = O
Acetaldehyde Acetaldehyde
OH H
Acetaldol
127


57.
CH3CHO 
dil.KOH
→ CH3 – CH – CH2 – C – H ∆
− H2 O
→ CH3 – CH = CH – C – H
Acetaldehyde
OH O O
α,β-Unsaturated aldehyde
58. Acetaldehyde does not show Cannizzaro reaction as it has α-hydrogen atom.
59. Hexan-2-one on oxidation gives a mixture butanoic acid and acetic acid.
CH3CH2CH2CH2COCH3 + 3[O]  CrO3
∆
→ CH3CH2CH2COOH + CH3COOH
Hexan-2-one Butanoic acid Acetic acid
O
CH2CH2CH3
61. CH3CH 2 COCl
→
AlCl3 CH2CH3
NH 2 .NH 2
→
base,Δ + N2 ↑ + H2O
62. The aldehydic (–CHO) group is electron-withdrawing by inductive as well as resonance effects. It
deactivates the benzene ring at ortho- and para- positions. This results in the formation of meta-product.
CHO CHO
conc. H 2SO4
+ HO − NO2  → + H2O
(Conc.HNO3)
Benzaldehyde
NO2
m-Nitrobenzaldehyde
63. –
O O
–
R – C – O ←→ R – C = O
Resonance structures of carboxylate ion
64. Among given options, BrCH2CH2COOH is least acidic or has less Ka i.e., dissociation constant because in
aliphatic carboxylic acids the inductive effect decreases rapidly as the substituents move farther from the
carboxyl group.
COOH COOH COOH COOH

66. NO2
NO2
NO2
Electron withdrawing group, increases the acidity of benzoic acid, ortho-isomer will have higher acidity than
corresponding meta and para-isomer due to ortho effect.
Conc H 2SO4
67. C2H5OH + CH3COOH  → CH3COOC2H5
Ethanol Acetic acid Ethyl acetate
It is called esterification reaction.
68. RCOOH + C2H5OH 
conc.H 2SO4
→ RCOOC2H5 + H2O
COOH COCl
69.
+ SOCl2 
∆
→ + SO2 ↑ + HCl ↑
O2N NO2 O 2N NO2
3,5-Dinitrobenzoic acid 3,5-Dinitrobenzoyl chloride
128
Carboxylic Acids
∆
70. HCOOH + PCl5  → HCOCl + POCl3 + HCl
Formic Formyl
acid chloride
–
→ CH3COO NH 4 
+
71. CH3Cl 
KCN
→ CH3CN 
H2 O
→ CH3COOH 
NH3 ∆
→ CH3CONH2 + H2O
− KCl
+
72. CH3 − C ≡ N 
H
H2 O
→ CH3COOH 
P2 O5 , ∆
→ (CH3CO)2O
Acetonitrile Acetic acid Acetic anhydride
(A) (B)
O O O O
73. CH3 – C – ONa + CH3 – C – Cl 

∆
→ CH3 – C – O – C – CH3 + NaCl
Sodium acetate Acetyl chloride Acetic anhydride
O
H3C β α
74. C CH C CH3
H3C
Mesityl oxide
(α,β-Unsaturated ketone)
75. Acetylene first gives acetaldehyde which on aldol condensation gives product i.e., option (D).
76. HC ≡ CH 
1% HgSO4
→ CH3CHO 
CH3 MgX [O]
→ CH3CHOHCH3 → CH3COCH3
20% H 2SO4 H O, H + 2
(A) (B) Acetone
1. CH3 – CH2 – CO – CH3

Butanone
(Mixed ketone)
2. CH2 − COOH CH2 − COOH HOOC − (CH2)2 − COOH HOOC − CH − CH2 − COOH
HO − C − COOH Succinic acid OH

COOH (Dicarboxylic acid)
Malonic acid Malic acid
CH2 − COOH (Dicarboxylic acid) (Dicarboxylic acid)
Citric acid
(Tricarboxylic acid)
3.
Compound Structure Compound Structure
COOH
Ethanoic acid CH3 − COOH Benzoic acid
OH
OH
O2N NO2
Picric acid Salicylic acid COOH
NO2
Among the given options, only picric acid does not have – COOH group.
129


4. CH3
5
1
4 CH2 CHO
CH3 – CH – CH – CH3
3 2
2,3-Dimethylpentanal
6. Isobutyric acid has structure as, CH3
CH3 – CH – COOH
2-Methylpropanoic acid
7. The IUPAC name of lactic acid is 2-hydroxypropanoic acid.

3 2 1
CH3 – CH – COOH
OH
2-Hydroxypropanoic acid
(Lactic acid)
O OH O OH CH3
8. ≡ H3C – C – CH2 – CH – CH – CH3

1 2 3 4 5 6
4-Hydroxy-5-methylhexan-2-one
10. O
O
3
H−C 4
1 2
5 6
3-Keto-2-methylhex-4-en-1-al
OH O
11. CH3 – CH – CH2 – CH3 + [O] 

K 2 Cr2 O7
dil.H 2SO4
→ CH3 – C – CH2 – CH3 + H2O
Butan-2-ol Ethyl methyl ketone
(Butanone)
aq.H2SO4
12. CH3 − CH2 − C ≡ CH →
HgSO4 CH3 – CH2 – CO – CH3
But-1-yne Butanone
O O
13. C2H5 – C – Cl 

H 2 / Pd-BaSO4
Quinoline
→ C2H5 – C – H + HCl
Propanoyl Propanal
chloride (X)
14. 2CH3 − C − Cl + (C6H5CH2)2Cd 

Dry ether
→ 2CH3 − C − CH2 − C6H5 + CdCl2
Dibenzyl
O O
cadmium
Acetyl Benzyl methyl
chloride ketone
16. DIBAL–H is an electrophilic reducing agent which reduces cyanide, esters, lactone, amide, carboxylic acids,
etc. into corresponding aldehyde (partial reduction).
130
Carboxylic Acids
18.
CH2CH3 COO–K+ COOH
KMnO4 − KOH +
Δ
→ H3 O
 →
Ethylbenzene Benzoic acid (X)
CH3 COO–K+ COOH
H3 O +
KMnO4 − KOH
Δ
→ →
Methylbenzene Benzoic acid (Y)
CH2CH2CH3 COO–K+ COOH

H3 O +
KMnO4 − KOH
Δ
→ →
n-Propylbenzene Benzoic acid (Z)
20. Benzaldehyde (C6H5CHO) is more reactive towards nucleophilic addition than acetophenone (C6H5COCH3).
Presence of electron withdrawing groups increase the positive polarity of carbonyl carbon and its
electrophilicity. Thus, presence of electron withdrawing group like −NO2 favours nucleophilic attack.
21. Fehling solution is a mixture of two solutions Fehling A and Fehling B.
Fehling solution A = Aqueous CuSO4 crystals dissolved in concentrated sulfuric acid (blue in colour).
Fehling solution B = Rochelle salt (sodium potassium tartarate) dissolved in NaOH.
22. (CH3)2CO does not have hydrogen atom directly attached to carbonyl carbon atom. Hence, it does not react
with Fehling’s solution.
23. Generally in nucleophilic addition reactions, aldehydes are more reactive than ketones due to both steric and
electronic reasons. Reaction of aldehydes and ketones with hydrogen cyanide forms corresponding
cyanohydrins. It is a reversible reaction and the order of reactivity is formaldehyde > other aldehydes >
ketones.
24. Aldehydes are more reactive than ketones towards nucleophilic addition reaction. The order is,
HCHO > CH3CHO > (CH3)2CO > CH3CH2COCH2CH3
25. Two molecules of alcohol are added to carbonyl group of an aldehyde to form acetal by elimination of one
water molecule.
O OR′
dry HCl
R – C – H + 2R′OH 
 R – CH

 + H2O
Aldehyde Alcohol OR′

Acetal
26. Aldehydes and ketones when treated with C6H5 – NH – NH2 give phenylhydrazone as follows:
C = O + H2N – NH – C6H5 → C = N – NH – C6H5

Aldehyde
Phenylhydrazone
or ketone
27. Ketones and secondary alcohols with free methyl group and acetaldehyde give iodoform reaction. Hence,
C2H5 − CH −C2H5 does not give iodoform test (haloform reaction).
OH
28. Alcohols with formula –CH(OH)CH3 give positive iodoform test. Acetaldehyde and ketones with at least
one –CH3 group attached to carbonyl carbon will give positive iodoform test. The structure of isopropyl
alcohol is,
OH
H3C – CH – CH3
Hence, it gives positive iodoform test.
131


29. CH3 – CH – CH3 CH3 – CH2 – C – CH3 CH3 – CH2 – CH2 – OH CH3 – C – C6H5
OH O Propan-1-ol O
Propan-2-ol Butan-2-one Acetophenone
Methyl ketones and alcohols having structure R – CH(OH)CH3 where R may be hydrogen, methyl group or
aryl group forms iodoform. Thus, among the given options, propan-1-ol cannot be used to prepare
iodoform.
30. Carbonyl compounds containing α-hydrogen atom undergo self aldol condensation. Hence, among the given
options, HCHO does not undergo self aldol condensation.
31. The carbonyl compound which undergoes aldol condensation must contain an α-hydrogen atom.
HCHO, (CH3)3CCHO and CCl3CHO do not contain α-hydrogen atom.
CH3 CH3
+
32. 2 H3CCOCH3 
Ba(OH)2
→ H3C – C – CH2 – C = O 
H /Δ
− H2 O
→ H3C – C = CHCOCH3
OH CH3
Diacetone alcohol Mesityl oxide
(Z)
+
33. HCHO + H2N – OH → H
CH2 = N – OH
HCHO + HCHO 
Aldol condensation
→ No reaction
34. O+O →
Mechanism: O
H H O O
O H
⊕
∆
O 
OH
→ O 
− H2 O
→
HO
+
35. CH3 − CH2 − OH 
Cu
573K
→ CH3 − CHO 
[Ag(NH 3 )2 ]
OH − / ∆
→ Silver mirror observed
Ethanol Ethanal
(X) (A)
H+ OH− /∆
CH3 − CH = N − NH − C − NH2 CH3 − CH = CH − CHO
NH2 − NH − C − NH2 (Aldol condensation)
Acetaldehyde But-2-enal
semicarbazone
O O (Crotonaldehyde)
(Z) (Y)
36. COCl CHO
+ H2 
Pd / BaSO4
→ + HCl
Benzoyl chloride Benzaldehyde

(P) (Q)
H H O
C=O C=O CH2OH C − OH

+ ()i conc. NaOH
 +
( ii ) dil.HCl →
Benzaldehyde Benzaldehyde Benzyl alcohol Benzoic acid

(R) (S)
Benzyl alcohol and benzoic acid undergo esterification reaction to form benzyl benzoate.
132
Carboxylic Acids
37. H – CHO + C6H5 – CHO 
50 % NaOH
∆
→ C6H5 – CH2OH + HCOONa
Formaldehyde Benzaldehyde Benzyl alcohol Sodium formate
38. H H O
− +
C=O C=O CH2OH C – ONa
+ + NaOH → +
(conc.)
NO2 NO2 NO2 NO2
Sodium
m-Nitrobenzaldehyde m-Nitrobenzaldehyde m-Nitrobenzyl alcohol m-nitrobenzoate
39. Product of Etard reaction is benzaldehyde. Thus, in the given reaction Y is benzaldehyde. Z undergoes
disproportionation reaction with concentrated alkali (i.e., Cannizzaro reaction). Thus, Z can be either
benzaldehyde or formaldehyde. Among the given options, only option (B) yields formaldehyde and
benzaldehyde as products of its ozonolysis and hence is a correct option.
CH = CH2 CHO
Ozonolysis
→
(Reductive)
+ HCHO
Formaldehyde
1-Phenylethene Benzaldehyde (Z)
(X) (Y)
41. Electron withdrawing substituents (like halogens) increase the acidity of carboxylic acids by dispersing
negative charge by inductive effect and stabilizing the carboxylate anion. In aliphatic carboxylic acids, the
inductive effect decreases rapidly as the substituent moves farther from the carboxyl group. Thus, among
given options, 2-chlorobutanoic acid is most acidic in nature.
42. –Cl group is electron withdrawing group and hence, increases the acidity of carboxylic acid by stabilizing
the carboxylate anion.
43. Presence of electron withdrawing groups like halogens increase the acidity of carboxylic acids.
Cl3CCOOH > Cl2CHCOOH > Cl − CH2 − COOH > CH3COOH
Trichloro Dichloro Monochloro Acetic acid
acetic acid acetic acid acetic acid (Least acidic)
(Most acidic)
44. The electron releasing substituents destabilize the carboxylate ion through inductive effect as the negative
charge is intensified. This decreases the strength of carboxylic acid. Thus, the acid strength of given
carboxylic acid increases in the order CH3CH2CH2COOH < CH3CH2COOH < CH3COOH < HCOOH.
45.
Acids HCOOH C6H5COOH CH3COOH
pKa 3.77 4.2 4.76
∴ Correct order of acidic strength for given acids is:

HCOOH > C6H5COOH > CH3COOH
46. Electron withdrawing group increases the acidity of the carboxylic acids. Also, the inductive effect decreases
as the substituent moves away from the carboxyl group.
O O
−
47. CH3 – CH2 – C – OH + NaHCO3 → CH3 – CH2 – C – O Na + + H2O + CO2 ↑
Propionic acid Sodium Sodium propanoate
bicarbonate
The C-atom of the evolved CO2 gas comes from sodium bicarbonate (NaHCO3).
133


O
48. CH3COOH + CH3OH 

Conc.H 2SO4
413 K
→ CH3 − C − OCH3 + H2O
Ethanoic acid Methanol Methyl acetate
49. In methanoic acid, there is an aldehydic group present.
O
Aldehydic
group H − C − OH
Methanoic acid
Hence, methanoic acid (HCOOH) reduces ammoniacal silver nitrate solution, i.e., Tollens’ reagent but
ethanoic acid (CH3COOH) does not.
50. O
COOH C – NH2
+ NH3 →
COOH C – NH2
Phthalic acid O
Δ
NH
O
Phthalimide
H3C – CH2 – C
51. 2 H3CCH2CO2H 
→ P2 O5
∆
H2 O
O  → 2 H3CCH2CO2H 
SOCl2
→ 2 H3CCH2COCl
Propanoic H3C – CH2 – C Propanoic acid Propanoyl
acid (Y) chloride
O (Z)
Propanoic
anhydride
(X)
52. O O O O
C Cl Na O C C O C
+ ∆
 →
Benzoyl Sodium Benzoic anhydride
chloride benzoate
+
KCN H O LiAIH
53. CH3 − Br 
→ CH3 − CN 
3
→ CH3 − COOH →
4
CH3 − CH2 − OH
(A) (B) (C)
Ethyl alcohol
55. Pyridinium chlorochromate (PCC) oxidizes primary alcohol to corresponding aldehyde.
134
Carboxylic Acids
56. O
O
C − CH2 − CH3
Anhydrous AlCl3
+ Cl − C − CH2 − CH3 →
Propionyl chloride
Benzene
NH2 − NH2 / KOH Ethylene glycol
CH2 − CH2 − CH3
n-Propylbenzene
57.
O O O HO CH3 HO CH3
+ CH 3MgBr /dry ether
 Ag ( NH3 )  OH − +
→
 2 H / CH3OH
 →
CH3 MgBr / dry ether
→ +
 + →
Tollens reagent H3 O H 3O
CHO C O = C − CH3 HO – C − CH3

CO2H
O OCH3 CH3
58.
O− O O OH OH OCOCH3
H O− COO− COOH
− O= C= O
COOH

o → C H
→
+
(CH3CO)2 O
125 C,  →
5atm O
Phenoxide Salicylate Salicylic
ion Aspirin
ion acid
(B) (C)
59. Keto-enol tautomerism is represented as:

H
α
–C–C=O – C = C – OH
Keto Enol
60. CH3 COOH COCl CHO
KMnO4
 → SOCl2
 →
H 2 / Pd

BaSO4
→
Toluene Benzoic acid Benzoyl chloride Benzaldehyde

(A) (B) (C)
61.
Option Will not be compound ‘X’ because
(A) Pentanal it will give positive Tollen’s test
(B) Pentan-2-one will give positive iodoform test as its a methyl ketone
(D) n-Amyl alcohol (i) will not yield phenyl hydrazone due to absence of carbonyl group
(ii) will not yield n-pentane as a product on its reduction
Thus, only option (C) satisfies all the given conditions and hence is the correct answer.
135


O O
62. I. CH3 − C − O − C − CH3 + H2O → 2CH3COOH
Acetic anhydride Acetic acid
CH3COOH + NaHCO3 → CH3COONa + CO2 + H2O

Acetic Sodium Sodium
acid bicarbonate acetate
II.
65.
Compound Neutral FeCl3 test Fehling solution test Iodoform test
(A) O Positive Negative Positive
CH3
OH
(B) OH Negative Negative Positive [As it contains
CH3CH(OH) – group]
CH3
C2H5
(C) O Negative Negative Negative

CH3
H
O
(D) O Negative Negative Negative
C2H5
CH3
O
Note : Aldehydes and ketones react with Grignard reagent to form corresponding alcohols.
OH 
i. CrO3 − H 2SO4
Cl ( CH ) Cd
66. ii. SOCl2
→ 3 2

(Y) →
O O
(X)
OH HCl(gas)
HO
(Z)
O O
67. On heating, ammonium salt of benzoic acid gives benzamide.

O O
C – + C
ONH4 Δ
NH2

− H2 O
→
Ammonium salt Benzamide

of benzoic acid
136


R R
23. R – CH – OH 
Cu
573 K
→ R – C = O + H2 ↑
2° Alcohol Ketone
OH OH OH
NO2
Room temperature
24. 2 + 2HNO3 
→ + + 2H2O
(dil)
Phenol o-Nitrophenol
NO2
p-Nitrophenol
26. On treating phenol with chloroform in the presence of sodium hydroxide, a −CHO group is introduced at
ortho position of benzene ring. This reaction is known as Reimer-Tiemann reaction.
− + − +
OH ONa ONa OH
CHCl2 CHO CHO
NaOH H+
CHCl3 + aq. NaOH

→ → →
Phenol Salicylaldehyde
Intermediate
29. At high temperature, the ether is completely cleaved by concentrated HI to give the corresponding alkyl
iodide.
C2H5 – O – C2H5 + 2HI ∆
 → 2CH3CH2I + H2O
Diethyl ether (conc.) Ethyl iodide
+ + -
H
30. C6H5− O − CH3 → C6H5− O − CH3 
I
SN 2
→ C6H5 − OH + I − CH3
Methyl phenyl Phenol Methyl
ether H iodide
31. In case of 3-methoxystyrene, protonation gives corresponding oxonium ion.

The bond between O−CH3 is weaker than the bond between O−C6H4 – CH = CH2 because the carbon atom
of phenyl group is sp2 hybridised and there is a partial double bond character. Hence, the attack by Br– ion
results into the cleavage of O−CH3 bond to yield CH3Br. 3-Vinyl phenol do not react further with HBr
because the sp2 hybridised carbon (of aromatic ring) of 3-vinyl phenol cannot undergo nucleophilic
substitution reaction. Instead addition reaction occurs at C = C double of the side chain.
⊕
OCH3 O – CH3 OH OH
→ Conc. HBr →
CH3 BR
HBR
( Excess )
Δ
H 
→
CH = CH2 CH = CH2 CH = CH2 (Br)CH – CH3

3-Methoxystyrene 3-Vinyl phenol 3-(1-Bromoethyl)phenol
32. Br
+ HBr → OH
O
1-methylethylene 2-Bromopropanol
oxide
Br Br
Br
OH + HBr (excess) →
1,2-Dibromopropane
111


3.
CH3 H CH3 O O CH3 O
3 2 1
CH3 − CH − C = C − H 
→ CH3 − CH − C − O − C − H → CH3 − CH − C + H − CHO
H3C − CH2 H3C − CH2 H CH2 − CH3 Formaldehyde

2-Ethyl-3-methylbut-1-ene 2-Methylpentan-3-one
CHO CH2 − OH
4. + H − CHO → NaOH
+ HCOONa
Benzaldehyde Formaldehyde Benzyl alcohol Sodium formate
5. Addition of HCN to carbonyl compounds is a nucleophilic addition. The lower reactivity of ketones over
aldehydes is due to +I effect of the alkyl group and steric hindrance. The aromatic aldehydes and ketones are
less reactive than their aliphatic analogous.
6. C6H5OH →
Zn dust
C6H6 
CH3Cl
Anhydrous AlCl3
→ C6H5CH3 
Alk.KMnO4
→ C6H5COOH
Phenol Benzene Toluene Benzoic acid
(X) (Y) (Z)
8. H−COOH is the strongest acid among the given set of acids, hence it has lower pKa value.
COO − C2H5 COONa

9.
+ NaOH 
∆
→ + C2H5 − OH
Ethyl benzoate Sodium benzoate Ethanol
10. For cross Cannizzaro reaction, both the aldehydes must not have α-hydrogen. Hence, C6H5CHO and HCHO.
i. dry ether
11. CO2 + C3H7MgBr → + C3H7COOH + Mg(Br)OH
ii. H /H 2 O
12. Formaldehyde does not contain α−H atoms. Hence, in presence of concentrated KOH, it undergoes self
oxidation-reduction to form one molecule of potassium salt of carboxylic acid and one molecule of alcohol.
This reaction is called as Cannizzaro reaction.
∆
HCHO + HCHO + KOH  → HCOOK + CH3OH
Formaldehyde Potassium Methyl
formate alcohol
14. Acetophenone gives iodoform with alkaline I2 , whereas benzophenone does not give the reaction.
C6H5 − C − CH3 →
I2 + NaOH
∆
CHI3 + C6H5COONa
Iodoform
O (yellow ppt)
Acetophenone
I2 + NaOH
C6H5 − C − C6H5  ∆
→ no reaction
O
Benzophenone
∆
15. CH3COOH + NH3  → CH3CONH2 + H2O
Acetic acid Acetamide
R OH R OR′
16. R − C = O + R′OH 
Dry HCl
 → C
Dry HCl


R ′OH

 C
H OR′ H OR′
H Acetal
Hemiacetal
Aldehyde
138
Carboxylic Acids
17. CH3 − CH − CH3
K 2 Cr2 O7

H 2SO4
→ CH3 − C− CH3
NaOH

I2
→ CHI3 + CH3COONa
Tri-iodomethane
OH O (Yellow ppt)
Isopropyl alcohol Acetone
(X) (Y)
18. CH3COOH 

P2 O5 / Δ
→ (CH3CO)2O 
C2 H5 OH
→ CH3COOC2H5 + CH3COOH
Acetic acid Acetic Ethyl acetate Acetic acid
anhydride
20. Presence of electron withdrawing groups like halogens increase the acidity of carboxylic acids.
Cl3CCOOH > Cl2CHCOOH > Cl − CH2 − COOH > CH3COOH
Trichloro Dichloro Monochloro Acetic acid
acetic acid acetic acid acetic acid (Least acidic)
(Most acidic)
139
13 Amines
Hints
Classical Thinking
+ −
1. (A) Amines: R–NH2 (B) Diazonium salts: Ar − N 2 X
(C) Isocyanides: R–NC (D) Nitrites: RONO
2. Amines are formed by replacing one, two or three H-atoms from ammonia molecule by alkyl groups
(aliphatic amines) or aryl groups (aromatic amines).
H H
CH3 N N
H H
Methylamine Aniline
(Aliphatic amine) (Aromatic amine)
4. A secondary amine has two alkyl/aryl groups directly attached to nitrogen atom and is known as imino group
(R–NH–R).
5. CH3 – CH(NH2) – CH3
Isopropylamine
7. In 3° amines, all the hydrogen atoms of NH3 are replaced by three same or different alkyl or aryl groups.
∴ R3N is a 3° amine.
8. (C2H5)2CH–NH2 - 1° Aliphatic amine
15. IUPAC name: N,N-dimethylbenzenamine
Common name: N,N-dimethylaniline
N – CH3
CH3
17. RX + alc. NH3 
100 ° C
sealed tube
→ R − NH2 + HX
Alkyl (Excess) 1° amine
halide (Y)
18. The order of reactivity of alkyl halides with ammonia is R–I > R–Br > R–Cl
19. Aliphatic and aromatic nitro compounds can be reduced to primary amines by using metal-acid mixture
(Sn/HCl or Fe/HCl or Zn/HCl) or catalytic hydrogenation (H2/Ni or Pt or Pd) or LiAlH4 in ether.
20. Ar – NO2 LiAlH 4 / Ether
 → Ar – NH2 + 2H2O
Aromatic nitro compound Aromatic 1° Amine
21. CH3 – CH – CH3 + 6[H] →

Sn / HCl
CH3 – CH – CH3 + 2H2O
NO2 NH2
2-Nitropropane Propan-2-amine
24. Mendius reduction: Alkyl cyanides or cyanoalkanes on reduction by sodium and ethanol give corresponding
primary amine.
R – C ≡ N + 4[H] 
Na / ethanol
→ R – CH2 – NH2
Alkyl cyanide 1° amine
140

Chapter 13: Amines

25. Primary amines having same number of carbon atoms can be obtained by the reduction of amides by LiAlH4
in ether.
O O O
C C C
– +
27. N−H 
Alc.KOH
− H2 O
→ N K
CH3 Br

− KBr
→ N−CH3
C C C
O O O
Phthalimide N-Methyl phthalimide
(A) (B)
O
– +
C O Na
aq.NaOH
+ CH3 – NH2
– + Methylamine
C O Na
(D)
O
Sodium salt of phthalic acid
(C)
28. n-Propylamine (1°aliphatic); Ethylmethylamine (2° aliphatic)

N-Phenylbenzenamine (2° aromatic); Aniline (1° aromatic)
Only aliphatic primary amines are prepared exclusively by Gabriel phthalimide synthesis.
Aromatic primary amines cannot be prepared by this method because aryl halides do not undergo
nucleophilic substitution with phthalimide anion.
30. Reduction of acetamide by LiAlH4 in ether or by Na/C2H5OH forms ethanamine.
O
LiAiH 4 /ether
CH3 – C – NH2 + 4[H] →
or Na /C2 H5 OH CH3 – CH2 – NH2
Acetamide Ethanamine
Reduction of acetamide by Br2/Conc. aq. KOH forms methanamine.
O
CH3 – C – NH2 + Br2 + 4KOH(aq) 

∆
→ CH3 – NH2 + 2KBr + K2CO3 +2H2O
Acetamide Methanamine
31. Hofmann hypobromite degradation:
O
R – C – NH2 + Br2 + 4KOH(aq) 

∆
→ R – NH2 + 2KBr + K2CO3 + 2H2O
Amide 1° Amine
32. The extent of intermolecular hydrogen bonding is more in isopropylamine (1°) than in ethylmethylamine
(2°), because primary amines have two hydrogen atoms bonded to nitrogen for hydrogen bond formation.
Triethylamine (3°) and diethylmethylamine (3°) do not have intermolecular hydrogen bonding due to the
absence of H-atom attached to nitrogen.
33. Tertiary amines cannot form intermolecular hydrogen bonds as there is no H-atom directly attached to the
N-atom.
34. Primary and secondary amines are associated by intermolecular hydrogen bonds. The association is more in
primary amines than that in secondary amines as there are two hydrogen atoms on nitrogen. Tertiary amines
cannot form intermolecular hydrogen bonds due to absence of hydrogen atoms on nitrogen. Hence, the order
of boiling points of isomeric amines is 1° > 2° > 3°.
141


35. The order of boiling point is 1° > 2° > 3° for isomeric amines.
38. Lower aliphatic amines are soluble in water due to formation of H-bonds. However, solubility decreases
with increase in molar mass.
39. N – H bonds in amines are less polar than O – H bond in alcohols. Thus, water solubilities of alcohols,
amines and alkanes of comparable molar mass in water decreases in the order:
alcohols > amines > alkanes.
40. The order of boiling points of alkanes, amines, alcohols and carboxylic acid of comparable molar mass is as
follows: alkanes < amines < alcohols < carboxylic acid.
Compound Molar mass B.P. (K)
C2H5COOH 74 414.4
n-C4H9OH 74 390.3
(CH3)3C–NH2 73 318.15
C2H5CH(CH3)2 72 300.8
41. In amines, the nitrogen atom of − NH2 group carries a lone pair of electrons in its hybrid orbital. They can
share the lone pair of electrons to the electron deficient species and, therefore, amines behave as Lewis base.
42. Stronger the base, smaller will be the pKb value. Aromatic amines are weaker bases than aliphatic amines.
Among aliphatic amines, secondary amines are the strongest bases (i.e., have the lowest pKb value).
Compound C2H5NH2 C6H5NH2 (C2H5)2NH C6H5NHCH3
pKb values 3.29 9.38 3.00 9.30
43. 3° Aliphatic amines are weaker base than 2° aliphatic amines because the stabilization of conjugate acid of
3° amines by solvation is very poor.
44. Aqueous solutions of amines are basic in nature and thus they turn red litmus blue.
47. R − NH2 + R − X → R2NH + HX
Primary Alkyl Secondary
amine halide amine
48. When a primary amine is heated with excess of primary alkyl halide, it gives a mixture of secondary amine,
tertiary amine and tetraalkylammonium halide.
+
R – NH2 
R −X
− HX
→ R2NH 
R −X
− HX
→ R3N 
R −X
− HX
→ R4 N X –
1° Amine 2° Amine 3° Amine Tetraalkyl
ammonium halide
49. Three molecules of methyl bromide react with ethylamine to give quaternary ammonium salt.
+
Et–NH2 
CH3 − Br
− HBr
→ (Et)2NH 
CH3 − Br
− HBr
→ (Et)3N 
CH3 − Br
− HBr
→ (Et)4 N Br–
Ethylamine Diethylamine Triethylamine Tetraethyl ammonium
bromide
50. (CH3)3N + H3C – I → (CH3)4N+I–
Trimethylamine Methyl iodide Tetramethylammonium iodide
51. Exhaustive methylation of benzylamine forms benzyltrimethylammonium iodide.

CH3
CH3 − I
C6H5CH2NH2 + CH3 − I 
→ C6H5CH2NH − CH3 → C6H5CH2 − N
∆
− HI
CH3 − I
− HI
Benzylamine Benzylmethylamine CH3

Benzyldimethylamine
+
CH3
C6H5CH2− N − CH3 I−
CH3
Benzyltrimethyl
ammonium iodide
(X)
142

Chapter 13: Amines

55. Due to availability of only one replaceable H-atom, secondary amines produce only monoacetyl derivatives
on acylation.
O O
56. C2H5 − NH2 + (CH3 − C )2 O →

Pyridine
∆
C2H5 − NH − C − CH3 + CH3 − C − OH
Ethylamine Acetic O
(Ethanamine) anhydride N-Acetylethylamine
(N-Ethylethanamide)
57. Acetylation of ethylamine:

O H O– O
C2H5 – N – H + C – CH3 →

Pyridine
C2H5 – N+ – C – CH3 → C2H5 – N – C – CH3 + HCl
H Cl H Cl H
Ethanamine Ethanoyl N-Ethylethanamide
chloride
58. Tertiary amines do not undergo acetylation reaction since there are no replaceable hydrogen atoms.
59. R – NH2 + CHCl3 + 3KOH 

∆
→ R – NC + 3KCl + 3H2O
1° Amine Alkyl
isocyanide
Secondary or tertiary amines do not give this test.

60. Carbylamine reaction is also known as isocyanide test.
R – NH2 + CHCl3 + 3KOH 
∆
→ R – NC + 3KCl + 3H2O
1° Amine Alkyl isocyanide
61. This reaction is a test for aliphatic or aromatic primary amines which on heating with chloroform give foul
(offensive) smelling products called alkyl/aryl isocyanides or carbylamines. Secondary and tertiary amines
do not give this test.
i. NaNO2 / HCl, 273 K
62. CH3 – CH2 – NH2 + HNO2 ii.H O+
→ CH3 – CH2 – OH + N2 ↑ H2O
3
Ethylamine Ethanol
H2 O
67. C6 H 5 N +2 Cl− 
283 K
→ C6H5 – OH + N2 + HCl
Benzenediazonium chloride Phenol (X)
69. C6H5 – N +2 X– 

HBF4
→ C6H5 – N +2 BF4− →
Aq. NaNO2 / Cu
∆
C6H5 – NO2 + N2 ↑ + BF3
Benzenediazonium Nitrobenzene
halide
+ −
70. Ph – N 2 Cl 
HBF4
→ Ph – N 2 BF4 
+ − ∆
→ Ph – F + N2↑ + BF3
Benzenediazonium Fluorobenzene
chloride
72. Reactions given in options (A), (C) and (D) involves displacement of diazo group. Only option (B) involves
retention of diazo group (azo coupling reaction).
+
– −
N ≡ NCl + OH 
OH
→ N =N OH + HCl
Benzenediazonium p-Hydroxyazobenzene
chloride Phenol (orange)
143


+ −
73. N ≡ NCl– + NH2 
OH
→ N =N NH2 + HCl
Benzenediazonium Aniline p-Aminoazobenzene

chloride (yellow)
74. Hinsberg’s reagent: Benzenesulphonyl chloride (C6H5SO2Cl)

75. Ethylamine (primary amine) reacts with benzenesulfonyl chloride to form N-ethylbenzene sulfonamide. The
hydrogen attached to nitrogen in N-ethylbenzene sulphonamide is strongly acidic. Hence, it is soluble in alkali.
O O
S – Cl + H – N – C2H5 → S – N – C2H5 + HCl
O H O H
Benzenesulphonyl Ethylamine N-Ethylbenzene sulfonamide
chloride (1° amine) (Soluble in alkali)
76. 2° Amines on reaction with Hinsberg’s reagent forms a product which does not contain any H-atom attached
to nitrogen atom. Hence, it is not acidic and does not dissolve in alkali.
77. –NH2 group in aniline is highly ring activating and o-/p- directing due to involvement of the lone pair of
electrons on ‘N’ in resonance with the ring.
78. Aniline reacts with bromine water at room temperature to give a white precipitate of 2,4,6-tribromoaniline.
NH2 NH2
Br Br
+ 3Br2 
Br2 / H 2 O
→ + 3HBr
Aniline
Br
2,4,6-Tribromoaniline
79. Direct nitration of aniline yields a mixture of ortho, meta and para nitroanilines.
NH2 NH2 NH2 NH2
NO2
Conc.HNO3 + Conc.H 2SO4
 → + +
288 K
NO2
Aniline NO2
(51%) (47%) (2%)
p-Nitroaniline m-Nitroaniline o-Nitroaniline
80. To get p-nitroaniline as major product, –NH2 group is first protected by acetylation and then nitration is
carried followed by hydrolysis of the amide.
O O
NH2 NH – C – CH3 NH – C – CH3 NH2
( 3 )2
CH CO O Conc.HNO3 + Conc H 2SO4

Pyridine
→  288 K
→ + −
H or OH
 →
Aniline Acetanilide
NO2 NO2
p-Nitroaetanilide p-Nitroaniline
+ –
NH2 NH3HSO4 NH2
81. H 2SO4
→ 453 − 473 K
 →
Aniline Anilinium
hydrogensulfate SO3H
(X) Sulfanilic acid
144

Chapter 13: Amines

+
82. C2H5NH2 
HNO2 / H
→ C2H5OH 
PCl5
→ C2H5Cl Alc.NH3

Excess
→ C2H5NH2
Ethylamine Ethanol Ethyl chloride Ethylamine
(A) (B) (C)
Critical Thinking
CH3
1. C6H5 − NH2 CH3 − CH − CH2 – NH2 CH3 − CH − CH2CH3

Aniline (1° amine) Isobutylamine (1° amine)
NH2
sec- Butylamine (1° amine)
CH3 CH3
CH3 H H H
|
| CH2
CH3 − C − N − C − CH3 CH3 − CH − NH − C2H5
6. CH3 − CH − CH2 − NH2
H3C − N − C − H
β-Methylpropylamine CH3 CH3 Ethylisopropylamine
(1° Amine) (Mixed 2° amine)
Di-isopropylamine H3C CH3
(Simple 2° amine) Dimethyl-sec-butylamine
(Mixed 3° amine)
C2H5 CH3
7. CH3 − CH2 − CH2 − NH2 CH3 − CH − NH2
NH CH3 − N
n-Propylamine (1° amine) CH3 CH3
CH3 Ethylmethylamine
Isopropylamine Trimethylamine
(1° amine) (2° amine) (3° amine)
8. (CH3)2CH– NH2
Common name: Isopropylamine ; IUPAC name: Propan-2-amine
CH3
2 1
9. CH3 – N – CH – CH3
3 CH3
N,N-Dimethylpropan-2-amine
CH3
2 3 4
10. CH3 – CH2 – CH2 – N – CH – CH2 – CH3
1CH
3
N-Methyl-N-propylbutan-2-amine
1
CH3 CH3
| 2
|
11. H3C − N − C − CH3
3|
CH3
N,N-Dimethyl-2-methylpropan-2-amine
12. When alkyl halide is heated with alcoholic ammonia, primary amine is obtained. However, the primary
amine obtained in the 1st step is stronger nucleophile than ammonia. Hence, it further reacts with alkyl
halide to form secondary and tertiary amines and finally quaternary ammonium salt if NH3 is not used in
large excess.
145

C2H5 − Br + NH3 →

373K, ∆
Pressure
C2H5 − NH2 + HBr
Ethyl Ethylamine
bromide
H5C2
C2H5 − NH2 + C2H5 − Br →
373K, ∆
Pressure NH + HBr
Ethylamine
H5C2
Diethylamine
H5C2
NH + C2H5 − Br →
373K, ∆
Pressure H5C2 − N − C2H5 + HBr
H5C2
C2H5
Diethylamine Triethylamine
C2H5
+
H5C2 − N − C2H5 + C2H5 − Br →
373K, ∆
Pressure H5C2 – N– C2H5 Br
−
C2H5 C2H5
Triethylamine
Tetraethylammonium bromide
13. C2H5 − NO2 

LiAlH 4 in ether
→ C2H5 − NH2 
C2 H5 Br
→ (C2H5)2NH 
C2 H5 Br
→ (C2H5)3N
Nitroethane Ethylamine Diethyl Triethyl
(X) amine amine
(Y) (Z)
14. CH3 − NO2 →

Fe/ HCl
CH3 − NH2 
C2 H5 Br
→ C2H5–NH–CH3 
C2 H5 Br
→ (C2H5)2N–CH3
Nitromethane Methylamine N-Methylethanamine N-Ethyl-N-methylethanamine
(X) (Y)
Cl

15. CH3 − CH − CH3 + K − C ≡ N →
boil
(H3C)2 − CH − CN + KCl
2-Chloropropane (alc.) 2-Methylpropanenitrile
(X)
Na / C2 H5 OH
(H3C)2 − CH − CN 
or LiAlH 4
→ (H3C)2CH − CH2 – NH2
2-Methylpropan-1-amine
(Y)
16. C2H5 − Cl 

Alc.AgCN
∆
→ C2H5N ≡ C 
Na / C2 H5 OH
→ C2H5 – N – CH3
Chloroethane Ethyl
(X) isocyanide H
N-Methylethanamine
∆
17. R – CO – NH2 + Br2 + 4KOH  → RNH2 + K2CO3 + 2KBr + 2H2O
Amide 1° Amine
18. CH3 – CO – NH2 

KOH / Br2
Hoffmann's bromamide
→ CH3 – NH2
Acetamide degradation
Methylamine
(Amide) (Amine)
[2 C-atoms] [1 C-atom]
146

Chapter 13: Amines

O
C − NH2 NH2
19. + Br2 + 4NaOH → + Na2CO3 + 2NaBr + 2H2O

(aqueous
Benzamide or alcoholic) Aniline
(X)
O = C – NH2 CH2NH2
LiAlH 4 / ether
 →
Benzamide Benzylamine
(Y)
20. CH3 − CH2− CH2 − C − NH2 + Br2 + 4NaOH → CH3 − CH2 − CH2 − NH2 + Na2CO3 + 2NaBr + 2H2O
Butanamide
Propan-1-amine
(C3H7CONH2)
22. The order of boiling point is 1° > 2° > 3° for isomeric amines.
∴ The correct order for given amines is: n-Propylamine > ethylmethylamine > trimethylamine
23. The order of boiling points of alkanes, amines, alcohols and carboxylic acid of comparable molar mass is as
follows: alkanes < amines < alcohols < carboxylic acid.
24. Since N – H bonds in amines are less polar than O – H bond in alcohols, water solubility of alcohols, amines
and alkanes of comparable molar mass in water decreases in the order:
alcohols > amines > alkanes.
25. In amines, nitrogen has a lone pair of e–. It can donate the electron pair. So, amines behave as a Lewis bases.
26. Stability of conjugate acids is influenced by +I effect of alkyl groups. Thus, conjugate acid of 3° amines
will be most stable. Order of stabilization of conjugate acid of 1°, 2°, 3° amines and ammonia is,
+ + + +
NH4 < R – NH3 < R2NH2 < R3N – H
28. Arylamines are weaker bases than aliphatic amines and ammonia.
Compound Ammonia Phenylmethanamine N-Methylmethanamine N-Methylaniline
pKb values 4.75 4.70 3.27 9.30

29. C6H5NH2 will have higher pKb value than (CH3)3N. That is, (CH3)3N will be more basic than C6H5NH2.
30. R4N+X− →
moist Ag 2 O
∆
R4N+OH–
31. Aliphatic and aromatic primary and secondary amines undergo acylation reaction. Trimethylamine is a
tertiary amine. It has no replaceable H-atom. Thus, it will not react with benzoyl chloride.
32. R – NH2 + CHCl3 + 3KOH(alc.) 
∆
→ RNC + 3KCl + 3H2O
Primary Alkyl
amine isocyanide
33. i. Offensive smell with CHCl3 and KOH
∴ The compound must be an isocyanide. Only primary amine forms isocyanide.
So, compound B is a primary amine.
ii. Formation of ethyl alcohol with nitrous acid
∴ Compound B must be ethylamine.
C2H5NH2 + HNO2 → C2H5OH + H2O + N2↑
iii. Reduction
Compound A + [H] → C2H5NH2
Compound A is CH3CN
∴ Compound A is methyl cyanide.
147

NH2 N +2 Cl−
34.
NaNO2 + HCl

0 − 5 °C
→ + NaCl + 2H2O
Aniline Diazonium salt
35. Hofmann elimination product is in contrast to Saytzeff elimination, that is, the least substituted alkene is
obtained as major product.
36. Aliphatic and aromatic primary and secondary amines undergo acylation reaction.
Aliphatic or aromatic primary amines will give both carbylamine and nitrous acid reaction. 2°, 3°amines also
react with nitrous acid but they will not answer carbylamine test. Thus, the set of amines given in option (C),
[CH3NH2, PhCH2NH2, Ph–NH2] will give all three reactions as it contains only aliphatic and aromatic
primary amines.
37. N +2 Cl− OH
H 2 O, 283 K

− N 2 , − HCl
→
Benzenediazonium chloride Phenol
+ − + −
H PO H O
38. (i) C6 H 5 − N 2 X →
3 2
H2 O
C6H6 (ii) C6 H 5 − N 2 X 2
283 K
→ C6H5OH
+ − + −
i.HBF
(iii) C6 H 5 − N 2 X 
ii. ∆
4
→ C6H5F (iv) CH3CH 2 OH
C6 H 5 − N 2 X  → C6H6
+ −
i.HBF
(v) C6 H 5 − N 2 X  4
ii. ∆ , aq.NaNO2 / Cu
→ C6H5NO2
39. Azo coupling reaction is an electrophilic aromatic substitution reaction in which electrophiles are positively
charged diazonium ions.
40. Benzenediazonium chloride reacts with phenol molecule and its para position gets coupled with the
diazonium salt to form p-Hydroxyazobenzene. This type of reaction is known as coupling reaction.
+ – −
N ≡ NCl + OH
OH  → N=N OH + HCl
Benzenediazonium Phenol p-Hydroxyazobenzene

chloride (orange dye)
41. Primary amines react with Hinsberg reagent to give alkali soluble product.
42. (A) C6H5 – CH2 – Cl 

Alc. NH3
→ C6H5 – CH2NH2 
2CH3 I
→ C6H5 – CH2 – N –CH3
Benzyl chloride Benzylamine
CH3
N,N-Dimethylbenzylamine
(3°)
(B) C2H5 − I 
Alc.AgCN
∆
→ C2H5N ≡ C 
Na / C2 H5 OH
→ C2H5 – N – CH3
Iodoethane Ethyl
isocyanide
H
N-Methylethanamine
(2°)
(C) Cl – (CH2)4 –Cl + KCN 

∆
→ N ≡ C – (CH2)4 – C ≡ N →
4[H], Na / C2 H5 OH
H2N – H2C – (CH2)4 – CH2 – NH2
1,4-Dichlorobutane Hexane-1,6-diamine
(1°)
Br2 / KOH
(D) CH3CH2COOH 
NH3
→ CH3CH2COONH4 
∆
→ CH3CH2CONH2 
(Hoffmann bromamide )
→ CH3CH2NH2
Propanoic acid Ethanamine (1°)
Only 1° and 2° amines react with Hinsberg’s reagent. 1° Amines react with Hinsberg’s reagent to give alkali
soluble product and 2° amines give alkali insoluble product. Thus, option (B) is the correct answer.
148

Chapter 13: Amines
1. Secondary or tertiary amines are named as N-substituted derivatives of primary amines. Since there are two
N-substituted groups in the given IUPAC name, it is a tertiary amine.
C2H5 – N – CH2 – CH2 – CH3
CH3
N-Ethyl-N-methylpropan-1-amine
(3° Amine)
2. Gabriel phthalimide reaction is useful to prepare unhindered aliphatic 1° amines. Thus, n-butylamine will be
most readily prepared by Gabriel phthalimide reaction.
CO CO
KOH ( alc.) H3C(CH2)2CH2Br
NH 
− H2 O
→ N−K+
CO CO
Phthalimide Potassium salt of phthalimide –KBr
COOH CO
H + / H 2 O or OH − / H 2 O
+ H3C(CH2)3NH2 ← Hydrolysis N − CH2(CH2)2CH3
COOH n-Butylamine CO
Phthalic acid N-Butylphthalimide
3. This reaction is known as Hofmann’s hypobromamide reaction.

Br / 4KOH
CH3 – C – NH2 
2 (aq)
→ CH3 – NH2 + 2KBr + K2CO3 + 2H2O
Methanamine
O
Acetamide
O
4. CH3 – C – NH2 + Br2 + 4NaOH → CH3 – NH2 + Na2CO3 + 2NaBr + 2H2O
Acetamide Methylamine
5. R – C – NH2 + 1Br2 + 4NaOH → R – NH2 + Na2CO3 + 2NaBr + 2H2O

6. Hofmann bromamide degradation is used only in the preparation of primary amines. It is useful for
decreasing the length of carbon chain by one carbon atom (step down reaction). In this reaction, amides are
treated with bromine and aqueous or alcoholic KOH / NaOH to obtain primary amine.
7. Trimethylamine [(CH3)3N] will be least soluble due to the absence of H-atoms attached to the nitrogen atom.
This prevents the formation of intermolecular hydrogen bonds.
8. As a consequence of combined effect of inductive effect, steric effect and solvation, the secondary amines
are the strongest bases among aliphatic amines in aqueous phase and the basic strength varies as:
2º amine > 3° amine > 1º amine > ammonia.
Hence, among the given options, dimethylamine (2º) is most basic in aqueous phase.
9. In aqueous phase, methylamines follow the basicity order as follows:
(CH3)2NH > CH3NH2 > (CH3)3N (2º > 1º > 3°)
pKb: 3.27 3.38 4.22
10. In alkylamines, +I effect of alkyl groups increases the electron density on nitrogen atom. This increases the
ease with which lone pair of electrons can be donated. Hence, ammonia will be least basic and (C2H5)2NH
will be most basic.
12. CHCl3 gives carbylamine test when heated with KOH and a primary amine.
RNH2 + CHCl3 + 3KOH (alc.)  ∆
→ RN C + 3KCl + 3H2O
Primary amine Alkyl isocyanide
149


13. When aliphatic or aromatic primary amines are heated with chloroform and alcoholic potassium hydroxide,
foul smelling alkyl isocyanides or carbylamines are formed. Secondary or tertiary amines do not undergo
such reaction. This reaction is known as carbylamine test or isocyanide test.

NH 2 N=C
14. + CHCl3 + 3KOH 

∆
→ + 3KCl + 3H2O
Aniline Phenyl isocyanide
(Phenyl isonitrile)
15. CH3COOH +  CH3COONH +4

NH3 
∆
 → CH3CONH2 + H2O
Acetic acid Ammonia Ammonium acetate Acetamide
(A)
CH3CONH2 
i. LiAlH 4 / diethyl ether
ii. H O+
→ CH3CH2NH2
3
Ethylamine
(B)
CH3CH2NH2 + CHCl3 + 3KOH 

∆
→ CH3 – CH2 – NC + 3KCl + 3H2O
Chloroform (alc.) Ethyl isocyanide
(C)
∴ B: CH3CH2NH2, C: CH3CH2NC
16. Aliphatic primary amines react with nitrous acid (HNO2) to give brisk effervescence due to evolution of N2
gas.
C2H5 − NH2 + HO − N = O NaNO2 + dil.HCl

273 K − 278 K
→ C2H5OH + HCl + N2↑
Ethyl alcohol
Ethylamine Nitrous
acid
17. In Sandmeyer reaction, copper (I) salts such as cuprous chloride, cuprous bromide or cuprous cyanide are
used to replace nitrogen in diazonium salt with –Cl, –Br or –CN respectively.
Hence, among the given options, C6H5I is not formed by Sandmeyer reaction.
NH2 N +2 Cl− CN
CuCN / KCN
18.
NaNO2 / HCl
 →  →
0 °C −5 °C ∆
+ N2 ↑
CH3 CH3 CH3

4-Aminotoluene 4-Methylbenzene 4-Methylbenzonitrile
diazonium chloride (E)
(D)
19. Hypophosphorus acid/phosphinic acid (H3PO2) reduces diazonium salts to corresponding arenes.
Me Me
H3 PO2
→
N +2 Cl− H
NH2 N +2 Cl− I
20. NaNO2 , HCl

 → KI / ∆
→
273 − 278 K − N 2 , − KCl
Aniline Benzenediazonium Iodobenzene

chloride (Z)
150

Chapter 13: Amines
NH2 N 2+ Cl−
21. + NaNO2 + 2HCl 

0 −5 °C
→ + 2H2O + NaCl
Aniline Benzene
(A) diazonium chloride
(B)
– +
(CH3)2N H + ClN ≡ N 
− HCl
→ (CH3)2N N=N
N,N-Dimethylaniline Benzene p-Dimethylaminoazobenzene

diazonium chloride (yellow dye)
(B) (C)
NO2 NH2 N +2 Cl−

22. 
→ Sn HNO2
→ Phenol
 → N=N OH
HCl 273 K
Nitrobenzene Aniline Benzenediazonium p−Hydroxyazobenzene

‘A’ chloride Azo dye
‘B’ ‘C’
(C12H10N2O)
23. The product ‘X’ obtained is known as methyl orange which is generally used in acid base titration as an
indicator.
-
N(CH3)2 + N a +SO3− N +2 Cl− 
OH
→ (CH3)2N N=N SO3− N a +
Dimethylaniline Sodium salt of Methyl orange

p-Azobenzenesulphonate (X)
24. Secondary amines react with Hinsberg reagent to give an alkali insoluble product.
25. Tertiary amines do not react with benzenesulphonyl chloride due to absence of hydrogen atom directly
attached to the nitrogen atom. Among the given options, tripropylamine is a tertiary amine and hence, option
(A) is the correct answer.
O
CH3 Cl − S O CH3
O S − NH − CH − CH2 − CH3
26. CH3 − CH2 −*CH − NH2
O
(X) (Y)
CH3 CH3
CH3 − CH2 −*CH − NH2 CH3COCl CH3 − CH2 − CH − NH − CO − CH3

(X) (Z)
O O
H +
27.
(H3CCO)2O

Pyridine / ∆
→ Br2
H3CCOOH
→ →
Aniline Acetanilide Br Br
(A) p-Bromoacetanilide p-Bromoaniline
(B) (C)
151


28. When aniline is nitrated with nitrating mixture in ice cold condition, the major product obtained is
p-nitroaniline.
NH2 NH2 NH2 NH2
NO2
Conc.HNO3 /
→
Conc.H 2SO4 , 288 K
+ +
NO2
Aniline
NO2
p-Nitroaniline m-Nitroaniline o-Nitroaniline
(51%) (47%) (2%)
29. In acidic medium, protonation of –NH2 group gives − NH3+ , which is m-directing and deactivating.
30. Treatment of t-butyl bromide with alcoholic ammonia results in elimination reaction instead of substitution.
Hence, the products obtained are (CH3)2C = CH2 + NH4Br.
CH3 CH3
CH3 − C − CH3 + NH3 

alcohol
→ CH3 − C = CH2 + NH4Br
Isobutylene
Br
t-Butyl bromide
31. In alkaline medium, coupling occurs at para position with respect to hydroxyl group. If p-position is blocked
then coupling will occur at o-position with respect to hydroxyl group. In this case, coupling will occur at
p-position with respect to hydroxyl group.
OH OH
C H N + Cl− / OH −
6 5 2

( pH ≈ 9 − 10 ) →
1-Naphthol
N
32. In case of substituted aniline, electron releasing groups like −OCH3, −CH3, −NH2 increase the basic strength
while electron withdrawing groups like −NO2, −C6H5, −SO3, −COOH, −CN, −X decrease the basicity of
amines.
33. Order of basic strength for the mentioned compounds is,
NH2 NH2 NH2
> >
CH3 H NO2
Electron Electron
donating withdrawing
34. C2H5 – NH2 + HO − N = O 

NaNO2 + HCl
273K -278K
→ C2H5 – OH + H2O + N2↑ [Effervescence due to nitrogen gas]
Ethylamine Ethanol (1 mol
(1 mol) = 28 g)
35. Amongst the given options, C6 H5 N +2 X − is the most stable diazonium salt due to resonance stabilization.
152

Chapter 13: Amines

36. Four isomeric amines are possible for C3H9N:
CH3 CH3
CH3 – CH2 – CH2 – NH2 CH3 – CH – NH2 CH3 – CH2 – NH – CH3 CH3 – N – CH3
Propan-1-amine Propan-2-amine N-Methylethanamine N,N-Dimethylmethanamine
37. Reaction of phthalimide with alkyl or benzyl halides in the presence of alcoholic KOH or aqueous NaOH
solution is called as Gabriel phthalimide synthesis. Aromatic primary amines like aniline are not prepared by
using this method because nucleophilic substitution of aryl halides with phthalimide anion is not possible.
COOH
Br Br Br Br
38. NaNO2 / HCl C2 H5 OH
 →  → KMnO4
273 − 278 K − →
OH
(Y)
NH2 N +2 Cl− (Z)
(X)
NO2 NH2 NH2

Br Br
39. i. Fe + HCl
→ →ii. Br2 / H 2 O iii. NaNO2 , HCl
→ 273 K
Nitrobenzene Aniline
Br
2,4,6-Tribromoaniline
N +2Cl−
Br Br Br Br
iv. H3 PO2
 →
Br Br
1,3,5-Tribromobenzene
CH3 CH3 CH3

Br Br
40. Br2
→
Bromination
Sn / conc.HCl

Reduction
→
NO2 NO2 NH2

p-Nitrotoluene
(P) (Q)
COOH CH3 CH3

Br Br Br NaNO2/HCl
− H 2 O / H3 PO2 / CuCl
KMnO4 / OH
←  ←
Re duction 273 – 278 K
Oxidation
(Diazotisation)
o-Bromobenzoic o-Bromotoluene N +2 Cl−
acid (R) Diazonium
salt
153

1. Mendius reduction: Alkyl cyanides or cyanoalkanes on reduction by sodium and ethanol give corresponding
primary amine.
R – C ≡ N + 4[H] 
Na / ethanol
→ R – CH2 – NH2
Alkyl 1° Amine
cyanide
2. Stronger the base, lower will be the value of pKb. Ammonia is a weaker base than amines. So the value of
pKb will be higher for NH3.
3. Isopropylamine (1°), ethylmethylisopropylamine (3°), methylphenylamine (2°), benzylamine (1°)
4. Four 1° amines are possible.
CH3CH2CH2CH2NH2, (CH3)2CHCH2NH2,
CH3CH(NH2)CH2CH3, (CH3)3CNH2
5. As ‘Z’ gives carbylamine test, it is a primary amine. ‘Y’ reacts with acetic anhydride and does not give
carbylamine, thus; it is secondary. ‘X’ does not react with acetic anhydride. ‘X’ is tertiary amine.
∴ X, Y and Z are tertiary, secondary and primary amines respectively.
6. Only primary aliphatic amines give nitrogen gas with nitrous acid. Aniline is an aromatic amine.
7. Gabriel phthalimide synthesis yields exclusively aliphatic primary amines. Phenylamine (aromatic 1° amine)
cannot be prepared by this method because aryl halides do not undergo nucleophilic substitution with
phthalimide anion.
8. Benzene sulphonyl chloride is used in Hinsberg’s test to find out acidic hydrogen atom which is soluble in
H2O.
Primary → one acidic H atom → soluble in alkali
Secondary → no acidic H atom → insoluble in alkali
Tertiary → does not react
10. Diazotisation reaction [action of nitrous acid (NaNO2 + HCl)] is given by an aromatic primary amine
(having −NH2 group directly attached to nucleus) which leads to the formation of diazonium salt. In option
(B), C6H5 – CH2 – CH2 – NH2, amino group is not directly attached to the benzene nucleus; hence, no
diazotisation.
11. Aliphatic or aromatic primary amines on heating with chloroform give foul smelling products called
alkyl/aryl isocyanides or carbylamines. This is known as carbylamines test.
Thus, propan-2-amine (1°) will give carbylamine test.
13. Basic strength of amines follow the basicity order as follows:

R2NH > RNH2 > R3N (2º > 1º > 3°)
14. Tertiary amines do not react with benzenesulphonyl chloride due to absence of hydrogen atom directly
attached to the nitrogen atom. Among the given options, ethyldimethylamine is a tertiary amine and hence,
option (A) is the correct answer.
NH2 N +2 Cl−
NaNO2 , HCl CH3CH 2 OH

15. 
273 − 278 K
→  →
Aniline Benzenediazonium Benzene

chloride (Z)
+ − + −
H PO H O
18. (A) C6 H 5 − N 2 X →
3 2
H2 O C6H6 (B) C6 H 5 − N 2 X 2
283 K
→ C6H5OH
+ − + −
i.HBF
(C) C6 H 5 − N 2 X 
ii. ∆
4
→ C6H5F (D) C6 H 5 − N 2 X 
CuBr / HBr
→ C6H5Br
154

Chapter 13: Amines

19. CH3 – CO – NH2 
NaOH / Br2
→ CH3 – NH2
Hoffmann's bromamide
Acetamide
degradation
Methylamine
(Amide) (Amine)
O O O
C C C
– +
20. N−H 
Alc.KOH
→ N K
CH3CH 2 Br
→ N− CH2CH3
C − H2 O
C C
O O O
Phthalimide N-Ethyl phthalimide
(P) (Q)
O
– +
C O Na
aq.NaOH
+ CH3CH2– NH2
– + Ethylamine
C O Na
(S)
O
Sodium salt of phthalic acid
(R)
155
Target Publications Pvt. Ltd. Std. XII : Triumph Chemistry
14 Biomolecules
Hints
Classical Thinking
2. Primary structural materials of organisms are proteins and cellulose.
3. Carbohydrates are polyhydroxy aldehydes or ketones or compounds which give rise to such units on
hydrolysis.
5. The sugar present in milk is called lactose.
7. Oligosaccharides on hydrolysis yield two to ten units of monosaccharides.
8. Lactose 
hydrolysis
→ Glucose + Galactose
Maltose 
hydrolysis
→ Glucose + Glucose
Sucrose 
hydrolysis
→ Glucose + Fructose
Ribose [CHO–(CHOH)3–CH2OH] itself is a monosaccharide; hence it does not give monosaccharide units
on hydrolysis.
9. Raffinose – Trisaccharides
Cellulose and glycogen – Polysaccharide
Stachyose – Tetrasaccharide
10. (A) Sucrose – disaccharide (B) Starch – polysaccharide
(C) Glucose – monosaccharide (D) Maltose – disaccharide
11. Ribose is an example of monosaccharide.
16. Given structure is of ribose which is a monosaccharide, containing aldehydic group and five C-atoms.
Hence, it can be called as aldopentose.
17. Carbohydrate present in cane sugar is sucrose.
C12H22O11 + H2O  dil.HCl
∆
→ C6H12O6 + C6H12O6
Sucrose Glucose Fructose
18. Hydrolysis of sucrose gives a mixture of glucose and fructose. Glucose is separated from fructose by the
addition of ethanol during cooling process. Glucose is almost insoluble in alcohol and hence, crystallizes out
first.
19. Commercially, glucose is obtained by hydrolysis of starch by boiling it with dilute sulphuric acid at 393 K
under 2 to 3 atm pressure.
H+
(C6H10O5)n + nH2O  393 K, 2 − 3atm
→ nC6H12O6
Starch Glucose
20. Structure of glucose can be represented as, OHC – (CHOH)4 – CH2OH.
22. The structure of glucose is,
CHO
|
(CHOH)4
|
CH2OH
Glucose
156
Carboxylic Acids
56. O
O
C − CH2 − CH3
Anhydrous AlCl3
+ Cl − C − CH2 − CH3 →
Propionyl chloride
Benzene
NH2 − NH2 / KOH Ethylene glycol
CH2 − CH2 − CH3
n-Propylbenzene
57.
O O O HO CH3 HO CH3
+ CH 3MgBr /dry ether
 Ag ( NH3 )  OH − +
→
 2 H / CH3OH
 →
CH3 MgBr / dry ether
→ +
 + →
Tollens reagent H3 O H 3O
CHO C O = C − CH3 HO – C − CH3

CO2H
O OCH3 CH3
58.
O− O O OH OH OCOCH3
H O− COO− COOH
− O= C= O
COOH

o → C H
→
+
(CH3CO)2 O
125 C,  →
5atm O
Phenoxide Salicylate Salicylic
ion Aspirin
ion acid
(B) (C)
59. Keto-enol tautomerism is represented as:

H
α
–C–C=O – C = C – OH
Keto Enol
60. CH3 COOH COCl CHO
KMnO4
 → SOCl2
 →
H 2 / Pd

BaSO4
→
Toluene Benzoic acid Benzoyl chloride Benzaldehyde

(A) (B) (C)
61.
Option Will not be compound ‘X’ because
(A) Pentanal it will give positive Tollen’s test
(B) Pentan-2-one will give positive iodoform test as its a methyl ketone
(D) n-Amyl alcohol (i) will not yield phenyl hydrazone due to absence of carbonyl group
(ii) will not yield n-pentane as a product on its reduction
Thus, only option (C) satisfies all the given conditions and hence is the correct answer.
135


O O
62. I. CH3 − C − O − C − CH3 + H2O → 2CH3COOH
Acetic anhydride Acetic acid

II.
65.
Compound Neutral FeCl3 test Fehling solution test Iodoform test
(A) O Positive Negative Positive
CH3
OH
(B) OH Negative Negative Positive [As it contains
CH3CH(OH) – group]
CH3
C2H5
(C) O Negative Negative Negative

CH3
H
O
(D) O Negative Negative Negative
C2H5
CH3
O
Note : Aldehydes and ketones react with Grignard reagent to form corresponding alcohols.
OH 
i. CrO3 − H 2SO4
Cl ( CH ) Cd
66. ii. SOCl2
→ 3 2

(Y) →
O O
(X)
OH HCl(gas)
HO
(Z)
O O
67. On heating, ammonium salt of benzoic acid gives benzamide.

O O
C – + C
ONH4 Δ
NH2

− H2 O
→
Ammonium salt Benzamide

of benzoic acid
136

Chapter 14: Biomolecules

58. A tripeptide will possess two peptide bonds and three amino acids. Hence, option (C) is the correct answer.
59. Myosin is a fibrous protein while the rest are globular proteins.
63. Hydrogen bonds are parallel to the axis of α-helix.
68. Chemically, enzymes are proteins.
70. Nucleic acids are polynucleotides.
71. DNA molecules contain several million nucleotides while RNA molecules contain a few thousand
nucleotides.
76. Nucleotide contains nitrogenous bases like adenine, guanine, thymine, cytosine and uracil, whereas tyrosine
is an amino acid.
O
||
5
77. O – P – O – CH2 Base
| Phos- O
O– phate 4 1
Sugar
ester
linkage
3 2
In the nucleotide of DNA and RNA, heterocyclic base and phosphate group are at C1 and C5 respectively of
the sugar molecule.
80. The polynucleotide chains of nucleic acids are named by the sequence of the bases, beginning at the 5' end
and using the one letter symbols of the bases. Hence, thymine is present at the 5′ end of the polynucleotide
chain. Thus, sequence can be represented as, 5′ - TGCTTCGAA - 3′.
81. The complementary strand runs in opposite direction from the 3' end to the 5' end. It has the base sequence
decided by complementary base pairs A - T and C - G.
Given strand 5' - A G G T C C - 3'
↓ ↓↓↓↓ ↓
Complementary strand 3' - T C C A G G - 5'
82. Glucose contains a aldehydic carbonyl group which is electrophilic in nature and is susceptible to attack by a
nucleophile.
CN
CHO CHOH
(CHOH)4 HCN

→ (CHOH)4
CH2OH CH2OH
Glucose Glucose cyanohydrin
83. Monosaccharides are named D- or L-based on the configuration of the lowest chiral carbon in its Fischer
projection formula.
84. Ribose : Aldopentose Fructose : Ketohexose Threose : Aldotetrose Glucose : Aldohexose
Critical Thinking
2. Lactose is a disaccharide, hence produces two monosaccharide units.
3. Four monosaccharide units are produced on hydrolysis; thus, X is a tetrasaccharide stachyose.
4. Raffinose on hydrolysis yields one unit each of glucose, fructose and galactose.
Stachyose on hydrolysis yields one unit each of glucose and fructose along with two units of galactose.
5. Ribose is an aldopentose HOCH2 – (CHOH)3 – CHO.
6. Ketohexose contains total of six C-atoms and a keto group.
159


7. Formation of oxime (X) confirms the presence of one carbonyl group in glucose molecule. While,
formation of n-hexane (Y) confirms the presence of six C-atoms in glucose molecule which form a
straight chain.
O = CH(CHOH)4CH2OH OH – N = CH –(CHOH)4CH2OH
NH 2 − OH
 →
Glucose Oxime
(X)
CHO(CHOH)4CH2OH 
∆ , HI
→ CH3−(CH2)4−CH3
Glucose n-Hexane
(Y)
8. CHO COOH CHO COOH

Dil.HNO3
(CHOH)4 [O]
→ (CHOH)4
Br2 water
(CHOH)4 + [O]  → (CHOH)4
CH2OH COOH CH2OH CH2OH

Dicarboxylic acid Glucose Monocarboxylic acid
Glucose (X) (Y)
9. Fischer projection formula (X) has –OH groups at the lowest C-5 chiral carbon on right side.
∴ It is D-aldohexose.
Fischer projection formula (Y) has –OH groups at the lowest C-5 chiral carbon on left side.
∴ It is L-aldohexose.
10. Fructose is a laevorotatory ketohexose and it is called laevulose as it shows laevorotation [α]20
D = –92.4°.
11. The laevorotation of fructose (–92.4°) is larger than the dextrorotation of glucose (+52.7°). Thus, ‘X’ is
fructose and ‘Y’ is glucose.
12. In the given structure, there are two monosaccharide units. So, it cannot be ribose (which is a
monosaccharide). The constituent monosaccharides have total of six C-atoms (i.e., hexose).
Both the monosaccharide units have same Haworth formulae. As we know, only maltose yields two glucose
units on hydrolysis. Thus, maltose is the correct answer. Sucrose and lactose yields two different
monosaccharide units on hydrolysis (Sucrose: Glucose + fructose; Lactose: Glucose + galactose).
15. (A) In maltose, C-1 of one α-D-glucopyranose is linked to C-4 of another α-D-glucopyranose molecule by
glycosidic linkage.
(B) In cellulose, C-1 of one β-D-glucopyranose is linked to C-4 of another β-D-glucopyranose molecule
by glycosidic linkage.
(C) In sucrose, C-1 of α-D-glucopyranose is linked to C-2 of β-D-fructofuranose by glycosidic linkage.
(D) In lactose, C-1 of β-D-galactopyranose is linked to C-4 of β-D-glucopyranose by glycosidic linkage.
16. α-Carbon in all the α-amino acids except glycine is chiral.
The α-carbon in α-amino acids obtained by hydrolysis of proteins has ‘L’- configuration.
α-Amino acids which cannot be synthesised in human body and have to be obtained through diet are called
essential amino acids.
17.
CH2 OH
H2N – CH – COOH
Tyrosine
20. α-Amino acids are generally represented as, R–CH(NH2)COOH (where R – Side chain)
If ‘R’ contains: –COOH group then the amino acid is acidic; an amino (1°, 2° or 3°) group then the amino
acid is basic, or having neutral/no functional group in ‘R’ then the amino acid is neutral.
Thus, Neutral α-amino acids: i, iii
Acidic α-amino acids: ii, v
Basic α-amino acids: iv
160


22. In peptide linkage i.e., – CONH – group, the carboxyl group of one amino acid molecule forms an amide by
combination with the amino group of the next amino acid molecule with the liberation of water molecule.
R1 O H R2 O R1 R2
H2N − CH − C − OH + H − N − CH − C − OH 
−H O
∆
→ 2
H2N − CH − CO − NH − CH − COOH
α-Amino acid α-Amino acid Peptide linkage
Protein molecule (dipeptide)
Dipeptide structure (B) is formed by combination of two different amino acids. (A) and (C) are formed by
the combination of same amino acid.
23. (II) In the dipeptide glycylalanine, glycine residue is N-terminal and alanine residue is C-terminal.
24. The structures of the amino acids obtained by adding water molecule across the peptide bond are as follows:
HO H HO H
HSCH2 – CH – CO – NH – CH – CO – NH – CH – COOH
NH2 CH(OH)–CH3 CH2COOH
→ HSCH2 – CH – COOH + H2N – CH – COOH + H2N – CH – COOH
NH2 CH(OH)–CH3 CH2COOH
25. Proteins are different from one another due to differences in number, nature and sequence of amino acids in
them.
26. α-Helix structure of proteins is formed when the chain of α-amino acid coil as a right handed spiral because
of the formation of hydrogen bonds between amide groups of the same peptide chain. This H-bonding is
responsible for holding helix in position.
29. Thymine occurs only in DNA. Uracil is not present in DNA. It is found only in RNA. Thus, option (B) is the
correct answer.
31. Base + sugar = nucleoside
Base + sugar + phosphate unit = nucleotide
32. (I) Adenine and guanine are derived from the parent compound purine.
(II) Nucleotides are formed by adding a phosphate group to the 5'-OH of a nucleoside.
34. Schematic representation of DNA segment can be given as,
Phosphate deoxyribose Phosphate deoxyribose

5′ 3′
G T
36. RNA contains pyrimidine bases as uracil and cytosine.

O NH2
NH N
N O N
O
H H
Uracil(U) Cytosine (C)
37. (C) A nucleic acid contains a backbone consisting of alternating sugar and phosphate groups.
161


38. On hydrolysis of sucrose, glucose and fructose are obtained.
Glucose contains an aldehydic (−CHO) group, while fructose contains a ketonic ( C = O) functional group.
CHO CH2OH
| |
(CHOH)4 C=O
| |
CH2OH (CHOH)3
(Glucose) |
CH2OH
(Fructose)
Both have same molecular formula C6H12O6.

41. (A) Disaccharides give rise to two units of same or different monosaccharides on hydrolysis.
(B) Glyceraldehyde has one chiral carbon.
(C) Glycogen constitutes storage carbohydrate of animals.
1. Raffinose 
Hydrolysis
→ Glucose + Fructose + Galactose
CN
CHO CHOH
3. (CHOH)4 HCN
→ (CHOH)4
CH2OH CH2OH
Glucose Glucose cyanohydrin
4. Glucose on reaction with mild oxidising agent like bromine water gets oxidised to six carbon carboxylic acid
i.e., gluconic acid. This confirms that the carbonyl group present in glucose is an aldehydic group.
5. It is called pyranose structure, in analogy with the six membered heterocyclic compound pyran.
Structure of α-D-Glucopyranose:
CH2OH O
O
H H
H
OH H Pyran
HO OH
H OH
6. There are five chiral carbon atoms (indicated by *) in β-D-(+)-glucose.
HO 1C* H
H 2C* OH
HO 3C* H O
H 4C* OH
H 5C*
6
CH2OH
β-D-(+)-Glucose
162


7. Sucrose is a disaccharide of α-D-glucopyranose and β-D-fructofuranose.
8. Maltose is a disaccharide made of α-D-glucopyranose units.
10. Maltose and lactose contains free aldehydic group while fructose contains free ketonic group. Thus, they are
reducing sugars. However, sucrose does not contain a free aldehydic or ketonic group as the reducing groups
of glucose and fructose present in the sucrose molecule are involved in the glycosidic bond formation.
Hence, sucrose is a non-reducing sugar.
11.
Carbohydrate Nature and units linked together
(A) Maltose Disaccharide having α-D-glucose units
(B) Sucrose Disaccharide having α-D-glucose and β-D-fructose units
(C) Cellulose Polysaccharide having β-D-glucose units
(D) Lactose Disaccharide having β-D-galactose and β-D-glucose units
12. In maltose, C-1 of one α-D-glucopyranose molecule is linked to C-4 of another α-D-glucopyranose
molecule by glycosidic linkage.
In lactose, C-1 of β-D-galactopyranose molecule is linked to C-4 of β-D-glucopyranose molecule by
glycosidic linkage.
In cellulose, C-1 of one β-D-glucopyranose molecule is linked to C-4 of another β-D-glucopyranose
molecule by glycosidic linkage. Thus, in maltose, lactose and cellulose, all the monosaccharide units are
joined by C-1 − O − C-4 chain.
Amylopectin is a branched chain polymer. In amylopectin, C-1 of one α-D-glucopyranose molecule is
linked to C-4 of another α-D-glucopyranose molecule by glycosidic linkage. However, branching occurs due
to the formation of a glycosidic linkage between C-1 of one glucopyranose and C-6 of another
glucopyranose. Thus, in amylopectin, all the monosaccharide units are not joined by C-1 – O – C-4 chain.
16. H2N – (CH2)3– CH2 CH2 – OH
H2N – CH – COOH H2N – CH – COOH

Lysine Serine
CH2 – SH CH2 OH
H2N – CH – COOH H2N – CH – COOH

Cysteine Tyrosine
17. Glycine ⇒ Neutral amino acid

Aspartic acid ⇒ Acidic amino acid
Lysine and arginine ⇒ Basic amino acid
18. Valine, Tyrosine and Leucine are neutral amino acids.
H
21. Only glycine: H − C − COOH is an optically inactive amino acid.
NH2
22. In the primary structure of a protein, the amino acids are linked by peptide bonds.
O CH3 O CH3
23. H2N−CH2−C−OH + H −N−CH−COOH

− H2 O
 → H2N−CH2−C−NH−CH−COOH
Glycine Dipeptide
H
Alanine
25. Denaturation results in disturbing the secondary, tertiary or quaternary structure of protein.
163


26. DNA contains D-2-deoxyribose sugar and it is present in furanose form.
5
HOH2C O OH
4 1
H H
H H
3
2
OH H
D-2-deoxyribose
27. In DNA, sugar component is 2-deoxy-D-ribose. It means that there is no −OH group at C2 position.
5
HO – CH2 O OH
1
4
3 2
OH
2- Deoxy-D-ribsoe
(present in DNA)
28. While numbering the atoms in a nucleoside, primes (') are used for furanose numbering to distinguish them
from the atoms of the base. So, sugar component in DNA is named 2′-deoxyribose (or 2′-deoxy-D-ribose).
30. A nucleoside is formed by joining the anomeric carbon of the furanose with nitrogen of a base.
32. In DNA, two bases adenine (A) and thymine (T) form complementary base pair. Similarly, guanine (G) and
cytosine (C) form complementary base pair.
33. Stachyose is a tetrasaccharide which contains two galactose, one glucose and one fructose molecules.
Glucose, fructose and galactose contain six carbon atoms each. Hence, the total number of carbon atoms in
stachyose is 4 × 6 = 24.
34. R O R′ O R′′ O R′′′

H2N – C – C – NH – C – C – NH – C – C – NH – C – C – OH
H 1 H 2 H 3 H O
Number of amino acids = 4
Number of peptide bonds = 3
Thus, in a linear tetrapeptide chain there are 4 amino acids which are linked to one another by means of
3 peptide bonds.
35. Acid hydrolysis of sucrose:
C12H22O11 + H2O Acid hydrolysis
∆
→ C6H12O6 + C6H12O6
Sucrose Glucose Fructose
1 mol sucrose requires 1 mol H2O for complete hydrolysis.

1.368 kg sucrose = 1368 g sucrose
1368
= mol sucrose
342
= 4 mol sucrose
∴ 4 mol sucrose requires 4 mol H2O for complete hydrolysis.
4 mol H2O = 4 × 18 = 72 g H2O
Density of water = 1 g/cm3
Massof water 72g
∴ Volume of water = = = 72 cm3 = 0.072 dm3
Densityof water 1g / cm3
38. Fibrous proteins are insoluble in water.

164


39. DNA contains 2-deoxy-D-ribose sugar. The message for the synthesis of a specific protein is present in
DNA and not in RNA.
41. Racemic alanine contains both (S)-alanine and (R)-alanine.
COOH COOH
C* C*
H NH2 H 2N H
CH3 CH3
(S)-alanine (R)-alanine
A linear dipeptide is formed when −COOH group of one alanine combines with −NH2 group of another
alanine. Thus, four combinations are possible: (S, S), (S, R), (R, R) and (R, S). Hence, the number of
possible dipeptides is 4.
2. Lactose is obtained by the condensation of one molecule of β-D-galactopyranose and one molecule of
β-D-glucopyranose. The glycosidic linkage is formed between C-1 of galactose and C-4 of glucose.
6
HOCH2 HOCH2
5 O 5 O
HO H OH
H H
4 1 4 1
OH H O OH H
H H H
3 2 3 2
H OH H OH
β-D-Galactose β-D-Glucose
β-1,4-glycosidic linkage
4. Sucrose is non-reducing sugar.

5. Open chain structure of glucose contains 4 asymmetric carbon atoms.
∴ number of optical isomers are 24 = 16
6. Carboxylic group of glycine reacts with amino group of tyrosine molecule to form dipeptide glycyltyrosine.
O CH2-Ph-OH-p O CH2-Ph-OH-p
H2N−CH2−C− OH + H −N−CH−COOH
− H2 O
 → H2N−CH2−C−NH−CH−COOH
Glycine Glycyltyrosine
H
Tyrosine
9. The carbon atom of −CHO group is sp2 hybridized while the rest of five carbons in glucose are sp3
hybridized.
−
12. NH 3+ − CH2 − COO
Dipolar ion
(Zwitter ion or internal salt)
CHO COOH
15. (CHOH)4 + [O] 

Bromine
water
→ (CHOH)4
CH2OH CH2OH
Glucose Gluconic acid
165

15 Introduction to Polymer Chemistry
Hints
Classical Thinking
1. Polymers are macromolecules having high molecular weights.
2. The simple molecules which combine to give polymers are called monomers.
5. Silk is protein, DNA is nucleic acid, starch is carbohydrate; hence, these are polymers.
6. Linen is a natural polymer obtained from flax plant.
8. Regenerated fibres are semisynthetic fibres obtained from natural polymers after their chemical treatment.
17. Dacron is a condensation polymer and rest are addition polymers.
30. It is a poor conductor of electricity and used for insulation in electrical cables.
36. Orlon (Polyacrylonitrile) is a homopolymer and prepared by addition polymerization of acrylonitrile using
peroxide initiator.
39. Nylon 6,6 is a condensation polymer. It is prepared by condensation polymerization of monomer (nylon salt)
formed by reaction of hexamethylenediamine and adipic acid.
43. Starting materials used for preparation of nylon 6,6 are,
Adipic acid [HOOC(CH2)4COOH]
Hexamethylenediamine [H2N(CH2)6NH2]
Total number of carbon atoms = 12
44. Nylon 6 and Nylon 6,6 both are polyamide polymers in which 6 and 6,6 represent the number of carbon
atoms present in their starting materials.
NH O
H2C C
46. n δ α H2 O
→ [ NH ( CH2)5 CO ]n
H2C CH2 533 − 543 K
(Nylon 6)
CH2 – CH2
γ β
∈-Caprolactam
47. Nylon 6 is prepared from cyclic monomer i.e., ε-caprolactum.

57. Bakelite contains many covalent crosslinks between polymeric chains which makes it rigid and an infusible
solid.
62. SBR (styrene butadiene rubber) obtained from 75 parts of butadiene and 25 parts of styrene.
64. Neoprene has the structure,
Cl
– CH2 – C = CH – CH2–
n
Neoprene
166

NH2 N +2 Cl−
34.
NaNO2 + HCl

0 − 5 °C
→ + NaCl + 2H2O
Aniline Diazonium salt
35. Hofmann elimination product is in contrast to Saytzeff elimination, that is, the least substituted alkene is
obtained as major product.
36. Aliphatic and aromatic primary and secondary amines undergo acylation reaction.
Aliphatic or aromatic primary amines will give both carbylamine and nitrous acid reaction. 2°, 3°amines also
react with nitrous acid but they will not answer carbylamine test. Thus, the set of amines given in option (C),
[CH3NH2, PhCH2NH2, Ph–NH2] will give all three reactions as it contains only aliphatic and aromatic
primary amines.
37. N +2 Cl− OH
H 2 O, 283 K

− N 2 , − HCl
→
Benzenediazonium chloride Phenol
+ − + −
H PO H O
38. (i) C6 H 5 − N 2 X →
3 2
H2 O
C6H6 (ii) C6 H 5 − N 2 X 2
283 K
→ C6H5OH
+ − + −
i.HBF
(iii) C6 H 5 − N 2 X 
ii. ∆
4
→ C6H5F (iv) CH3CH 2 OH
C6 H 5 − N 2 X  → C6H6
+ −
i.HBF
(v) C6 H 5 − N 2 X  4
ii. ∆ , aq.NaNO2 / Cu
→ C6H5NO2
39. Azo coupling reaction is an electrophilic aromatic substitution reaction in which electrophiles are positively
charged diazonium ions.
40. Benzenediazonium chloride reacts with phenol molecule and its para position gets coupled with the
diazonium salt to form p-Hydroxyazobenzene. This type of reaction is known as coupling reaction.
+ – −
N ≡ NCl + OH
OH  → N=N OH + HCl
Benzenediazonium Phenol p-Hydroxyazobenzene

chloride (orange dye)
41. Primary amines react with Hinsberg reagent to give alkali soluble product.
42. (A) C6H5 – CH2 – Cl 

Alc. NH3
→ C6H5 – CH2NH2 
2CH3 I
→ C6H5 – CH2 – N –CH3
Benzyl chloride Benzylamine
CH3
N,N-Dimethylbenzylamine
(3°)
(B) C2H5 − I 
Alc.AgCN
∆
→ C2H5N ≡ C 
Na / C2 H5 OH
→ C2H5 – N – CH3
Iodoethane Ethyl
isocyanide
H
N-Methylethanamine
(2°)
(C) Cl – (CH2)4 –Cl + KCN 

∆
→ N ≡ C – (CH2)4 – C ≡ N →
4[H], Na / C2 H5 OH
H2N – H2C – (CH2)4 – CH2 – NH2
1,4-Dichlorobutane Hexane-1,6-diamine
(1°)
Br2 / KOH
(D) CH3CH2COOH 
NH3
→ CH3CH2COONH4 
∆
→ CH3CH2CONH2 
(Hoffmann bromamide )
→ CH3CH2NH2
Propanoic acid Ethanamine (1°)
Only 1° and 2° amines react with Hinsberg’s reagent. 1° Amines react with Hinsberg’s reagent to give alkali
soluble product and 2° amines give alkali insoluble product. Thus, option (B) is the correct answer.
148

Chapter 13: Amines
1. Secondary or tertiary amines are named as N-substituted derivatives of primary amines. Since there are two
N-substituted groups in the given IUPAC name, it is a tertiary amine.
C2H5 – N – CH2 – CH2 – CH3
CH3
N-Ethyl-N-methylpropan-1-amine
(3° Amine)
2. Gabriel phthalimide reaction is useful to prepare unhindered aliphatic 1° amines. Thus, n-butylamine will be
most readily prepared by Gabriel phthalimide reaction.
CO CO
KOH ( alc.) H3C(CH2)2CH2Br
NH 
− H2 O
→ N−K+
CO CO
Phthalimide Potassium salt of phthalimide –KBr
COOH CO
H + / H 2 O or OH − / H 2 O
+ H3C(CH2)3NH2 ← Hydrolysis N − CH2(CH2)2CH3
COOH n-Butylamine CO
Phthalic acid N-Butylphthalimide
3. This reaction is known as Hofmann’s hypobromamide reaction.

Br / 4KOH
CH3 – C – NH2 
2 (aq)
→ CH3 – NH2 + 2KBr + K2CO3 + 2H2O
Methanamine
O
Acetamide
O
4. CH3 – C – NH2 + Br2 + 4NaOH → CH3 – NH2 + Na2CO3 + 2NaBr + 2H2O
Acetamide Methylamine
5. R – C – NH2 + 1Br2 + 4NaOH → R – NH2 + Na2CO3 + 2NaBr + 2H2O

6. Hofmann bromamide degradation is used only in the preparation of primary amines. It is useful for
decreasing the length of carbon chain by one carbon atom (step down reaction). In this reaction, amides are
treated with bromine and aqueous or alcoholic KOH / NaOH to obtain primary amine.
7. Trimethylamine [(CH3)3N] will be least soluble due to the absence of H-atoms attached to the nitrogen atom.
This prevents the formation of intermolecular hydrogen bonds.
8. As a consequence of combined effect of inductive effect, steric effect and solvation, the secondary amines
are the strongest bases among aliphatic amines in aqueous phase and the basic strength varies as:
2º amine > 3° amine > 1º amine > ammonia.
Hence, among the given options, dimethylamine (2º) is most basic in aqueous phase.
9. In aqueous phase, methylamines follow the basicity order as follows:
(CH3)2NH > CH3NH2 > (CH3)3N (2º > 1º > 3°)
pKb: 3.27 3.38 4.22
10. In alkylamines, +I effect of alkyl groups increases the electron density on nitrogen atom. This increases the
ease with which lone pair of electrons can be donated. Hence, ammonia will be least basic and (C2H5)2NH
will be most basic.
12. CHCl3 gives carbylamine test when heated with KOH and a primary amine.
RNH2 + CHCl3 + 3KOH (alc.)  ∆
→ RN C + 3KCl + 3H2O
Primary amine Alkyl isocyanide
149


13. When aliphatic or aromatic primary amines are heated with chloroform and alcoholic potassium hydroxide,
foul smelling alkyl isocyanides or carbylamines are formed. Secondary or tertiary amines do not undergo
such reaction. This reaction is known as carbylamine test or isocyanide test.

NH 2 N=C
14. + CHCl3 + 3KOH 

∆
→ + 3KCl + 3H2O
Aniline Phenyl isocyanide
(Phenyl isonitrile)
15. CH3COOH +  CH3COONH +4

NH3 
∆
 → CH3CONH2 + H2O
Acetic acid Ammonia Ammonium acetate Acetamide
(A)
CH3CONH2 
i. LiAlH 4 / diethyl ether
ii. H O+
→ CH3CH2NH2
3
Ethylamine
(B)
CH3CH2NH2 + CHCl3 + 3KOH 

∆
→ CH3 – CH2 – NC + 3KCl + 3H2O
Chloroform (alc.) Ethyl isocyanide
(C)
∴ B: CH3CH2NH2, C: CH3CH2NC
16. Aliphatic primary amines react with nitrous acid (HNO2) to give brisk effervescence due to evolution of N2
gas.
C2H5 − NH2 + HO − N = O NaNO2 + dil.HCl

273 K − 278 K
→ C2H5OH + HCl + N2↑
Ethyl alcohol
Ethylamine Nitrous
acid
17. In Sandmeyer reaction, copper (I) salts such as cuprous chloride, cuprous bromide or cuprous cyanide are
used to replace nitrogen in diazonium salt with –Cl, –Br or –CN respectively.
Hence, among the given options, C6H5I is not formed by Sandmeyer reaction.
NH2 N +2 Cl− CN
CuCN / KCN
18.
NaNO2 / HCl
 →  →
0 °C −5 °C ∆
+ N2 ↑
CH3 CH3 CH3

4-Aminotoluene 4-Methylbenzene 4-Methylbenzonitrile
diazonium chloride (E)
(D)
19. Hypophosphorus acid/phosphinic acid (H3PO2) reduces diazonium salts to corresponding arenes.
Me Me
H3 PO2
→
N +2 Cl− H
NH2 N +2 Cl− I
20. NaNO2 , HCl

 → KI / ∆
→
273 − 278 K − N 2 , − KCl
Aniline Benzenediazonium Iodobenzene

chloride (Z)
150

1. nH2N− CH2− COOH + nNH2 ( CH2 )5 COOH 

Polymerization
→ C CH2− NH C (CH2 )5NH
n
Glycine ε-Amino caproic acid O O
Nylon 2-nylon 6
3. Orlon is prepared by polymerization of vinyl cyanide or acrylonitrile in the presence of hydrogen peroxide.
CH2 CH
Polymerisation
nCH2 = CHCN H 2 O2
→
CN
n
Acrylonitrile
or Polyacrylonitrile
Vinyl cyanide or
or Orlon
Prop-2-enenitrile or
Acrilan
6. The structure of nylon 6,6 is:

O O H
C ( CH2)4 – C – NH – (CH2)6 – N n
There are 10 methylene (CH2) groups.

7. Cellulose nitrate is a semisynthetic polymer.
CN CN
9. nCH2 = CH – CH = CH2 + nCH2 = CH Polymerization

→ − CH2− CH = CH − CH2− CH2− CH −
Buta-1,3-diene Acrylonitrile Buna-N
n
10. For polymers containing strong intermolecular forces, the critical degree of polymerization is lower than
those containing weak intermolecular forces. Strong intermolecular forces of attraction like hydrogen
bonding are present in nylon 6, 6 ; hence it has lowest critical degree of polymerization.
12. Polyisoprene is natural rubber with weak van der Waals forces, dacron is a fibre with strong dipole-dipole
interactions called hydrogen bonding, polystyrene is thermoplastic with strength of intermolecular forces
between elastomer and fibre.
O H
13. (A) CF2 CF2 (B) C (CH2)5 N
n n
Teflon
Nylon 6
(D) CH2 CH
(C) C C O CH2 CH2 O
n
O O n Cl
PVC
Terylene
15. Glyptal is a condensation polymer of ethylene glycol and phthalic acid.
170
16 Green Chemistry and Nanochemistry
Hints
Classical Thinking
4. ZWT stands for zero waste technology.
6. DDT is harmful to living things. Thus, benzene hexachloride (BHC) is used as insecticide.
13. PVC/vinyl is believed to contain phthalates that interfere with hormonal development.
15. The green chemistry helps to reduce capital expenditure.

The green chemistry promotes manufacturing process to minimize any negative environmental effects.
Ozone layer present in stratosphere can be protected by green chemistry.
18. Nanomaterials are larger than single atoms but smaller than bacteria and cells (and even a tennis ball).
21. Two dimensions < 100 nm: Nanotubes, fibres, nanowires

All three dimensions < 100 nm: Nanoshells
24. If a bulk material is sub divided into a group of individual nanoparticles, then the total volume remains the
same, but the collective surface area is largely increased.
26. Nanomaterial-based catalysts are heterogeneous catalyst hence can be easily separated and can be
recycled. They show increase in catalytic activity due to increase in surface area with decrease in particle
size.
33. Scanning Electron Microscopy (SEM) gives information about structure of surface of material i.e.,
morphology.
37. Nanotechnology can cause pollution which is called as nano pollution.
38. High surface-to-volume ratio is an important characteristic of nanoparticles.

39. One nanometer is one billionth of a meter.
Critical Thinking
Formula weight of the desired product
1. % atom economy = ´ 100
Sum of formula weight of all the reactants used in the reaction
2. Reaction:
COOH COOH
+ CH3COCl pyridine
→ + HCl
OH Acetyl chloride
OCOCH3
Salicylic acid (C2H3OCl) Aspirin
(C7H6O3) (C9H8O4)
(X)
171


Calculation:
Formula weight of the desired product
% atom economy = ´ 100
Sum of formula weight of all the reactants used in the reaction
mass of (9C + 8H + 4O) atoms

% atom economy = × 100
mass of (7C + 6H + 3O) ) (2C ) 3H ) 1O ) 1Cl)atoms
180
= × 100
216.5
H Cl
OH C
Cl H
C C
∆ H Cl
3. + Zn  →
Cl2 , UV light
 →
H
Cl C C
Phenol Benzene H Cl
(X)
C
Cl H
Benzene hexachloride (BHC)
(Y)
O
C − ONa
+ NaOH 
CaO
→ + Na2CO3
4. ∆
Benzene
Sodium benzoate
(X)
Benzene is used as a starting material for the preparation of adipic acid.

5. The green technology developed by Drath and Frost is used for the synthesis of adipic acid having a
formula: HOOC – (CH2)4 – COOH
7. Polystyrene is used in making disposable cups and plates, take-out containers, etc.
Polyethylene terephthalate is used in making microwavable food trays.
8. The possibility of accidents including explosion is relatively higher for chemical processes involving
gaseous substances as compared to non-volatile liquids.
Design for degradation is most important to reduce the bioaccumulation or environmental persistent of
particular chemical or substance.
9. A one dimensional nanostructure is one in which two dimensions are in the nanoscale.
A two-dimensional nanostructure is one in which one dimension is in the nanoscale.
10. Nanowires have two dimensions < 100 nm.
12. Conversion of but-1-ene to n-butane involves hydrogenation (i.e., addition of hydrogen across pi bond).
Hydrogenation can be effectively carried out in the presence of Pd or Pt metal nanoparticles.
13. Sols are dispersions of colloidal particles in a liquid.
17. γ-isomer of BHC is called as gammexane or lindane.
DDT is dichlorodiphenyltrichloroethane.
DDT was used as an insecticide.
Cl
Cl Cl
Cl Cl
172

Chapter 16: Green Chemistry
and Nanochemistry
18.
(A) CHO CHO COOH COOH
Deprotection of
C6 H5 CH 2 Cl [O]
→  →
 → − OH group
OH
protection of
− OH group OCH2C6H5 OCH2C6H5 OH
m-Hydroxybenzoic acid
m-Hydroxybenzaldehyde
(B) O O
( 3 )2
CH CO O / Base +

(Pr otection of − NH 2 )
→ → Br2 H (Deprotection
 →
( Acetic acid solvent ) of − NH 2 group)
Aniline Acetanilide Br Br
p-Bromoacetanilide p-Bromoaniline
(C) O
O
NH2 NH – C – CH3 NH2
NH – C – CH3
( 3 )2
CH CO O / Base +
H (Deprotection
Conc.HNO3 + Conc H 2SO4

(Pr otection of − NH 2 )
→  288 K
→ 
of − NH 2 group)
→
Aniline
Acetanilide NO2 NO2
p-Nitroaetanilide p-Nitroaniline
19. (II) The leaves of lotus plant are superhydrophobic.

(III) Invention of Scanning Tunneling Microscope (STM) led to the discovery of fullerenes in 1986.
9. Drath and Frost developed a green technology for the preparation of adipic acid using glucose.
The IUPAC name of adipic acid is hexanedioic acid [HOOC(CH2)4COOH].
173

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MHT-CET Triumph Chemistry (Hints)

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MHT-CET Triumph Chemistry (Hints)

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MHT-CET Triumph Chemistry (Hints)

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MHT-CET Triumph Chemistry (Hints)

Chapter 04: Chemical Thermodynamics

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MHT-CET Triumph Chemistry (Hints)

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