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Textbook
Chapter No. Chapter 01: Some Basic Concepts of Chemistry

01 Some Basic Concepts of Chemistry

Hints

4. Mixture of any two liquids may be

Classical Thinking homogeneous or heterogeneous mixtures.
5. A rusty nail is a mixture.
17. BaCl2 + H2SO4  HCl + BaSO4
 20.8 + 9.8 = 7.3 + x 9. 1 L = 103 m3 = 103 cm3 = 1 dm3 = 103 mL.
x = 23.3
10. (A) The mass of a body does not vary as its
26. Isotopes are the atoms of the same element position changes.
having same atomic number (i.e., containing (B) The SI unit of length is metre.
same number of protons and electrons) but (C) A volumetric flask is used to prepare a
different mass number (i.e., different number of known volume of a solution.
neutrons).
9
32. Molecular formula of benzene is C6H6. 11. F = (C) + 32
5
 Molar mass = 12  6 + 6  1 = 72 + 6 9
= 78 g mol1 = (40) + 32
5
 1 mole of benzene is equal to 78 g of C6H6. = 72 + 32
33. Molar mass of H2 = 2 g mol 1 = 104 F
2 g will contain 6.022  1023 molecules of H2. 9
6.022  10 23
12. F = (C) + 32
 1 g of H2 will contain molecules 5
2 9
= 3.011  1023 molecules 50 = (C) + 32
5
 3  1023 molecules  50 – 32   5 = 10 C
C =
36. Atomic mass of the element 9
= 1.792  1022  6.022  1023 = 108 17. 32 g of sulphur combine with 32 g oxygen to
form 64 g of sulphur dioxide as follows:
37. 1 mole of ozone (O3) = 48 g Sulphur + Oxygen  Sulphur dioxide
0.5  48
 0.5 mole of ozone (O3) = = 24 g 32 g 32 g 64 g
1

38. Number of molecules = n  6.022  1023 Hence, (0.5 × 32 = 16 g) of sulphur will

mass of oxygen 16 combine with (0.5 × 32 = 16 g) of oxygen to
Now, n = = = 0.5 mol
molar mass of oxygen 32 give (0.5 × 64 = 32 g) sulphur dioxide.
 Number of molecules = 0.5  6.022  1023 18. N2 + 3H2  2NH3
= 3.011  1023 (1 vol.) (3 vol.) (2 vol.)
40. At S.T.P, 3 volumes of H2 give 2 volumes of ammonia
22.4 dm3 of any gas  6.022  1023 molecules 2 2
 2 L of H2 will give = L of ammonia
 6.022  1023 SO2 molecules 3
 6.022  1023 S atoms = 1.33 L of ammonia
22. Average atomic mass of Boron (B) =
10 11
(At. mass of B × %Abundance) + (At. mass of B × %Abundance)
Critical Thinking 100
3. The constituents of a compound cannot be =
10.13 u  19.60  + 11.009 u  80.40  = 10.84 u
easily separated by physical method. 100

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MHT-CET Triumph Chemistry (Hints)

23. Average atomic mass of X 1 1
4.4 g of CO2  mole  3   NA atoms
200  90  199  8  202  2 10 10
= = 199.96  200 u
100 16 g of CH4  1 mole = 5  NA atoms
24. Molecular mass of C6H5Cl  Maximum number of atoms is present in 16 g of
= (6 × Average atomic mass of C) CH4.
+ (5 × Average atomic mass of H)
+ (1 × Average atomic mass of Cl) 33. Number of atoms = n  NA  Atomicity
= (6 × 12.0 u) + (5 × 1.0 u) + (1 × 35.5 u) Number of S atoms
= 112.5 u = 6.022  1023  0.2  8
25. Molecular mass of O2 = 32 u  9.63  1023
∴ Mass of 1 molecule = 32 u
34. Molecular weight of C60H122
∴ Mass of 1 molecule of O2
= 32 × 1.66 × 10–24 g = 53.1 × 10–24 g = 12  60 + 122  1
= 720 + 122 = 842 u
26. Formula mass of KCl  6.022  1023 molecules = 842 g
= Average atomic mass of K
842
+ Average atomic mass of Cl 1 molecule = + (1 × Average atomic mass of Cl)
6.022  10 23
= 39.1 + 35.5 = 74.6 u
= 139.82  1023
27. Molecular weight of sodium oxide (Na2O)
≈ 1.4  1021 g
= 46 + 16 = 62 u
62 g of Na2O = 1 mole 35. 1 mole of BaCO3 contains 3 moles of oxygen
620 g of Na2O = 10 moles. atoms
29. 6.022  1023 atoms of H weighs 1 g.  1.5 moles of oxygen 
1
 1.5 =
1
1 3 2
 Mass of 1 atom of hydrogen =
6.0221023 = 0.5 moles of BaCO3
24
= 1.6  10 g 36. 1 L of air = 1000 mL = 1000 cc.
23
30. 1 mole  6.022  10 electrons 1000 cc of air contains 210 cc of O2
One electron weighs 9.108  1031 kg 1 mole = 22.4 L = 22400 cc.
 1 mole of electrons weighs 210
 Number of moles of O2 =
6.022  1023  9.108  10–31 kg 22400
 Number of moles that will weigh 1 kg = 0.0093 moles
1
= moles
6.022  1023  9.108  1031 16 1
37. 16 g O2 has number of moles  
1 32 2
  108 moles of electrons will weigh
9.108  6.022 14 1
14 g N2 has number of moles  
one kilogram. 28 2
31. Molar mass of NH3 = 14 + (3  1) = 17 g mol1 Number of moles is same, so number of
4.25 molecules is same.
Number of moles = = 0.25 mol
17 M
Number of molecules of NH3 = 0.25  NA 38. d= (d = density, M= mass, V = volume)
V
= 1.506  1023 molecules Since d = 1 g/mL
One molecule of NH3 contains 4 atoms.
So, M = V
 1.506  1023 molecules will contain
18 g = 18 mL
= 1.506  1023  4
= 6.024  1023 atoms  6  1023 atoms. 18 mL = NA molecules (NA = Avogadro's
number)
32. Number of atoms = n  NA  Atomicity NA
Where atomicity is the number of atoms in one 1000 mL =  1000 = 55.55 NA.
18
molecule
18 g of H2O  1 mole = 3  NA atoms 39. 1 mole of nitrogen gas  22.4 L of N2
1 1 (molar volume at S.T.P.)
16 g of O2  mole = 2  NA atoms
2 2 0.5 mole of nitrogen gas = 11.2 L of N2 at S.T.P.
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Chapter 01: Some Basic Concepts of Chemistry

40. Volume occupied by 1 mole of any gas at STP 46. 100 g of haemoglobin contains 0.33 g of Fe.
= 22.4 dm3  67200 g of haemoglobin contains
 Volume occupied by 4.4 g of CO2 i.e., 0.1 mole 67200  0.33
=
of CO2 at STP = 2.24 dm3 = 2.24 L 100
41. At STP, 22.4 L (22400 cm3) oxygen gas = 221.76 g of Fe
= 1 mole oxygen gas 221.76
Number of atoms of Fe =
Hence, 11.2 cm3 corresponds to 56
11.2 = 3.96  4
= 0.0005 mole
22400
Competitive Thinking
Massof a substance
42. Number of moles =
Molar massof thesubstance 4. Average atomic mass =
10
B  percentage+atomic mass of 11B  percentage
= 6 0.0 g –1 = 2 mol atomic mass of
30 g m ol 100
Number of moles of a gas (n) Let the % abundance of 10B isotope = x.
Volume of the gas at STP % abundance of 11B isotope = 100 – x.
= Average atomic mass = 10.81
Molar volume of the gas
From formula, Average atomic mass
 Volume of the gas at STP
10  x  11  100  x 
= n × Molar volume of the gas = = 10.81
= 2 mol × 22.4 dm3 mol–1 = 44.8 dm3 1 00
10 x + 1100 – 11x = 10.81 × 100
43. Vn –x = –1100 + 1081
Number of moles (n) x = 19
Mass of the substance Percentage abundance of lighter isotope,
= 10
Molar mass of the substance B = 19%.
mass 1
 n=  Vn 5. 6.022 1023 dioxygen molecules are present in
atomic mass(M) M 1 mole i.e., 32 g of dioxygen.
Atomic Mass of O = 16  1.8  1022 dioxygen molecules will be present in
Atomic Mass of N = 14 1.8  10 22  32
V(O) n (O) M ( N) = 0.96 g of dioxygen.
   6.022  10 23
V( N) n ( N) M (O)
6. Number of moles in 4.4 g of CO2
V(O) 14 7 4.4
  = = 0.1
V( N) 16 8 44
 The ratio is 7 : 8 Number of oxygen atoms in 1 mole of CO2
= 2  NA
44. Baking soda or sodium hydrogen carbonate
 Number of oxygen atoms in 0.1 mole of CO2
(NaHCO3) is a compound. Diamond and
charcoal are different forms of the element = 0.1  2  NA
carbon. 22 carat gold is an alloy of gold with = 0.2  6.022  1023
other metals (mainly copper). Hence, it is a = 1.20  1023
mixture. 7. Total number of atoms in a given amount of
45. In compound B, 32 parts of X react with 84 H2O = n  NA  3
parts of Y. 0.05
=  6.022  1023  3
 In compound B, 16 parts of X react with 42 18
parts of Y. = 5.05  1021
In compound C, 16 parts of X react with x parts
of Y. 8. Total number of atoms in a molecule
The ratio of masses of Y, which combine with = n  NA  Atomicity
fixed mass of X in compounds B and C, is 3:5. Atomicity of NH3, O2, H2 and He molecules are
4, 2, 2 and 1 respectively.
B 42 3 17 g of NH3 = 4  NA atoms
C x 5
4.25 g of NH3 = 
4.25 
   4  NA = NA atoms
42  5  17 
 x= = 70
3 32 g of O2 = 2  NA atoms
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MHT-CET Triumph Chemistry (Hints)

28 N  1 mol of X3Y2 = 180 g
 8 g of O2 =  NA = A atoms
32 2 i.e., Molecular weight of X3Y2 = 180
2 g of H2 = 2  NA atoms = 2NA atoms Let atomic weights of X and Y be x and y
4 g of He = NA atoms respectively.
Thus, the system that contains 2 g of H2 has
 x + 2y = 100 ….(1)
maximum numbers of atoms.
3x + 2y = 180 ….(2)
9. 1 mole of water Subtracting (1) from (2),
= 18 g of water
2x = 180  100
= 6.022 1023 molecules of water
 x = 40
 18 moles of water
Substituting x = 40 in (1),
= 18  6.022  1023 molecules of water
40 + 2y = 100
= 1.08396  1025 molecules of water
 y = 30
10. Option (A):
18 mL of water = 18 g = 1 mol of water 15. Let the mass of CH4 and SO2 be w1 and w2,
Option (B): respectively.
0.18 w1 1
0.18 g water = = 0.01 mol of water 
18 w2 2
Option (C): n1 w1 M 2 1 64 2
     
0.00224 L of water vapours at 1 atm and 273 K n 2 M1 w 2 16 2 1
(STP conditions) = 2.24 mL of water
n2 1
2.24  
= = 0.1 mol of water n1 2
22.4
Option (D) has 10–3 mol of water. Therefore, the ratio of number of molecules of
SO2 to CH4 is 1:2.
Hence, 18 mL of water, i.e., option (A) has
maximum mol of water and hence, it contains
16. 98 mg H2SO4 = 98  10–3 = 0.098 g
maximum number of water molecules.
98 g H2SO4 = 6.023  1023 molecules
12. Total weight of person = 75 kg
6.023  10 23
10
 0.098 g H2SO4 =  0.098
Mass due to 1H atoms = 75  = 7.5 kg 98
100
= 6.023  1020 molecules
Mass of 2H atom is twice that of 1H atom.
Now, 3.01  1020 molecules are removed so the
All 1H atoms are replaced by 2H atoms.
remaining molecules are
Hence, mass increase is twice i.e., by 7.5 kg.
= 6.023  1020 – 3.01  1020
13. When Avogadro number is 6.022  1023 mol1, = 1020 (6.023 – 3.01)
the mass of 1 mol of carbon = 12 g
= 3.0123  1020
 Mass of 1 mol of carbon when Avogadro
Number of moles of H2SO4 left
number is 6.022  1020 mol1
3.013  10 20
=
12  6.022  10 20
= 12  103 g = = 0.5  10–3
6.023  10 23
6.022  10 23

Thus, the mass of 1 mol of carbon is changed.

17. 5.6 L at S.T.P. weighs 7.5 g.
14. 0.1 mol of XY2 = 10 g 7.5  22.4
 22.4 L at S.T.P weighs = 30 g
 1 mol of XY2 = 100 g 5.6
i.e, Molecular weight of XY2 = 100  Molar mass of gas = 30 g mol–1
0.05 mol of X3Y2 = 9 g Hence, the gas is NO.
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Chapter 01: Some Basic Concepts of Chemistry

40. Volume occupied by 1 mole of any gas at STP 46. 100 g of haemoglobin contains 0.33 g of Fe.
= 22.4 dm3  67200 g of haemoglobin contains
 Volume occupied by 4.4 g of CO2 i.e., 0.1 mole 67200  0.33
=
of CO2 at STP = 2.24 dm3 = 2.24 L 100
41. At STP, 22.4 L (22400 cm3) oxygen gas = 221.76 g of Fe
= 1 mole oxygen gas 221.76
Number of atoms of Fe =
Hence, 11.2 cm3 corresponds to 56
11.2 = 3.96  4
= 0.0005 mole
22400
Competitive Thinking
Massof a substance
42. Number of moles =
Molar massof thesubstance 4. Average atomic mass =
10
B  percentage+atomic mass of 11B  percentage
= 6 0.0 g –1 = 2 mol atomic mass of
30 g m ol 100
Number of moles of a gas (n) Let the % abundance of 10B isotope = x.
Volume of the gas at STP % abundance of 11B isotope = 100 – x.
= Average atomic mass = 10.81
Molar volume of the gas
From formula, Average atomic mass
 Volume of the gas at STP
10  x  11  100  x 
= n × Molar volume of the gas = = 10.81
= 2 mol × 22.4 dm3 mol–1 = 44.8 dm3 1 00
10 x + 1100 – 11x = 10.81 × 100
43. Vn –x = –1100 + 1081
Number of moles (n) x = 19
Mass of the substance Percentage abundance of lighter isotope,
= 10
Molar mass of the substance B = 19%.
mass 1
 n=  Vn 5. 6.022 1023 dioxygen molecules are present in
atomic mass(M) M 1 mole i.e., 32 g of dioxygen.
Atomic Mass of O = 16  1.8  1022 dioxygen molecules will be present in
Atomic Mass of N = 14 1.8  10 22  32
V(O) n (O) M ( N) = 0.96 g of dioxygen.
   6.022  10 23
V( N) n ( N) M (O)
6. Number of moles in 4.4 g of CO2
V(O) 14 7 4.4
  = = 0.1
V( N) 16 8 44
 The ratio is 7 : 8 Number of oxygen atoms in 1 mole of CO2
= 2  NA
44. Baking soda or sodium hydrogen carbonate
 Number of oxygen atoms in 0.1 mole of CO2
(NaHCO3) is a compound. Diamond and
charcoal are different forms of the element = 0.1  2  NA
carbon. 22 carat gold is an alloy of gold with = 0.2  6.022  1023
other metals (mainly copper). Hence, it is a = 1.20  1023
mixture. 7. Total number of atoms in a given amount of
45. In compound B, 32 parts of X react with 84 H2O = n  NA  3
parts of Y. 0.05
=  6.022  1023  3
 In compound B, 16 parts of X react with 42 18
parts of Y. = 5.05  1021
In compound C, 16 parts of X react with x parts
of Y. 8. Total number of atoms in a molecule
The ratio of masses of Y, which combine with = n  NA  Atomicity
fixed mass of X in compounds B and C, is 3:5. Atomicity of NH3, O2, H2 and He molecules are
4, 2, 2 and 1 respectively.
B 42 3 17 g of NH3 = 4  NA atoms
C x 5
4.25 g of NH3 = 
4.25 
   4  NA = NA atoms
42  5  17 
 x= = 70
3 32 g of O2 = 2  NA atoms
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Textbook
Std. XI :No.
Chapter Triumph Chemistry

04 Structure of Atom

Hints

Protons and neutrons are collectively called as

Classical Thinking nucleons. Also, the mass number is the sum of
protons and neutrons present in the nucleus of
1. The nucleus of an atom consists of protons and an atom. Therefore, isobars always have the
neutrons which are collectively called as same number of nucleons.
nucleons.
19. Atoms with different atomic numbers but same
7. An -particle is the nucleus of helium atom. It mass number are known as isobars.
has a mass of approximately 4 u and a charge of
+2 units. It is represented as 42 He or 42  . 28. According to the Planck’s quantum theory of
radiation, the energy of one quantum of
11. The atomic number of the element is Z. radiation is directly proportional to its frequency
 Number of protons = Z i.e., E = h.
Mass number (A) = Number of protons (Z)
+ Number of neutrons 34. For Pfund series in the infrared region, n1 = 5.
 Number of neutrons = Mass number (A) 36. When an electron jumps from K to L shell,
 Number of protons (Z) energy is absorbed as L shell is of higher energy
=AZ as compared to K shell.
13. A nuclide is represented as AZ X . 37. According to Bohr’s theory, the angular
Here, Z = 6 momentum of electron, mvr is integral multiple
Now, A = Z + N = 6 + 8 = 14 of h/2.
Hence, nuclide is represented as 146 X . nh
mvr =
12 2
14. For C, mass number (A) = 12
Also, atomic number of C is 6. The electron is in the fourth Bohr’s orbit,
Therefore, number of protons (Z) = 6 therefore, n = 4.
 Number of neutrons = Mass number (A) h 2h
 mvr = 4 =
 Number of protons (Z) 2 
=AZ n2
= 12  6 = 6 39. Radius of Bohr’s orbit (rn) = 52.9  pm
Z
15. In a neutral atom of the element 231
89 X , where n = principal quantum number
atomic number (Z) is 89 and the mass number Z = atomic number of the atom/ion
2
(A) is 231. rn  n [ Z = 1]
 Atomic number (Z) = Number of protons
r2 n2 (2)2 4
= number of electrons  = 22 = =
= 89 r1 n1 (1)2 1
Number of neutrons = Mass number (A) Thus, the ratio of radii of second and first
 Number of protons (Z) Bohr’s orbits of H-atom is 4 : 1.
 Number of neutrons = 231  89 = 142
42. According to de-Broglie, the wavelength  of a
16. Isotopes have same atomic number i.e., same particle of mass m moving with a velocity v is
number of protons but different mass number given as
i.e., different number of neutrons. h
=
18. The atoms of different neighbouring elements mv
having the same mass number but different h
 mv =
atomic number are called isobars. 

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Chapter 04: Structure of Atom

44. According to de Broglie equation, 68. d-orbitals have l = 2. So, m has 5 different
h values i.e., 2, 1, 0, +1 and +2. Hence,
 = where h is Planck’s constant.
p d-orbitals have 5 orientations.
1 69.
 
p Orbital Shape
s spherical
46. Mathematically, Heisenberg’s uncertainty px dumb-bell
principle is expressed as: dxy double dumb-bell
h pz dumb-bell
x  px  Where h is Planck’s constant,
4
70. The energy of an orbital in the hydrogen atom or
x is the uncertainty in the determination of hydrogen-like species is determined by the
position and px is the uncertainty in the principal quantum number alone.
determination of momentum of a very small
moving particle. 71. The ground state of an atom corresponds to the
lowest total electronic energy. It is also the most
48. To fully specify an electron in an atom, four stable state of an atom.
quantum numbers are required. These quantum If two orbitals have the same (n + l) values then
numbers which designate and distinguish orbital with the lower value of n is of lower
electrons in atomic orbitals are viz., principal energy.
quantum number (n), azimuthal quantum In hydrogen atom, 2s and 2p are degenerate
number (l), magnetic quantum number (ml) and orbitals.
electron spin quantum number (ms). 73. Hund’s rule states that When several orbitals of
2 equal energy (degenerate orbitals) are available,
51. Each main shell contains a maximum of 2n
electrons. the electrons first fill all the orbitals singly
For ‘M’ shell, n = 3. before pairing in any of these orbitals”.
Therefore, the maximum numbers of electrons Thus, this principle helps in understanding the
present in the ‘M’ shell = 2 × (3)2 = 18. filling of electrons in p, d and f orbitals, which
have more than one kind of orbitals.
54. For N shell, n = 4. The total number of subshells
in a main shell is equal to n. Therefore, N shell 74. According to Hund’s rule when several orbitals
has 4 subshells (4s, 4p, 4d, 4f). of equal energy (degenerate orbitals) are
available, the electrons first fill all the orbitals
57. The maximum number of electrons in a given singly before pairing in any of these orbitals.
sub-shell is given by 2(2l + 1). According to Aufbau principle, in the ground
Thus, for f-subshell, l = 3. state of the atoms, the orbitals are filled with
 Number of electrons = 2(2l + 1) electrons in order of the increasing energies.
= 2(2  3 + 1) Electron
= 2  7 = 14 Hund’s Aufbau
distributions in
rule principle
58. 3f orbital does not exist because for n = 3, ground state
l = 0, 1, 2 i.e., it can have s, p and d subshell 2s 2p Violated Not violated
only.
59. The magnetic quantum number (ml) can have
any integral value between –l to +l through 2s 2p Not Violated
zero. For l = 3, ml can have values: –3, –2, –1, violated
   
0, +1, +2, +3.
61. (A) Azimuthal quantum number (l) can have 2s 2p Violated Violated
only positive values between 0 and (n  1).  
(B) Electron spin quantum number describes
the spin state of the electron in an orbital. Not Not violated
(C) Magnetic orbital quantum number 2s 2p violated
describes the relative spatial orientation of
  
the orbitals in a given subshell.
64. There is only one orientation for s-orbital 76. Iron (Fe) has atomic number 26. The electronic
( l = 0) and so, it is spherically symmetrical configuration for iron is:
about the nucleus. 1s2 2s2 2p6 3s2 3p6 4s2 3d6
7
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MHT-CET Triumph Chemistry (Hints)

78. When 2p orbital is completely filled then 6. Number of protons = Atomic number (Z) = 17
electrons enter the 3s. Thus, the electronic Number of neutrons = 18
configuration given in option (D) is not possible  Mass number (A) = 17 + 18 = 35
in the ground state of an atom. A neutral atom is represented as AZX .
79. 8O =   Hence, the given neutral atom of element X is
1s 2s 2p Unpaired electrons represented as 1735 X .

80. The atomic number of Cu is 29. Its electronic 7. Number of neutrons = Mass number (A)
configuration is [Ar] 4s1 3d10.  Atomic number (Z)
The 3d orbital is completely filled. So, the
number of unpaired electrons in the d-orbitals of Atom Number of neutrons
an atom of the element with atomic number 29 235
92 U 235  92 = 143
is zero. 238
U 238  92 = 146
92
1
81. The electronic configuration of H is 1s . The 239
93 Np 239  93 = 146
negative charge on the H atom indicates that one 240
Np 240  93 = 147
electron is added to the 1s orbital. 93

Hence, electronic configuration of H is 1s2.  Among the given atoms, the least number of
82. Isoelectronic species have same number of neutrons is in 235
92 U.

electrons.
8. Neutrons are neutral in nature so they do not
83. Electrons do not lose energy as long as they are contribute in the charge on the atom.
revolving in a particular orbit, also referred to as Protons have unit positive charge while
stationary orbit. electrons have unit negative charge. In the given
atom, there are 17 protons, 18 neutrons and
84. Protium  H  , an isotope of hydrogen
1
1 contains 18 electrons.
only one proton and one electron. So, number of electrons is more than number of
protons by 1. So, the charge on the given atom
85. n = 3, l = 0 refer to 3s-level. The electronic is 1.
configuration of 19K is 1s2 2s2 2p6 3s2 3p6 4s1.
1
Therefore, 19K has 2 electrons with n = 3, 9. The atomic number of  1940 K  is 19.
l = 0.
 The number of electrons in neutral K atom = 19.
86. According to Aufbau principle, in the ground Since, the atom has one negative charge, so, the
state of the atoms, the orbitals are filled with 1
number of electrons in  1940 K  ion
electrons in order of the increasing energies.
The increasing order of energy of different = 19 + 1 = 20
orbitals in an atom is:
10. Number of electrons is determined by the
1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d atomic number. Chemical nature of the atom is
< 5p < 6s < 4f < 5d and so on. Hence, the next determined by the electrons and its
37th electron will go into the subshell of 5s. configuration. The atomic number is number of
88. According to Bohr’s theory, stationary states protons or electrons. Hence, addition of a
with smaller values of ‘n’ have large and neutron do not affect the number of electrons or
negative energy. the chemical nature of the atom or the atomic
number. As atomic mass is sum of protons and
Critical Thinking neutrons, introduction of a neutron into the
nucleus of an atom would lead to a change in
1. When electric field of fixed strength is applied, the mass number.
cathode rays are deflected towards positive
electrode since cathode rays consists of 11. 35
17 Cl and 37
17 Cl are isotopes of chlorine. They
negatively charged particles. differ in mass number i.e., number of neutrons +
number of protons = number of nucleons.
5. In a neutral atom, the number of protons is
exactly equal to the number of electrons present 12. Isotopes have similar chemical properties and
in it. Hence, the number of electrons in a neutral occupy same position in the periodic table.
atom is equal to its atomic number i.e., the Isobars have different chemical properties and
number of protons. occupy different position in the periodic table.
88
 

Chapter 04: Structure of Atom

14. Chlorine has two stable isotopes: Cl-35 and  Z2 
Cl-37. 23. En = – 2.18  10–18  2 
J
n 
Let the natural abundance of Cl-35 isotope be x
 22 
% and that of Cl-37 be (100 – x)%. E2 = – 2.18  10–18  2 
J
Hence, 2 
Average atomic mass = – 2.18  10–18 J
 Atomic mass of Cl  35  x  24. According to Bohr’s theory,
  Atomic mass of Cl  37  100  x   rn  n2
= r1 = , n1 = 1, n3 = 3
100
2
35  x + 37  100  x  r1  1  1
  
35.5 = r3  3  9
100
 x = 75  r3 = 9r1 = 9
100 – x = 25 n2
Natural abundance of Cl-35 = 75% 25. Radius of Bohr’s orbit (rn) = 52.9  pm
Z
Natural abundance of Cl-37 = 25% where n = principal quantum number
Hence, the ratio of Cl-37 and Cl-35 is 1:3. Z = atomic number of the atom/ion
15. Phenomena such as diffraction and interference rH = 52.9 pm [ n = 1 and Z = 1]
of light could be explained by treating light as n2 4
electromagnetic wave. r
He
= 52.9   52.9  = 105.8 pm
Z 2
2
16. All the electromagnetic radiations such as n 4
r
Li 2 
= 52.9  = 52.9  = 70.5 pm
X-rays,  rays, visible light, etc., have same Z 3
speed i.e., speed of light. n2 9
r
Li 2 
= 52.9  = 52.9  = 158.7 pm
Z 3
17.
n2 4
Radiation Frequency (Hz) r = 52.9  = 52.9  = 52.9 pm
Be3  Z 4
Microwaves 1010
Thus, the radius of Be3+(n = 2) orbit is same as
UV rays 1016
that of the first Bohr’s orbit of hydrogen atom.
IR rays 1013
Radio waves 106 26. Speed =
distance
time
 distance
18. =  Time =
c speed
c 3  108 For an electron to complete one revolution in
= = = 1.5  102 m
 2  106 the Bohr’s orbit of H atom,
Distance = circumference of orbit of radius r
19.  = 600 nm = 600  109 m
= 2r
c 3  108 ms 1
= = = 5.0  1014 Hz According to Bohr’s theory, the angular momentum
 600  109 m of electron, mvr is integral multiple of h/2.
 c nh
20.  (   ) mvr =
c  2
nh
12  1014 s 1  Speed (v) =
 = 2mr
3.0  108 ms 1
nh
 = 4  10 m
6 1
or 4
 = 4  10 cm
1  Time = 2r 
2mr
21. Quantum refers to the smallest quantity of 2mr
= 2r 
energy that can be emitted or absorbed in the nh
form of electromagnetic radiation. 42 mr 2
=
nh
22. Bohr’s model of an atom could explain the
atomic spectra of hydrogen and hydrogen like 27. For Balmer series, n1 = 2. The 1st line in Balmer
species (i.e., species containing only one series is due to electronic transition from n2 = 3
electron). Li+ has 2 electrons and hence its to n1 = 2. Hence, the 2nd line in Balmer series
atomic spectrum could not be explained by will be due to the electronic transition from n2 =
Bohr’s model of an atom. 4 to n1 = 2.
9
 

MHT-CET Triumph Chemistry (Hints)

28. For Balmer series, n1 = 2. 36. According to Heisenberg’s uncertainty
The first line in the series is obtained for h
principle, x  vx ≥
electronic transition: n1 = 2 and n2 = 3. 4m
The second line in the series is obtained for h
electronic transition: n1 = 2 and n2 = 4.  x 
4m  v x
So, the third line in the series is obtained for
electronic transition: n1 = 2 and n2 = 5 i.e., Fifth 6.626  1034

Bohr orbit to second one. 4  3.14  0.02  9.218  106
 2.86  1028 m
29. For Lyman series, n1 = 1 i.e., stationary orbit is
K. So, transition from any higher orbit to K 37. According to Heisenberg’s uncertainty principle,
shell will give Lyman series. h
x  px 
 1 1  4
30. E = – 2.18  10–18   2
2
 n1 n 2  x = px
h
= – 2.18  10–18 1 1  px  px 
 2 2 4
3 4 
h
 42  32  px2 
= – 2.18  10–18  2 2 4
3 4 
1 h
–18  7  px 
= – 2.18  10   2 
 144 
1 h
= – 2.18  10–18  0.0486 m  vx  ( px = m  vx)
2 
= – 0.106  10–18 J
1 h
= – 1.06  10–19 J  vx 
2m 
32. According to de-Broglie equation,
h 38. vA = 0.05 ms1
= .
mv vB = 0.02 ms1
1 mB = 5 mA
For same velocity,   .
m According to Heisenberg’s uncertainty
SO2 molecule has least wavelength because its principle,
mass is highest among given options. h
x  vx 
33. According to de Broglie equation, 4m
h h xA vA mB
= =   
mv p xB vB mA

h 6.6  1034 xA 0.05

 p= = = 3  1023 kg m s1   5
 2.2  1011 xB 0.02
xA
34. v = 1.0  103 m/s  2
xB
m = 1.67  1027 kg
h = 6.63  1034 J s 39. Mass of an electron = 9  1028 g
According to de Broglie equation,
px = 1  1018 g cm s1
h 6.63  1034
 =  m vx = 1  1018 g cm s1
mv 1.67  1027  1.0  103
1  1018
= 3.97  1010 m = 0.397  109 m vx = = 0.11  1010 cm s1
9  1028
= 0.40 nm
= 1.1  109 cm s1
35. According to Heisenberg’s uncertainty principle,  1  109 cm s1
h
x  vx 
4m 42. ml can have any integral values between l and
6.626  1034 +l through zero.

4  3.14  9.1  1031 When l = 2, ml = 2, 1, 0, + 1, +2.
 5.8  105 m2 s1 Thus, ml = 3 is not permissible, when l = 2.
10
 

Chapter 04: Structure of Atom

43. ml has seven values, so ml = 3, 2, 1, 0, +1, 52. According to Aufbau principle, in the ground
+2, +3. Hence, l should be 3. state of the atoms, the orbitals are filled with
OR electrons in order of the increasing energies.
The relationship between ml and l is given by: The increasing order of energy of different
ml = 2l + 1 orbitals in an atom is:
7 = 2l + 1 1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d
6 = 2l < 5p < 6s < 4f < 5d and so on. Hence, new
6 electron will enter in 4p orbitals.
l= =3
2 53. According to Aufbau principle, in the ground
44. Each subshell contains a maximum of state of the atoms, the orbitals are filled with
2(2l + 1) electrons. electrons in order of the increasing energies.
For l = 3, The increasing order of energy of different
2(2l + 1) = 2(2  3 + 1) = 14 electrons orbitals in an atom is:
1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d
45. The f subshell contains seven orbitals. Each < 5p < 6s < 4f < 5d and so on. Hence, the
1 correct sequence as per Aufbau principle is
orbital can have an electron with spin  .
2 1s < 2p < 4s < 3d.
Hence, the maximum number of 4f electrons
55. According to Pauli’s exclusion principle, no two
1
having spin quantum number  is 7. electrons in an atom can have the same set of
2 four quantum numbers.
46. When n = 3, the permissible values of l = 0, 1 56. According to Hund’s rule, each of the five-
and 2. Therefore, the set of quantum numbers degenerate d-orbitals must get one electron of
given in option (A) is not permitted. parallel spin before any one of them receives the
47. For 4f-orbital, n = 4 and l = 3. second electron of opposite spin.
 ml = + 3, + 2, +1, 0, – 1, – 2, – 3 58. = [Ar] 3d5 4s1.
24Cr
ms = +1/2, 1/2
Thus, among the given options, the set of      
quantum numbers in option (A) is correct for an
electron in 4f orbital. Number of unpaired electrons = 6.
49. d 2 has two lobes along z-axis and a doughnut 59. 30Zn = 1s2 2s2 2p6 3s2 3p6 4s2 3d10
Total number of electrons in all p-orbitals
z

shaped ring around the nucleus in xy-plane. The

= 6 + 6 = 12
remaining four d-orbitals have four lobes.
60. Both Ne and O2– have 10 electrons each.
50. The energy of the main shell increases as the
value of n increases. Hence, orbitals described 61. Lithium (Li) with atomic number 3 forms the
by n = 1, n = 2 and n = 3 will have different Li+ ion on loss of an electron from its outermost
energies. orbit. The charge on Li+ ion will be same in
Orbitals having n = 3 and l = 2 indicates 3d magnitude to that of lost electron, but opposite
subshell. d subshell contains five d-orbitals. In in sign. Hence, the value of free charge on Li+
the absence of electric and magnetic fields, all ion will be 1.6  1019 C.
the five d-orbitals are degenerate i.e., of same
energy. 62.
Thus, the orbitals described by the three Charge Mass
quantum numbers n = 3, l = 2, m = 0 and n Species Charge/Mass
(units) (amu)
= 3, l = 2, m = 1 will have the same energy in Proton +1 1 1
the absence of magnetic and electric fields. =1
1
51. Lower is the value of (n + l), lower is the energy Electron 1  1/1837 1
of the atomic orbital. Since, the given atomic = 1837
1 / 1837
orbitals belong to the same shell, they have
same value of n. So, the atomic orbital with Neutron 0 1 0
lower value of l will have lower energy. The l Alpha +2 4 2 1
particle 
values for s, p, d and f orbitals are 0, 1, 2 and 3 4 2
respectively. Therefore, energy of atomic
orbitals in a particular shell is in the order s < p  Thus, among the given options, electron has
< d < f. greater charge to mass ratio.
11
 

MHT-CET Triumph Chemistry (Hints)

63. n + l = 6 and the permissible values of l are 0 to 3. E1 = 25 eV
(n  1), which suggest that n > l. E2 = 50 eV
So, the possible number of subshells would be E2 = 2 E1
n = 4, l = 2 According to Planck’s quantum theory of radiation,
n = 5, l = 1 hc
n = 6, l = 0 E=

 3 subshells are possible.
hc hc
65.   2
2 1
Species Al3+ C O2 F
Number of protons 13 6 8 9 1 2

(Z)  2 1
Mass number (A) 27 12 16 19  λ1 = 2 λ2
Number of neutrons 14 6 8 10
(A  Z) 7. For Balmer series, n1 = 2 and n2 = 3, 4, 5,…..
Number of electrons 10 6 10 9  1 1  5R 1
 1  R  2  2   cm
Among the given species, O 2
has more  2 3  36
electrons than neutrons.
66. The set of quantum numbers n = 3, l = 0, m  1 1  3R 1
2  R  2  2   cm
= 0, s = 1/2 represent 3s subshell.  2 4  16
Element Electronic configuration
Mg 1s2 2s2 2p6 3s2  1 1  21R 1
3  R  2  2   cm
He 1s2  2 5  100
Ne 1s2 2s2 2p6
F 1s2 2s2 2p5 8. 1 J = 6.242  1018 eV
Thus, among the given elements, only Mg has  Z2 
electrons in 3s subshell. So, the given set of En = – 2.18 × 10 –18
 2  J atom1
quantum numbers represents an electron of the n 
element Mg. 1
= –2.18 × 10–18 × × 6.242  1018 eV atom1
67. When ml = 1, the lowest possible value of l = 1. n2
For s-orbital, l = 0. So, an electron having ml = 13.6 1
1 cannot be present in the s-orbital. =  eV atom
n2

13.6
Competitive Thinking 9. En = eV
n2
1. Mass of one electron = 9.108  10–31 kg For excited state, n  1.
1 13.6
Number of electrons in 1 kg = When n = 2, E2 = = – 3.4 eV
9.108  1031 (2) 2
Number of moles of electrons in 1 kg
1 13.6
= When n = 3, E3 = = – 1.5 eV
31 (3) 2
9.108  10  6.023  1023
1  Among the given options, the energy of a
= possible excited state of hydrogen is
9.108  6.023  108
1 – 3.4 eV.
=  108
9.108  6.023 10. E∞ = 0
2. Atomic number of P = 15 2.18  1018
Mass number of P = 31 E3 = J atom1
 3
2

 Number of protons = 15
Number of neutrons =  0.242  1018 J atom1
= Mass number  number of protons
n2 n2
= 31  15 11. rn = 52.9  pm = 0.529  Å
= 16 Z Z
The phosphorus atom gains 3 electrons and For hydrogen; n = 2 and Z = 1, therefore
forms P3 ion. Thus, the number of electrons in  Radius of second Bohr orbit
P3 = 15 + 3 = 18 = 0.529  (2)2 = 2.12 Å
12
 

Chapter 04: Structure of Atom

n2 19. When l = 2, ml = +2, +1, 0, 1, 2, and not 3.
12. rn = 52.9  pm Therefore, the set of quantum numbers in option
Z
n2 (D) is not permissible.
52.9 pm = 52.9  pm
Z 22. Higher the value of (n + l), the greater is the
n2 energy. For same value of (n + l), higher the
 1 value of ‘n’, the greater is the energy.
Z
This is possible when n = 2 and Z = 4. P : n = 4; l = 3; (n + l) = 7,
2.18  1018 Z2 Q : n = 5; l = 2; (n + l) = 7,
En = R : n = 5; l = 1; (n + l) = 6,
n2
18 S : n = 4; l = 2; (n + l) = 6.
= 2.18  10 2  (4)
2

(2)
Thus, the order of energy of the given electrons
is, S < R < P < Q
= 8.72  1018 J
23. (i) n = 4, l = 1 4p-orbital
13. Mass = 100 gm = 0.1 kg
(ii) n = 4, l = 0 4s-orbital
Velocity = 100 cm/s = 1.0 m/s
(iii) n = 3, l = 2 3d-orbital
h = 6.6  1034 J s = 6.6  1034 kg m2/s
(iv) n = 3, l = 1 3p-orbital
According to de Broglie equation,
Hence, 3p < 4s < 3d < 4p
h 6.6  1034
= = = 6.6  10–33 m
mv 0.1  1.0 24. The orbitals are 4d (I), 3d (II), 4p (III) and
31 3p (IV).
= 6.6  10 cm
2 The increasing order of energy is:
14. r = a0n 3p < 3d <4p < 4d.
 r = 52.9  (2)2 pm
Now, 25. According to (n + l) rule, higher the value of
n = 2r (n + l), higher is the energy of the electron.
2r For P; (n + l) = 3 + 2 = 5,
= For Q; (n + l) = 3 + 0 = 3.
n
Thus, P has greater energy than Q.
2  52.9  22
=
2 28. An orbital can accommodate maximum of two
= 211.6  pm electrons only.
15. According to de Broglie equation: 29. Cu (Z = 29) has electronic configuration as:
1 1 [Ne] 3s2 3p6 3d10 4s1.
A = and B =
pA pB
30. 19th electron of chromium is 4s1; n = 4, l = 0, ml
h 1
(  = where, h = Planck’s constant) = 0, ms = +
p 2
A 13
= 31. Electronic configuration of chlorine atom is 1s2
B 1
2s2 3s2 3p5. Therefore, one of the three 3p
B = 33.33  3 orbitals contains an unpaired electron. For 3p
= 99.99 nm orbital, n = 3, l = 1.
 100 nm or 1  10–7 m
32. Rubidium (Z = 37)  1s2 2s2 2p6 3s2 3p6 4s2
17. Maximum number of orbital in a shell is n2. 3d10 4p6 5s1
 Maximum number of orbital in 5th shell = 52 So, last electron enters 5s orbital.
= 25 Hence, n = 5, l = 0, m = 0, s = ± 1/2.
Each of these orbital is associated with both ms
= +1/2 and −1/2. 35. Energy required for breaking 1 mole of Cl  Cl
 The number of orbitals associated with quantum bonds in Cl2 = 242 kJ
numbers n = 5, ms = +1/2 is 25. i.e., Energy required for breaking Cl  Cl bonds
in 6.02  1023 molecules = 242  103 J.
18. For a given value of azimuthal quantum number
(l), the magnetic orbital quantum number (ml)  Energy required to break a single Cl  Cl bond
have values between l and +l through 0. 242  103
= J
In option (C), value of ml is 1 which is not 6.02  1023
possible as the azimuthal quantum number is hc
E=
zero. 
13
 

MHT-CET Triumph Chemistry (Hints)

hc 6.626  1034  3  108 hc
= = E=
E 242  103 / 6.02  1023 
= 0.494  106 m  E
1
= 494  109 m 
= 494 nm Energy of a photon is inversely proportional to
wavelength. Hence, among the given options,
36. According to Rydberg equation, the transition from n = 6 to n = 5 will give rise
1  1 1  to the least energetic photon.
  RH  2  2 
  n1 n 2 
37. When the original element  X
A
Z emits a beta
Values of 1 () particle (i.e., an electron), the daughter
cm1  cm
n1 and n2  element formed has same mass number while
(A) n1 = 5, n2 = 6 1340.5 7.46  104 the atomic number increases by 1. Since the
(B) n1 = 3, n2 = 5 7799.3 1.28  104 daughter element formed is 147 N , the original
(C) n1 = 1, n2 = 6 106631.4 9.38  106 element has A = 14 and Z = 6.
(D) n1 = 4, n2 = 5 2467.8 4.05  104  The number of neutrons in the nucleus of the
original element = A – Z = 14 – 6 = 8.
Energy of a photon is given as

Hints to Evaluation Test

1. l = l represents a p-orbital, which can 4. The elements, from atomic number 1 to 30,
accommodate a maximum of six electrons. which have an unpaired electron in their
s-subshell are:
3. When the value of n = 4, the values of l are 0, 1,
2 and 3. Condensed
Atomic
Value of l Values of ml Element outer electronic
number
0 0 configuration
1 1, 0, +1 Hydrogen 1 1s1
2 2, 1, 0, +1, +2 Lithium 3 [He] 2s1
3 3, 2, 1, 0, +1, +2, +3 Sodium 11 [Ne] 3s1
Potassium 19 [Ar] 4s1
For each value of n, l and m, the spin quantum
number (ms) can have two values: +1/2 and Chromium 24 [Ar] 3d5 4s1
1/2. Copper 29 [Ar] 3d10 4s1

Values Values Values Values 5. Electronic configuration of the element

of n of l of ml of ms = 2, 8, 18, 1
1  Number of electrons = 2 + 8 + 18 + 1 = 29
4 1 –1 –
2  Number of protons = 29
1
4 1 +1 – Mass number = 63
2
 Number of neutrons = 63  29 = 34
1
4 2 –1 –
2 6. The atomic number of Cr is 24 and its outer
1 electronic configuration is represented as:
4 2 +1 –
2 3d5 4s1
1 Cr (Z = 24)      
4 3 –1 –
2
1 The outer electronic configuration of Cr3+ ion is
4 3 +1 – represented as:
2
3d3 4s0
3+
Therefore, an atom can have only six electrons Cr   
with quantum numbers n = 4, ml = +1 or 1 and
ms = 1/2. Hence, Cr3+ ion will have 3 unpaired electrons.
14
 

Chapter 04: Structure of Atom

14. Chlorine has two stable isotopes: Cl-35 and  Z2 
Cl-37. 23. En = – 2.18  10–18  2 
J
n 
Let the natural abundance of Cl-35 isotope be x
 22 
% and that of Cl-37 be (100 – x)%. E2 = – 2.18  10–18  2 
J
Hence, 2 
Average atomic mass = – 2.18  10–18 J
 Atomic mass of Cl  35  x  24. According to Bohr’s theory,
  Atomic mass of Cl  37  100  x   rn  n2
= r1 = , n1 = 1, n3 = 3
100
2
35  x + 37  100  x  r1  1  1
  
35.5 = r3  3  9
100
 x = 75  r3 = 9r1 = 9
100 – x = 25 n2
Natural abundance of Cl-35 = 75% 25. Radius of Bohr’s orbit (rn) = 52.9  pm
Z
Natural abundance of Cl-37 = 25% where n = principal quantum number
Hence, the ratio of Cl-37 and Cl-35 is 1:3. Z = atomic number of the atom/ion
15. Phenomena such as diffraction and interference rH = 52.9 pm [ n = 1 and Z = 1]
of light could be explained by treating light as n2 4
electromagnetic wave. r
He
= 52.9   52.9  = 105.8 pm
Z 2
2
16. All the electromagnetic radiations such as n 4
r
Li 2 
= 52.9  = 52.9  = 70.5 pm
X-rays,  rays, visible light, etc., have same Z 3
speed i.e., speed of light. n2 9
r
Li 2 
= 52.9  = 52.9  = 158.7 pm
Z 3
17.
n2 4
Radiation Frequency (Hz) r = 52.9  = 52.9  = 52.9 pm
Be3  Z 4
Microwaves 1010
Thus, the radius of Be3+(n = 2) orbit is same as
UV rays 1016
that of the first Bohr’s orbit of hydrogen atom.
IR rays 1013
Radio waves 106 26. Speed =
distance
time
 distance
18. =  Time =
c speed
c 3  108 For an electron to complete one revolution in
= = = 1.5  102 m
 2  106 the Bohr’s orbit of H atom,
Distance = circumference of orbit of radius r
19.  = 600 nm = 600  109 m
= 2r
c 3  108 ms 1
= = = 5.0  1014 Hz According to Bohr’s theory, the angular momentum
 600  109 m of electron, mvr is integral multiple of h/2.
 c nh
20.  (   ) mvr =
c  2
nh
12  1014 s 1  Speed (v) =
 = 2mr
3.0  108 ms 1
nh
 = 4  10 m
6 1
or 4
 = 4  10 cm
1  Time = 2r 
2mr
21. Quantum refers to the smallest quantity of 2mr
= 2r 
energy that can be emitted or absorbed in the nh
form of electromagnetic radiation. 42 mr 2
=
nh
22. Bohr’s model of an atom could explain the
atomic spectra of hydrogen and hydrogen like 27. For Balmer series, n1 = 2. The 1st line in Balmer
species (i.e., species containing only one series is due to electronic transition from n2 = 3
electron). Li+ has 2 electrons and hence its to n1 = 2. Hence, the 2nd line in Balmer series
atomic spectrum could not be explained by will be due to the electronic transition from n2 =
Bohr’s model of an atom. 4 to n1 = 2.
9
 Textbook
Chapter No.

05 Chemical Bonding

Hints

In PCl5, P contains 10 electrons in the outermost

Classical Thinking orbit while Cl contains 8 electrons in the
5. According to octet rule, atoms try to achieve a outermost orbit.
complete octet in the valence shell. Since the In BF3, B contains 6 electrons in the outermost
given element ‘X’ already has six electrons in orbit while F contains 8 electrons in the
the valence shell, it accepts two more electrons outermost orbit.
and thus completes its octet. Therefore, its ions Thus, among given options, PCl5 is having an
will have two negative charges (2–). expanded octet.

8. Lower the ionization enthalpy of an atom, 18. Six covalent bonds with six fluorine atoms will
greater is the ease of losing the valence result in twelve electrons around S, which is the
electron(s) to form the corresponding cations. central element in SF6 molecule.
Higher the negative value of electron gain 22. ClF3 is a T-shaped molecule.
enthalpy, greater is the ease of formation of F
corresponding anion. Thus, when an element
with very low ionization enthalpy combines F  Cl
with an element having high negative value of
electron gain enthalpy, a strong ionic bond is F
formed.
23. SF4 molecule contains 1 lone pair and 4 bond
10. As size of cation decrease, lattice energy pair of electrons. Hence, the geometry of the
increases. molecule SF4, according to VSEPR theory, is
12. Two electrons from each atom are shared, see saw.
F
thereby four shared electrons form a double
bond. F
S
13. The correct Lewis symbol for oxygen atom:
F
O F
See saw shape
15. Formal charge, F.C. = V.E. – N.E. – (B.E./2) 25. SF6 has octahedral geometry. Hence, FSF
= X – Y – (Z/2) bond angles are 180 and 90.
16. Formal charge, F.C. = V.E. – N.E. – (B.E./2) 27. (B) The covalent bond is directional in nature.
Oxygen atom 1: (C) At equilibrium distance between the
1 nuclei of the bonded atoms, the total
F.C. = 6  4  (4) = 0
2 energy of the bonded atoms is minimum.
Oxygen atom 2: (D) The electrons in the half-filled valence
1 orbitals must have opposite spins.
F.C. = 6  2  (6) = +1
2 33. Electronic configuration of excited state of Be:
Oxygen atom 3:
1s 2s 2p
1
F.C. = 6  6  (2) = 1
2
17. In AlCl3, Al contains 6 electrons in the 34. Orbitals having nearly same energy can undergo
outermost orbit while Cl contains 8 electrons in hybridization, so 2s and 2p orbitals undergo
the outermost orbit. hybridization.
In CCl4, both C and Cl contain 8 electrons in 45. Bonding molecular orbitals (MO’s) have high
their respective outermost orbits. electron density between the two nuclei.

16
 

Chapter 05: Chemical Bonding

48. Helium molecule is not stable as the bond order Similarly, the Y atom will form the
of He2 = 0. corresponding univalent anion and attain the
noble gas configuration of argon.
50. (B) Bond angle of BF3 molecule is more than Y = 2, 8, 8 (valence = 1 and electronic
the bond angle of NH3 molecule. configuration similar to argon).
(C) The bond between two N-atoms in N2
4. Ionization is always an endothermic process.
(i.e., triple bond) is stronger than the bond
between O-atoms in O2 (double bond). 5. Cations having higher charge have large lattice
energies: AlCl3 > CaCl2 > NaCl
(D) The bond enthalpies of two O−H bonds in
As size of cation decrease, lattice energy
water are different. This difference arises increases: LiCl > NaCl.
since cleavage of the two O−H bonds in Thus, among the given compounds, NaCl has
water takes place in two steps. In the first lowest magnitude of lattice enthalpy.
step, one O−H bond breaks leaving
7. When the single covalent bond is formed
behind OH radical. The electronic between two atoms, each combining atom
environment around oxygen to which contributes one electron to the shared pair.
hydrogen is attached in the OH radical is Thus, during the formation of CCl4 molecule,
different than that around oxygen in H2O each chlorine atom contributes one electron to
molecule. This causes a change in the the shared pair.
successive bond dissociation energy.
Cl
53. Lower the bond order, greater will be the bond
length. Thus, bond length in NO (bond order Cl Cl
C
2.5) is greater than in NO+ (bond order 3).
55. HF has largest dipole moment because
electronegativity difference between H and F is Cl
highest among other given options, so it is
highly polar.
8. Element ‘X’ has atomic number 7. So, its
64.   electronic configuration is 2, 5.
CH3  CH = CH  CH2  C  CH
 Thus, its electron dot symbol would be X
Carbon-carbon triple bond contains 2 bonds (as it has 5 valence electrons).
and the carbon-carbon double bond contain one
12. Formal charge, F.C. = V.E. – N.E. – (B.E./2)
 bond, therefore, a total of three  bonds in all.
⸫ Formal charge on S = 6 − 2 − 1/2(6) = +1
16. NH3, PH3 and PCl3 have one lone pair in
Critical Thinking valence shell of their corresponding central
atoms while BF3 has none.
1. Octet rule is not valid for H and Li atoms. These 18.
atoms tend to have only two electrons in their Molecule H2O NH3 CH4 CO2
valence shell like that of Helium (1s2) which Bond 10435 10718 10928 180
called duplet. angle
2. Charge on the given cation M is +2 while that Hence, among given options, the bond angle
on the given anion A is 3. Thus, the between two covalent bonds is greatest in CO2.
electrovalence of M is 2 while that of A is 3.
Hence, the compound formed will have the 24. (A) The covalent bonds formed by hybrid
formula M3A2. orbitals are stronger than those formed by
pure atomic orbitals.
3. Electronic configuration of X(Z = 12) = 2, 8, 2 (C) The number of hybrid orbitals formed is
Electronic configuration of Y(Z = 17) = 2, 8, 7 same as the number of orbitals taking part
Thus, the X atom will form the corresponding in hybridization.
dipositive ion and attain the noble gas (D) Atomic orbitals of same atom can take
configuration of neon. part in hybridization.
X+2 = 2, 8 (valence = 2 and electronic Thus, among given options only option (B) is
configuration similar to neon). correct.

17
 

MHT-CET Triumph Chemistry (Hints)

26. The % distribution indicates 2 p-orbitals and 43. Larger the charge on cation, greater is extent of
one s-orbital to be the components, therefore sp2 polarisation in an ionic compound. So, among
hybridization. given options, Al3+ has high polarising power
than Na+ and Mg2+. Greater the size of anion
27. In BeCl2, Be-atom undergoes sp hybridization.
greater is the extent of polarisation. Among I
 % of s-character = 50%
and Cl, I has larger atomic size than Cl. Thus,
29. (B) A pi bonding molecular orbital has large among the given options, AlI3 has maximum
electron density above and below the covalent character.
internuclear axis.
44. In BF3 molecule, boron is sp2 hybridised. Hence,
(C) A  molecular orbital has a node between it will have planar trigonal geometry. So, all its
the nuclei. atoms are co-planar.
(D) Linear combination of two 1s orbitals
give two σ molecular orbitals. 45. As the electronegativity increases from I to F,
the bonding electron pairs are attracted more
31. Atomic orbitals having same or nearly same towards the halogen i.e., they move away from
energy will not combine if they do not have nucleus of phosphorus atom thus allowing
same symmetry. maximum expansion of the lone pair. So, the
Nb  Na 10  4 bond angle decreases from PI3 to PF3.
32. Bond order (B.O.) = = =3
2 2 P
P
34. Electronic configuration of N 2 molecule is I 102 I Br 101.5
2 2 2
N : 1s *1s 2s *2s 2p
 2 2
2p  2p
2 1 Br
2 x y z I
Bond order of N 2 ion Br
P
P
Nb  Na 94 5
= = = = 2.5
2 2 2 Cl 100.3 Cl F 97.8
35. Cl F
Species EC Magnetic F
nature Competitive Thinking
He2+ 1s2 *1s1 Paramagnetic
1. Given element X can lose two electrons from its
H2 1s2 Diamagnetic
outermost shell to form a divalent cation. So, its
H2+ 1s1 Paramagnetic chloride will have the formula XCl2.
H2 1s2 *1s1 Paramagnetic
2. Ammonium chloride (NH4Cl):
36. Nitrogen molecule has highest bond enthalpy +
H
due to presence of triple bond.
H – N  H C l–
38. Isoelectronic molecules and ions have identical
bond order. H
N2 and CO are isoelectronic species with each
Here, nitrogen forms 3 covalent bonds with 3
molecule containing 14 electrons and having
hydrogen atoms, a coordinate bond by donating
three shared pairs of electrons. Hence, their
the lone pair of electrons to another hydrogen
bond order is same (i.e., B.O. = 3)
ion, thus forming a cation of NH 4 , which forms
39. As we move across a period from left to right, ionic bond with Cl anion.
the electronegativity increases. Therefore,
correct order of increasing electronegativity is C 4. Lewis structure of I3 :
< N < O < F. –
Greater the difference in electronegativity of the I I I
two atoms forming covalent bonds more is its
polar nature. The electronegativity difference
Total number of lone pairs of electrons is 9.
between carbon and fluorine is maximum.
5. The phosphorus atom in PF5 is surrounded by
Hence, among the given options, CF bond is
10 electrons and the sulphur atom in H2SO4 is
most polar.
surrounded by 12 electrons respectively. In both
42. CO2 is a symmetrical molecule so its dipole these molecules the central atom has expanded
moment is zero. octet.
18
 

Chapter 05: Chemical Bonding

6. The forces of repulsion between electron pairs Stability of the molecule or species  Bond
decrease in the following order: order
lone pair – lone pair > lone pair – bond pair > Bond order decreases as: O 2 > O2 > O 2 > O 22 
bond pair – bond pair
 Stability decreases as: O 2 > O2 > O 2 > O 22 
7. Due to the repulsion between lonepair and
bond pair, the tetrahedral geometry gets 21. Electronic configuration of H 22  is σ1s2 σ*1s2.
distorted to trigonal pyramidal structure. 1
Bond order = (2–2) = 0
8. 2
P
Hence, H 22  will not be viable.
Cl Cl
Cl
22. O2: (1s)2 (*1s)2 (2s)2 (*2s)2 (2pz)2 (2px)2
Each bond represents one bond pair. Thus, in = (2py)2 (*2px)1  (*2py)1
PCl3, the molecule contains three bond pairs and Hence, O2 contains two unpaired electrons and
a lone pair around the central phosphorus atom. is paramagnetic.
9. I3 has two lone pairs of electrons on the central 24.
iodine atom. Molecule Bond angle
H2O has two lone pairs of electrons on the CH4 H  C  H: 109 28
central oxygen atom. NH3 H  N  H: 107 18
11. PCl5, PF5  Trigonal bipyramidal H2O H  O  H: 104 35
BrF5 , ClF5, IF5  Square pyramidal
25.
ClF3  T-Shaped
CH4 NH3 H2O
XeF4  Square planar, XeF2  linear (A)
109.5 107 104.5
13. BCl3 has bond angles of 120. H2O BeCl2 BF3
Cl (B)
sp2 hybridized boron with 104.5 180 120
B no lone pairs H2S CH4 SO2
(C)
Cl Cl 92 109.5 119.5
120
BF3 NH3 SF6
16. The combining atomic orbitals must have same (D)
120 107 90
symmetry about the molecular axis. Since the z
axis is considered as the molecular axis, pz 26. As a general rule, if the electronegativity
orbital of one atom combines with pz orbital of difference between the two combining atoms is
the other atom to form two sigma molecular more than 1.7, the bond will have an ionic
orbitals. However, px orbital of one atom cannot character. If the electronegativity difference is
combine with py orbital of the other atom between 0.4 and 1.7, the bond will have a polar
because of their different symmetries. covalent character. If the electronegativity
difference is less than 0.4, the bond will have a
10  8 nonpolar covalent character. Therefore, if the
19. O22 : B.O. =  1,
2 electronegativity difference is 1.7, the bond will
10  7 have approximately 50% ionic character.
O2 : B.O. =  1.5,
2
28.
10  6
O2 : B.O. =  2, Dipole moment of
2 Nature of
Molecule the molecule,
10  5 bonds
O2 : B.O. =  2.5  (D)
2
NH3 N  H, 1.47 (Polar)
20. Polar
Species Bond order CH4 C  H, 0 (Non-polar)
O2 2 Non-polar
O 2 1.5 CHCl3 C  Cl, 1.04 (Polar)
Polar
O 2 2.5
H2S H  S, 0.95 (Polar)
O 2
2
1 Polar

19
 

Chapter 04: Structure of Atom

8
7.   RH
9
 1 1 
  RH  2  2 
n
 1 n 2 

1 1 8
  
n12 n 2 2 9

Values of  1 1 
n1 and n2  2  2
 n1 n2 
(A) n1 = 1, n2 = 3  1 1  8
 2  2
 1  3  9
(B) n1 = 1, n2 = 4  1 1  15
 2 2

 1  4   16
(C) n1 = 1, n2 = 9  1 1  80
 2 2

 1  9   81
(D) n1 = 1, n2 = 2  1 1  3
 2 2

 1  2   4

Thus,  = 8/9 RH if the electron jumps from

n = 3 to n = 1.
8. Maximum number of electrons in N-shell
(n = 4) = 2n2 = 2  42 = 32.
9. The electronic configuration of Na (Z = 11) is
1s2 2s2 2p6 3s1.
The valence electron occupies 3s orbital.
Therefore, n = 3 and l = 0.
10. The black-body radiation and photoelectric
effect could not be explained by wave nature of
light, and could be accounted for by considering
particle nature of light.
11. Mass of an electron = 9.1  1028 g
 Mass of one mole of electrons
= 9.1  1028  6.022  1023
= 54.8  105 g = 0.55 mg
hc
12. Energy (E) =

1
 E

Radiation Wavelength ()
A 30 Å = 30  10–10 m = 3  10–9 m
B 30 nm = 30  10–9 m = 3  10–8 m
C 300 m = 300  10–6 m = 3  10–4 m
Thus, the increasing order of energy is
C < B < A.

15
 
Textbook
Chapter No. Chapter 06: Redox Reactions

06 Redox Reactions
Subtopics

Hints

+1 x –2
Classical Thinking 17. HClO4
Let x be the oxidation number of Cl.
3. According to the classical concept, reduction  (+1) + (x) + 4(– 2) = 0
involves removal of oxygen from a compound.  +1 + x – 8 = 0
In reaction (i) and (iii), there is removal of  x–7=0
oxygen from HgO and Fe2O3, respectively.
 x = +7
Thus, they both undergo reduction.
18. x 2
5. Sn2+  Sn4+ + 2e. In this reaction Sn2+ S2O72
changes to Sn4+, it is called an oxidation reaction, Let x be the oxidation number of S.
because of loss of two electrons from Sn2+.  2(x) + 7(– 2) = –2
6. A substance that causes oxidation is an 2x – 14 = –2
oxidizing agent or oxidant. It accepts electron(s) 2x = +12
and itself gets reduced. Thus, in the course of a  x = +6
chemical reaction, an oxidant gains electron(s). 19. +1 x –2
8. A reducing agent or reductant causes reduction NaIO3
of the other chemical species involved in the x+16=0
reaction. While doing so it itself undergoes x = +5
oxidation by donating its electron(s). Thus, there
x 2
is an increase in its oxidation number. I O 4
9. Zn + Cu2+  Zn2+ + Cu IO 4 is an ionic species.
Oxidation is increase in oxidation number. For  Sum of the oxidation numbers of all atoms =  1
the given reaction, the oxidation number of Zn  x + 4  (–2) =  1
increases from 0 to +2.  x = 1 + 8 = +7
Hence, Zn is oxidized to Zn2+.
x +1
10. The oxidation number of each atom of an 20. (A) CH4  x + 4(+ 1) = 0  x = –4
element in free state is zero. Thus, each atom in x –1
Cl2 and S8 has oxidation number of zero. (B) CF4  x + 4(– 1) = 0  x = +4
x –2
13. Hydrogen has oxidation number of 1 when it is
(C) CO2  x + 2(– 2) = 0  x = +4
bonded to metals, zero in H2 and +1 when
bonded to non-metals. x –1
(D) CCl4  x + 4(– 1) = 0  x = +4
14. The oxidation number of F is always 1 in all of Thus, among the given options, carbon has
its compounds i.e., it never has a positive lowest oxidation state in CH4.
oxidation number in any of its compounds.
21. +5 +1
x +1 –1 HNO3  N2O
15. CH2Cl2
x + 2(+1) + 2(1) = 0 When HNO3 changes to N2O, the oxidation
number of N changes from +5 to +1 i.e., the
 x=0
oxidation number is changed by
x +1 2 (+5) – (+1) = +4 units
16. C12H22O11
Let x be the oxidation number of C. 22. The oxidation number of Cl in the given
compounds is as follows:
 12x + 22  ( + 1) + 11  ( 2) = 0 1 x
 12x + 22 – 22 = 0 KCl  +1 + x = 0
 x=0  x = 1
21
 

MHT-CET Triumph Chemistry (Hints)

1 x 2
34. In balancing of equations by oxidation number
HClO  +1 + x + (2) = 0
method, the first step involves writing the
 x = +1 unbalanced net equation and balancing it for all
1 x 2
HClO2  +1 + x + (2  2) = 0 atoms (except H and O).
 x = +3
2Bi(OH)3(s) + 3SnO2(aq) 
2-
1 x 2
35.
HClO4  +1 + x + (2  4) = 0 2-
3SnO3(aq) + 2Bi(s) + 3H2O(l)
 x = +7
 In HClO4, Cl has highest oxidation number of 36. In Daniel cell, oxidation takes place at zinc
+7. electrode and reduction at copper electrode.
2+
25. Copper(I) chloride: CuCl Oxidation: Zn(s)  Zn(aq) + 2e–
0 1 2+
Reduction: Cu(aq) + 2e–  Cu(s)
26. (A) Br2  HBr (Reduction)
+2 1 +1 1 37. Li has larger negative value of E0 than Na.
(B) 2HgCl2  Hg2Cl2 (Reduction) Thus, Li is stronger reducing agent than Na.
1 0
(C) 2KI  I2 (Oxidation)
+1
Critical Thinking
+2
(D) 2Cu2+  Cu2I2 (Reduction) 1. Oxidation can be defined as the addition of
electronegative element to a substance.
Only in option (C) the oxidation number of I
Reduction can be defined as the removal of
increases from 1 to 0 and hence KI gets
electronegative element from a substance.
oxidised to I2.
Thus, (i) involves oxidation of Mg and (ii)
0 0 +1 1 involves reduction of FeCl3.
27. 2Na + Cl2  2NaCl 3. Oxidation reaction:
The oxidation number of Na increases from 0 to
+ 2e
2
+1 while the oxidation number of Cl2 decreases Fe(s)  Fe(aq)
Iron Iron(II)
from 0 to 1. ion
So, Na gets oxidized while Cl2 gets reduced.
Reduction reaction:
28. Oxidation 2
Cu(aq) + 2e–  Cu(s)
0 0 +1 –1 Copper(II) Copper
H2 + Br2  2HBr ion

Reduction Iron acts as a reducing agent as it donates

electrons while copper(II) ion acts as an
Hydrogen undergoes oxidation and bromine oxidising agent as it accepts electrons.
undergoes reduction. Thus, the reaction involves
both, oxidation and reduction and is a redox 5. Reactions given in option (A) and (B) are
reaction. neutralization reactions whereas reaction in
option (C) is a precipitation reaction. Reaction
29. +2 +4 2 +2 2 +4 2 given in option (D) represents redox reaction as
CaCO3  CaO + CO2 there is a net transfer of electrons from Fe atoms
Calcium Calcium Carbon to Cu+2 ions.
carbonate oxide dioxide
This is not a redox reaction since no element –1 x
undergoes a change in oxidation number. 7. F2O
+1 1 +1 1
 2(–1) + x = 0
30. +1 +5 2 +1 +5 2
AgNO3 + NaCl  AgCl + NaNO3  x = +2
None of the elements in reaction (C) undergoes 8. Let x be the oxidation number of C in C3O2
a change in oxidation number; therefore, (C) is  3x + 2  ( 2) = 0
not a redox reaction.  x = +4/3
31. In reaction (D), Ag2O gets reduced to Ag by Structure of C3O2:
H2O2 hence it acts as a reducing agent. +2 0 +2
O = C = C* = C = O
33. Balanced equation: Structure of C3O2
2H2SO4(aq) + C(s)  CO2(g) + 2SO2(g) + 2H2O(l) (Carbon suboxide)

22
 

Chapter 06: Redox Reactions

x  1 + x + (2  4) = 0
9. (A) Oxidation number of N in HNO3  x = +7.
 + 1 + x + 3 (2) = 0 Whereas oxidation numbers of Mn in
 x = +5 manganese dioxide (MnO2), manganese
x
(B) Oxidation number of N in NH2OH chloride (MnCl2) and manganese sulphate
(MnSO4) are +4, +2 and +2 respectively.
 x + (2  1)  2 + 1= 0
 x = 1 +1 x –2
x 16. HIO4
Oxidation number of N in  N 2 H 5 2
2
(C)
+1 + x + 4(2) = 0
 2 [(2  x) + (5  1)] = +2  x = +7
 x = 2 x +1 x –2
(D) Oxidation number of N in Mg3N2 H3IO5
 3  (+2) + 2x = 0 3(+1) + x + 5(2) = 0
 x = +7
 x = 3
Thus, option (D) is correct. +1 x –2
 H5IO6
10. In I , let the oxidation number of I be x
3 5(+1) + x + 6(2) = 0
 3x =  1  x = +7
 x = 1/3.
+1 x –2
11. 0 +1 1 +12 17. H 4 IO6 
S8, S2F2, H2S The oxidation state of I is
 Oxidation number of S in S8, S2F2 and H2S 4(+1) + x + 6(2) = –1
respectively are 0, +1 and 2.  4 + x – 12 = –1
+1 x 2  x = +7
12.
K4P2O7 18.
4(+1) + 2x + 7(–2) = 0 +1 x –2
2x – 10 = 0 i. H2SO4
2x = +10  x+2–8=0
 x = +5  x = +6
13. Let x be the oxidation state of Cu in YBa2Cu3O7  Oxidation number of S in H2SO4 = +6
(+3) + 2(+2) + 3x + 7(2) = 0 +1 x –2
(+3) + 4 + 3x – 14 = 0 ii. H2S4O6
3x – 7 = 0  4  (x) + 2 – 12 = 0
7 10
 x=+  x=+
3 4
 Oxidation number of S in H2S4O6 = +2.5
14.
Compound Oxidation state of metal +1 x –2
MnO2 Mn(+4) iii. Na2S2O3
FeCl3 Fe(+3)  2  (x) + 2  6 = 0
V2O5 V(+5) 4
 x=+
CrO3 Cr(+6) 2
Mn2O3 Mn(+3)  Oxidation number of S in Na2S2O3 = +2
V2O3 V(+3) x –2
SnCl2 Sn(+2) iv. SO32
Thus, among the given pairs of compounds, (x) + 3 × (–2) = – 2
V2O5 and CrO3 is the pair, which has metals in  x=–2+6
their highest oxidation state.  Oxidation number of S in SO32 = +4
15. Potassium permanganate is KMnO4.
19. Stock notation for H2PtCl6: H2Pt(IV)Cl6
Let x be the oxidation number of Mn in KMnO4.
+1 x 2 20. M2+  M5+ + 3e
KMnO4 Thus, the O.N. of metal = +5.
23
 

MHT-CET Triumph Chemistry (Hints)

+5 3 28. Oxidation
21. NO3  NH 4
Here, oxidation number of N decreases from +5 0 0 +2 –1
in NO 3 to 3 in NH 4 and hence NO 3 gets Zn + I2  ZnI2
reduced to NH 4 .
Reduction
+4 +3 +5 +2 In this reaction, Zn atom gets oxidised to
22. NO2  NO 2 , NO 3  NO,
Zn2+ ion and iodine gets reduced to I.
+5 3 3 0
NO 3  NH 4 , NH 4  N2. 29. Al is the reductant as it gets oxidised to Al2O3.
Al  Al+3
Thus in option (D) the oxidation number of N
Thus, in oxidising one Al atom 3 electrons are
increases from 3 to 0 i.e., N gets oxidised. transferred.
+7 +2  For oxidising 8 Al atoms, the electrons
transferred = 8  3 = 24
23. (A) MnO4–  Mn
(involves gain of 5es) 30. Oxidation
+6 +3
0 +1 –1
(B) CrO42–  Cr
H2O + Br2  HOBr + HBr
(involves gain of 3es)
+6 +4
(C) MnO42–  MnO2 Reduction
(involves gain of 2es) Thus, in given reaction, Br2 is oxidised as well
as reduced.
+6 +3
(D) Cr2O72–  2Cr 31. In the equation, (A), iodine in HI gets oxidised
(involves gain of 3es) to I2. Hence, in this equation H2SO4 acts as an
Hence, option (A) is correct. oxidising agent.
24. Only in reaction (D), the oxidation numbers of 34. The balanced equation is
the elements undergo a change. 2C2H6 + 7O2  4CO2 + 6H2O.
Oxidation Ratio of the coefficients of CO2 and H2O is 4 : 6
or 2 : 3.
+1 2 +2 0 0 +4
Cu2S + 2FeO  2Cu + 2Fe + SO2 35. Balanced redox reaction:
2- +
3H2O2(aq) + Cr2O7(aq) + 8H(aq)
Reduction
 3O2(g) + 2Cr(aq)
3+
+ 7H2O(l)
Reduction
36. Given reaction:
+2 +4
25. (A) CO  CO2
2-
SeO3(aq) + Cl2(g)  SeO24(aq)
-
+ Cl-(aq)
+2 +2
(B) CuO  CuCl2 +4 2 0 +6 2 1
+1 0 
39. 2 Ag 
+ 2e  2Ag(s) ; E0 = 0.80 V
(C) H2O  H2 (aq)

0 +4
Cu(s)  Cu (aq)
2
+ 2e ; E0 = −0.34 V
(D) C  CO2 The sum of E0 values = 0.80 – 0.34 = 0.46 V.
Only in option (C), oxidation number of
40. Option (A):
hydrogen decreases from +1 to 0 and hence H2O
The sum of E0 values – 0.76 − 0.54 = –1.3 V
gets reduced to H2.
is negative, therefore, reaction is not
26. In the given reaction, nickel (Ni) gets oxidized spontaneous.
from Ni(0) to Ni(II) and reduces Cr(VI) to Cr(III) Option (B):
thus, Ni serves as a reducing agent. The sum of E0 values – 0.76 – 1.09 = –1.85 V
is negative, therefore, reaction is not
27. Here, NO acts as a reducing agent and reduces
spontaneous.
I2 to I. Also, NO itself undergoes oxidation Option (C):
since the oxidation number of nitrogen changes The sum of E0 values 0.92 – 0.54 = 0.38 V
from +2 in NO to +5 in NO3 . is positive, therefore, reaction is spontaneous.
24
 

Chapter 06: Redox Reactions

Option (D): 3. x –2
The sum of E0 values 0.92 – 1.09 = –0.17 V Fe3O4
is negative, therefore, reaction is not The oxidation state of Fe is
spontaneous. 3x + 4(–2) = 0
 3x – 8 = 0
41. (I) Cl2 has larger positive value of E0 than
8
Br2. Thus, Cl2 is stronger oxidizing agent  x=+
than Br2. 3
(II) Br2 has larger positive value of E0 than I2. 4. MnO 4
Thus, Br2 is stronger oxidizing agent than
 x + (2  4) = –1 or x = +7
I2.
5. PO 34 SO 24  Cr2O 72 
42. Ferrous ions (Fe+2) and ferric ions (Fe+3) have
net charge of +2 and +3 respectively. x – 8 = 3 x – 8 = 2 2x – 14 = 2
x = 3 + 8 x = 2 + 8 2x = 2 + 14
0 0 +1 1
43. 2Li + H2  2LiH x = +5 x = +6 2x = 12
Here, H2 acts as an oxidizing agent since the x = +6
oxidation number of Li increases from 0 to + 1
and that of H decreases from 0 to 1. 6. Let the oxidation state of N be x.
x 1
N2H4  2x + 4(+1) = 0
44. (A) H2SO4 + 2NaOH  Na2SO4 + 2H2O
This is a neutralization reaction.  2x = 4
0 0
 x = 2
x 1
(B) 2O3  3O2 NH3  x + 3(+1) = 0
Oxidation number of O in both O3 and O2  x = 3
is zero, therefore, it is not a redox x 1

reaction. N3H  3x + 1 = 0
0 0 +22  x = 1/3
x 1 2 1
(C) 2N2 + O2  2NO NH 2O H  x + 2(+1)  2 + 1
Here oxidation number of N increases  x = 1
from 0 in N2 to + 2 in NO and that of O
 Nitrogen in N3H exhibits highest oxidation
decreases from 0 in O2 to  2 in NO state.
therefore, it is a redox reaction.
(D) H2O(l)  H2O(g) 7. The oxidation state of N in the following
Only state of matter changes and hence compounds can be given as,
there is no change in oxidation number. HNO3 : + 1 + x + 3(2) = 0
Thus, among given options only  x = +5
option(C) represents redox reaction. NO : x  2 = 0
 x = +2
45. The oxidation numbers of the elements in their
NH4Cl : x + 4(+1) – 1 = 0
compounds are as follows:
 x = –3
N :  3,  2, + 1 to + 5
N2 : x = 0
O :  1,  1/2, + 2  The ordering of compounds according to the
C :  4, + 2, + 4 decreasing order of the oxidation state of
Cl :  1, + 1, + 3, + 4, + 5, + 6, + 7 nitrogen will be HNO3, NO, N2, NH4Cl.
Thus, Cl exhibit highest oxidation number of +7
among the given options. +4 –1 +1 –1 +6 –1 0
8. (A) XeF4 + O2F2  XeF6 + O2
+2 +5 +2 +5
Competitive Thinking (B) XeF2 + PF5 [XeF]+ PF6

1. Oxidation number of alkali metal, i.e., K is (C) +6 –1 +1 –2 +6 –2 –1 +1 –1

XeF6 + H2O  XeOF4 + 2HF
always +1.
(D) +6 –1 +1 –2 +6 –2 –1 +1 –1
x 
 XeF6 + 2H2O  XeO2F2 + 4HF
2.  AuCl4 
The reaction in option (A) is an example of a
x + 4(–1) = –1 redox reaction since xenon undergoes oxidation
 x = +3 and oxygen undergoes reduction.

25
 

MHT-CET Triumph Chemistry (Hints)

+ 2+
+6 +6 11. 2MnO 4 + 5C 2O 24  +16H  2Mn +10CO2
9. CaF2 + H2SO4  CaSO4 + 2HF + 8H2O
The oxidation number of S remains unchanged. –
Hence, reaction given in option (A) is the one 12. Cl has eight valence electrons (i.e., complete
that does not show oxidizing behaviour of octet). Hence, it cannot accept electrons i.e., it
H2SO4. cannot function as an oxidising agent.
In ClO4 and MnO4 , the central atoms Cl and Mn
10. After balancing the equations by ion-electron
method we get, are in their highest oxidation states (i.e., +7).
+  2+ Hence, these species cannot donate electrons
MnO4 + 8H + 5e  Mn + 4H2O  2

i.e., these species cannot function as reducing
C2O24   2CO2 + 2e  5 agents.
2MnO4 + 5C2O24  + 16H
+ In ClO, the oxidation number of Cl is +1. The
2Mn2+ + 10CO2 + 8H2O highest oxidation number of Cl is +7 and the
lowest is 1. Hence, ClO– can accept or donate
Thus, the coefficient of MnO4 , C2O24  and H+
electrons and can function both as oxidising as
in the above balanced equation are 2, 5, 16 well as reducing agent.
respectively.

Hints to Evaluation Test

1. When an elemental sulphur atom becomes a x –1

sulphide ion, the oxidation number of S changes 5. Mo2Cl84 
from 0 to –2 by the gain of two electrons. 2x + 8(– 1) = –4
2x – 8 = –4
2. KO2 : + 1 + 2(x) = 0 2x = +4
 2x = –1  x = +2
1
 x= or – 0.5 +2 +1 x 2
2
x 6. Ba(H2PO2)2
Na 2 O 2 : 2(+1) + 2x = 0  2 + 2 [2  (+ 1) + x + 2  ( 2)] = 0 or
 2x = –2  2 + 4 + 2x  8 = 0
 x = –1  x = +1
7. The oxidation number of each atom of an
3. In the reaction, element in free state is zero. Thus, the oxidation
0 1 +5
 state of O in O3 and P in P4 is 0.
3Br2  5Br + BrO3
The oxidation number of Br changes from 0 to 8. C4H4 O62
1 and also from 0 to +5. Thus, Br undergoes Oxidation number of H = +1
both reduction and oxidation. Oxidation number of O = –2
Sum of the oxidation states of all atoms = –2
4. IO3– + aI  + bH+  cI2 + dH2O  4  (Oxidation number of C) + 4  (Oxidation
Step 1 : I 1  I2 (oxidation) number of H) + 6  (Oxidation number of O)
IO3–  I2 (reduction) = –2
Step 2 : 2IO3– + 12H+  I2 + 6H2O  4  (Oxidation number of C) + 4  (+1) +6
 (–2) = –2
Step 3 : 2IO3– + 12H+ + 10e–  I2 + 6H2O
 4  (Oxidation number of C) + 4 – 12 = –2
2I   I2 + 2e–
 4  (Oxidation number of C) = –2 + 8 = +6
Step 4 : 2IO3– + 12H+ + 10e–  I2 + 6H2O Oxidation number of C = +1.5
[2I   I2 + 2e–]5
10. Oxidation number of oxygen = 2; Oxidation
Step 5 : 2IO3– + 10I  + 12H+  6I2 + 6H2O
number of hydrogen = +1
Dividing by 2, Oxidation number of nitrogen = 3; Oxidation
IO3– + 5I  + 6H+  3I2 + 3H2O number of zinc = +2
On comparing, a = 5, b = 6, c = 3, d = 3 Sum of the oxidation states of all atoms = 0
26
 

Chapter 05: Chemical Bonding

6. The forces of repulsion between electron pairs Stability of the molecule or species  Bond
decrease in the following order: order
lone pair – lone pair > lone pair – bond pair > Bond order decreases as: O 2 > O2 > O 2 > O 22 
bond pair – bond pair
 Stability decreases as: O 2 > O2 > O 2 > O 22 
7. Due to the repulsion between lonepair and
bond pair, the tetrahedral geometry gets 21. Electronic configuration of H 22  is σ1s2 σ*1s2.
distorted to trigonal pyramidal structure. 1
Bond order = (2–2) = 0
8. 2
P
Hence, H 22  will not be viable.
Cl Cl
Cl
22. O2: (1s)2 (*1s)2 (2s)2 (*2s)2 (2pz)2 (2px)2
Each bond represents one bond pair. Thus, in = (2py)2 (*2px)1  (*2py)1
PCl3, the molecule contains three bond pairs and Hence, O2 contains two unpaired electrons and
a lone pair around the central phosphorus atom. is paramagnetic.
9. I3 has two lone pairs of electrons on the central 24.
iodine atom. Molecule Bond angle
H2O has two lone pairs of electrons on the CH4 H  C  H: 109 28
central oxygen atom. NH3 H  N  H: 107 18
11. PCl5, PF5  Trigonal bipyramidal H2O H  O  H: 104 35
BrF5 , ClF5, IF5  Square pyramidal
25.
ClF3  T-Shaped
CH4 NH3 H2O
XeF4  Square planar, XeF2  linear (A)
109.5 107 104.5
13. BCl3 has bond angles of 120. H2O BeCl2 BF3
Cl (B)
sp2 hybridized boron with 104.5 180 120
B no lone pairs H2S CH4 SO2
(C)
Cl Cl 92 109.5 119.5
120
BF3 NH3 SF6
16. The combining atomic orbitals must have same (D)
120 107 90
symmetry about the molecular axis. Since the z
axis is considered as the molecular axis, pz 26. As a general rule, if the electronegativity
orbital of one atom combines with pz orbital of difference between the two combining atoms is
the other atom to form two sigma molecular more than 1.7, the bond will have an ionic
orbitals. However, px orbital of one atom cannot character. If the electronegativity difference is
combine with py orbital of the other atom between 0.4 and 1.7, the bond will have a polar
because of their different symmetries. covalent character. If the electronegativity
difference is less than 0.4, the bond will have a
10  8 nonpolar covalent character. Therefore, if the
19. O22 : B.O. =  1,
2 electronegativity difference is 1.7, the bond will
10  7 have approximately 50% ionic character.
O2 : B.O. =  1.5,
2
28.
10  6
O2 : B.O. =  2, Dipole moment of
2 Nature of
Molecule the molecule,
10  5 bonds
O2 : B.O. =  2.5  (D)
2
NH3 N  H, 1.47 (Polar)
20. Polar
Species Bond order CH4 C  H, 0 (Non-polar)
O2 2 Non-polar
O 2 1.5 CHCl3 C  Cl, 1.04 (Polar)
Polar
O 2 2.5
H2S H  S, 0.95 (Polar)
O 2
2
1 Polar

19
 
Textbook
MHT-CET
Chapter No.Triumph Chemistry (Hints)

08 Elements of Group 1 and Group 2

Hints

24. The general outer electronic configuration of

Classical Thinking alkali metals is ns1. They readily lose one
5. Hydrogen has three isotopes viz., valence shell electron to achieve stable noble
Hydrogen or Protium ( 11 H or H), gas configuration and hence, they are highly
electropositive and are good reducing agents.
Deuterium ( 12H or D), Hence, standard reduction potentials of alkali
Tritium ( 13H or T) metals have high negative values.
25. The electropositive character increases down the
6. Tritium is a -particle emitter.
group from Be to Ba. Thus, the most
7. Number of neutrons electropositive amongst the given alkaline earth
= Mass number – Atomic number metals is barium.
=3–1 26. Sodium reacts with oxygen to form sodium
=2 peroxide.

8. Zn + 2NaOH  Na2ZnO2 + H2 2Na + O2   Na2O2
Zinc Sodium Sodium Sodium Sodium
hydroxide zincate metal peroxide
(Alkali)
27. When magnesium combines with oxygen,
Zn + 2HCl  ZnCl2 + H2 magnesium oxide is formed.
Zinc Hydrochloric Zinc 1
acid chloride Mg + O2  MgO
2
(Acid)
28. 2Na + 2H2O  2Na+ + 2OH + H2
12. Among the halogens, fluorine has great affinity Sodium Hydrogen gas
for hydrogen and combines even at very low
temperature (−250 °C) forming hydrogen 32. 6Li + N2 
air
 2Li3N
fluoride. Lithium Lithium nitride
Other alkali metals cannot form such nitride
13. Hydrogenation of vegetable oils using nickel as compounds.
catalyst gives edible fats (margarine and
vanaspati ghee). 33. Lithium forms monoxide (Li2O).
Vegetable oil + H2  Solid fat
Finelydivided Ni
450K,810 atm
34. Be mostly forms covalent compounds due to its
(i.e., vanaspati ghee) anomalous properties.

18. Caesium (Z = 55), rubidium (Z = 37) and 40. All extracellular fluids have high concentration
potassium (Z = 19) are alkali metals while of sodium ion (Na+) and low concentration of
strontium (Z = 38) is an alkaline earth metal. potassium ion (K+).
44. In the Solvay process, NH4Cl is treated with
20. Radium is radioactive and is not easy to find.
slaked lime to recover NH3.
21. 2NH4Cl + Ca(OH)2  CaCl2 + 2H2O + 2NH3
Element Electronic configuration Ammonium Slaked lime Calcium Ammonia
Ca [Ar] 4s2 chloride chloride
Sr [Kr] 5s2 45. Sodium hydrogen carbonate on heating forms
Ba [Xe] 6s2 sodium carbonate, liberating carbon dioxide.
Ra [Rn] 7s2 2NaHCO3  373 K
 Na2CO3 + CO2 + H2O
Sodium Sodium
23. Ionization enthalpies of alkali metals decrease hydrogen carbonate
down the group from Li to Cs. carbonate
28
 

Chapter 08: Elements of Group 1 and Group 2

47. KHCO3 being highly soluble in water (than
NaHCO3) cannot be precipitated. Hence, K2CO3 Critical Thinking
cannot be prepared using Solvay process. 2
1. H or D has 2 nucleons (1 proton + 1 neutron)
1
48. Na2CO3 is used to make hard water soft as it and one electron, so sum of these is 2 + 1 = 3.
precipitates out the soluble calcium and
magnesium salts in hard water as carbonates. 3. Only tritium is radioactive.
Ca(HCO3)2(aq) + Na2CO3(aq)  CaCO3(s) 4.
+ 2NaHCO3(aq)
Property Hydrogen Deuterium Tritium
49. During electrolysis of sodium chloride in Atomic mass
1 2 3
Castner-Kellner cell, the following reactions number
take place: Atomic
1 1 1
Cathode: Na+ + e  Na number
Na + Hg  NaHg Number of
0 1 2
1 neutrons
Anode: Cl  Cl2 + e

Abundance
2 99.98 0.015 Trace
(%)
Thus, chlorine gas is evolved at anode.
5. During electrolysis, of acidified water using
50. During electrolysis of sodium chloride in platinum electrodes, dihydrogen is liberated at
Castner-Kellner cell, the following reactions cathode and dioxygen is liberated at anode.
take place:
Cathode: Na+ + e  Na 6. The reactivity of hydrogen towards halogens
decreases in the order F2 > Cl2 > Br2 > I2.
Na + Hg  NaHg
Fluorine has great affinity for hydrogen and
1
Anode: Cl  Cl2 + e reacts with it at low temperature or even in dark
2 to form HF.
The amalgam is then treated with water to give
sodium hydroxide and hydrogen gas. 10. The element Rb (Z = 37) is an alkali metal and
is placed in the fifth period in the periodic table.
2NaHg + 2H2O  2NaOH + 2Hg + H2 Hence, the valence shell electronic
Sodium configuration of Rb is 5s1.
hydroxide
11. The ability to lose an electron (electropositive
52. CaCO3 + 2HCl  CaCl2 + H2O + CO2 character) of alkali metals increases down the
Calcium (dil.) Calcium Carbon group from Li to Cs. Thus, among given
carbonate chloride dioxide options, Cs is most electropositive element.
53. Calcium carbonate (CaCO3) is insoluble in 12. As we move down the group, the first ionization
water. enthalpy decreases.
55. When hydrated barium peroxide is treated with Element Mg Ca Sr Ba
ice-cold dilute sulphuric acid, the precipitate of Ionization enthalpy 737 590 549 503
barium sulphate is obtained. (kJ/mol)
Low temp.
BaO2.8H2O(s) + H2SO4(dil) 
273K

 14. Na, K and Cs belong to the group 1. Cs and K
have larger valence shells than Na and therefore,
BaSO4 + H2O2(aq) + 8H2O(l)
the atomic radii of K and Cs are larger than that
57. 30 volume H2O2 means that 1 L of this solution of Na.
gives 30 L of oxygen at STP. Na and Mg belong to the same period and
 1 cm3 of this solution will give 30 cm3 of hence, both have the same valence shell.
oxygen at STP. However, the nuclear charge on Mg is greater
than that of Na. Therefore, the valence electrons
60. D2 molecule has two atoms of deuterium of Mg are held more tightly and its atomic
(D or 12H ). radius is smaller than that of Na. Hence, Mg is
Each deuterium atom has 1 proton and 1 the smallest atom among given.
neutron. 15. Alkaline earth metals have two valence
 Number of nucleons in D2 molecule electrons which can be lost easily during a
= 2 protons + 2 neutrons reaction. Hence, alkaline earth metals are highly
= 4 nucleons reactive and do not occur in free state.
29
 

MHT-CET Triumph Chemistry (Hints)

16. In dry air, alkali metals react with oxygen to 30. Ca2+ ions are required for contraction and
form corresponding oxides. This reaction stretching of muscles.
tarnishes the alkali metals. When these oxides
31. Na2CO3.H2O(s) 
above 373 K
Na2CO3(s) + H2O(g)
react with moisture, they form corresponding
Soda ash
hydroxides.
(Anhydrous
17. Potassium superoxide has ability to absorb white powder)
carbon dioxide and give out oxygen at the same
time. 32. In Solvay process, CO2 is bubbled through the
4KO2 + 2CO2  2K2CO3 + 3O2↑ solution of brine (NaCl) saturated with NH3.
Potassium Carbon Potassium Oxygen Precipitate of NaHCO3 is obtained which on
superoxide dioxide carbonate ignition gives Na2CO3, H2O and CO2.
NH3 + H2O + CO2  NH4HCO3 ...(i)
18. Among the alkali metal ions, Li+ ion is the (From brine Ammonium hydrogen
smallest cation while among halides, anion I solution) carbonate
has the largest size. Thus, electron cloud around
I ion is easily distorted by Li+ ion leading to NaCl + NH4HCO3  NaHCO3  + NH4Cl
polarisation of anion and covalency. Also, the ....(ii)
(From brine Ammonium Sodium
difference in electronegativities of Li and I is solution) hydrogen hydrogen
small. Hence, lithium iodide is most covalent in carbonate carbonate (ppt.)
nature among alkali halides.
20. The alkali metals are soluble in liquid ammonia

2NaHCO3   Na2CO3 + CO2  + H2O
as follows: Filtered precipitate of Sodium
sodium hydrogen carbonate
M + (x + y)NH3  [M(NH3)x]+ + [e(NH3)y] carbonate
The blue colour of the solution is due to the
ammoniated electron. CO2 obtained in reaction (iii) is again used in
21. The solution formed by dissolving alkali metals reaction (i). NH4Cl obtained in reaction (ii) is
in ammonia is paramagnetic and on standing treated with Ca(OH)2 to recover NH3.
slowly liberates hydrogen resulting in the 2NH4Cl + Ca(OH)2  CaCl2 + 2H2O + 2NH3
formation of metal amide. ....(iv)
Ammonium Calcium
M+am  + e−(am) + NH3(l)  MNH2(am) + 1 H2(g) chloride chloride
2
(where ‘am’ denotes solution in ammonia.) NH3 obtained in reaction (iv) is used in reaction
As a result, the blue colour of the solution (i). Thus, CO2 and NH3 are recovered in the
changes to bronze and the solution becomes Solvay process.
diamagnetic.
34. NaOH is highly water soluble and gives a
22. Chloride of lithium (LiCl) is deliquescent and strongly alkaline solution.
crystallizes as a hydrate (LiCl.2H2O) whereas
chlorides of other alkali metals do not form 36. 2H2O2  2H2O + O2
hydrates. 2  34 g 22.7 L
 2  34 g = 68 g of H2O2 liberates 22.7 L O2 at
23. All group 2 elements form chlorides that are
STP
deliquescent.
0.68  22.7
24. The first member of the group-2 (i.e., Be)  0.68 g of H2O2 liberates =
68
elements exhibits diagonal relationship with the = 0.227 L
second member of group-13 (i.e., Al) of the
modern periodic table. 38. When small amount of H2O2 is added to ferrous
sulphate solution, an electron is lost by Fe+2 ion
25. (A) BeCl2 and AlCl3 act as Lewis acids.
and it gets oxidised to Fe+3 ion.
(C) Both Be and Al form amphoteric oxides.
2Fe2+ + H2O2  2Fe3+ + 2OH–
(D) Be and Al have tendency to form covalent
Hydrogen Hydroxide
chlorides.
peroxide ion
26. BeO is amphoteric in nature while oxides and
hydroxides of other alkaline earth metals are 39. 8LiH + Al2Cl6  2LiAlH4 + 6LiCl
Lithium Lithium Lithium
basic in nature.
hydride aluminium chloride
27. Potassium chloride is used as a fertilizer. hydride

30
 

Chapter 08: Elements of Group 1 and Group 2

40. LiAlH4 is used as a reducing agent in organic 8. The carbonates of lithium and magnesium
synthesis. decompose easily on heating to form their
O oxides and CO2 while other alkali metal
carbonates do not.
R – C – OR 
LiAlH4
 R – CH2 – OH + R – OH
dry ether 9. Be exhibits anomalous properties because it is
Ester Alcohol the smallest and the most electronegative
element in group 2.
41. Alkaline earth metals are placed in group 2 in
the periodic table. These metals have two 14. 10 volume solution of H2O2 means that 1 L of
valence electrons and hence, they form divalent this H2O2 will give 10 L of oxygen at STP.
M2+ ions. Thus, the common oxidation state for 2H2O2  O2(g) + 2H2O(l)
alkaline earth metals is +2. 2  34 g  22.7 L at STP
68 g  22.7 L at STP
43. Alkali metals form monovalent M+ ions very
22.7 L of O2 at STP is produced from 68 g of
easily by the loss of one valence electron. The
H2O2.
M+ ion has noble gas electronic configuration
 10 L of O2 at STP is produced from H2O2
and therefore, removing an outer electron from
M+ ion requires high energy i.e., alkali metals 6810g
= = 29.956 = 30 g
have high second ionization enthalpy. Hence, 22.7
alkali metals do not form dipositive ions.  Strength of H2O2 in 10 volume solution
= 30 g/L
44. Though density of alkali metals shows an
increasing trend down the group, density of K is 15. 10 volume solution of H2O2 means that 1 L of
slightly less than that of Na. So, correct order is H2O2 will give 10 L of oxygen at STP.
Li < Na > K 2H2O2  O2(g) + 2H2O(l)
2  34 g  22.7 L at STP
 68 g  22.7 L at STP
Competitive Thinking Thus, 22.7 L of O2 at STP is produced from
H2O2 = 68 g
1. Unlike alkali metals, hydrogen does not exhibit  10 L of O2 at STP is produced from H2O2
metallic character. 6810
= g ≈ 30 g
3. Melting points of alkali metals decrease from Li 22.7
to Cs as metallic bond strength decreases on Thus, strength of H2O2 in 10 volume H2O2 = 30
moving down the group. g/L = 30 g H2O2 / 1000 g water
 Percentage strength of H2O2 in 10 volume H2O2
4. The first ionization enthalpy of alkaline earth =3%
metals are higher than those of corresponding
16. 100 volume H2O2 means that 1 L of this H2O2
alkali metals. Among alkaline earth metals, Be
will give 100 L of oxygen at STP.
has highest ionization enthalpy.
 200 mL of this H2O2 will give
Elements Be Mg Na K 100  200 103
= 20 L of oxygen at STP
1st I.E. kJ/mol) 899 737 496 419 1
2H2O2  2H2O + O2
5. Alkali metals burn vigorously in oxygen (68 g) (22.7 L)
forming oxides. Lithium forms monoxide
 22.7 L of O2 at STP is produced from H2O2 = 68 g
(Li2O), sodium forms peroxide (Na2O2) and
other alkali metals (K, Rb, Cs) form  20 L of O2 at STP is produced from
superoxides. 68 20
= 59.91 ≈ 60 g of H2O2
4Li + O2  2Li2O 22.7
Monoxide
18. In a group, ionic radii increase from top to
2Na+ O2  Na2O2 bottom while in a period, ionic radii decrease
Peroxide from left to right.
K + O2  KO2 Ion Ionic radii (pm)
Superoxide
Na+ 102
7. The hydration enthalpy of lithium ion is high. Li+ 76
So, among alkali metal chlorides, only LiCl Mg2+ 72
forms hydrates. Be2+ 31
31
 

MHT-CET Triumph Chemistry (Hints)

19. The electronic configuration of X is: M + 2H2O  M(OH)2 + H2 
1s2 2s2 2p3. Alkaline earth Water Hydrogen
 The valency of X will be 3. metal
We know valency of Mg (1s22s22p63s2) is 2.  0.5 mol of alkaline earth metal will give 0.5 mol
Magnesium reacts with X to form an ionic of hydrogen.
compound. Hence, the formula of this Hence, among the given samples of metals, 0.5
compound will be Mg3X2. mol of Ba will give the most hydrogen by
20. BeO is amphoteric while MgO, CaO and BaO reacting with water.
are basic oxides. 22. The ratio of sizes of cation to anion will be
Comparing all the oxides in the mentioned smallest for the cation having smallest size and
options, BeO is considered to be the most acidic anion having largest size.
oxide. Among Na+, K+, Mg2+ and Ca2+, the ionic radius
21. Alkali metals react with water to form is smallest for Mg2+. Among F and Cl, the
corresponding hydroxides and evolve hydrogen ionic radius is largest for Cl.
gas. 24. Due to covalent nature, chlorides of Li and Mg
2M + 2H2O  2M+ + 2OH– + H2  are soluble in alcohol and pyridine while
Alkali Water Hydrogen
metal
chlorides of other alkali metals are not soluble.
25. In peroxide, the oxidation state of oxygen is –1.
 0.5 mol of alkali metal will give 0.25 mol of
In BaO2, oxygen is in −1 oxidation state.
hydrogen.
Alkaline earth metals (such as Mg, Ca, Sr or Ba)
react with water to form corresponding
hydroxides and evolve hydrogen gas.

Hints to Evaluation Test

1. Following six diatomic molecules are possible. 10. H2O2 is prepared industrially by the air
1 1 1
H  H, H  H 2 oxidation of 2-ethylanthraquinol.
2
H  2H, 2H  3H OH
3 3 1 3
H  H, H  H C2H5
O2

 
Na+ and K+ are stable because they have
H 2 / Pd
2.
completely filled octet. So, Na and K are more
electropositive compared to Na+ and K+. Among OH
Na and K, K is more electropositive because of 2-Ethylanthraquinol
its larger atomic radius. Thus, among the given
O
species, K is most electropositive.
C2H5
4. The element having electronic configuration + H2O2
1s2 2s2 2p6 3s2 3p6 4s1 is potassium, which
forms basic oxide.
O
5. First element of a group shows diagonal 2-Ethylanthraquinone
relationship with the second element of the
succeeding group. Na is the second element of 15. First ionization enthalpy decreases down the
group 1 and Mg is the second element of group.
group 2. Li > Na > K > Rb

8. Zn + 2HCl  ZnCl2 + H2

Zinc chloride

Zn + 2NaOH  Na2ZnO2 + H2

Sodium
zincate

 Ratio of volumes of H2 evolved is 1 : 1.

32
 
Textbook
Chapter No. Chapter 10: States of Matter (Gases and Liquids)

10 States of Matter: Gaseous and Liquid States

Hints

According to Gay Lussac’s law this happens

Classical Thinking when V is constant.
14. Hydrogen bond which occurs within one single  V will remain same i.e., 5 L
molecule represents intramolecular hydrogen 42. One mole of a pure gas always occupies
bond. 22.4 L at STP.
e.g. H-bonding in ethylene glycol:
CH2 – Oδ– – Hδ+ 43. According to Avogadro’s law, V  n
m
Now, n = (where, m is the mass of the gas
CH2 – Oδ– – Hδ+ M
and M is the molar mass of the gas)
21. The SI unit of pressure is Newton per square m m
meter (N m2). It is called Pascal (Pa).  V  M
M V
30. According to Boyle’s law, at a constant m
temperature for a given mass of an ideal gas, But, = d (where, d is the density of the gas)
V
pressure is inversely proportional to the volume.  dM
1
P  49. PV = nRT
V
n P
 P
1
 P
d  =
(m/d) m V RT

 P  d ( m = constant) PV 2.46 atm  10 L

52. T= =
nR 1 mol  0.0821 Latm mol1 K 1
32. Temperature in K = 10 + 273 = 263 K = 299.63 K
35. According to Charles’ law, V  T. 54. According to Dalton’s law, the total pressure of
36. initial volume = V1 a mixture of two or more non-reactive gases is
the sum of the partial pressures of the individual
final volume = V2 = 2V1
gases in the mixture.
initial temperature = T1 = 0C = 273.15 K
final temperature = T2 62. Water reaches its critical temperature first (i.e.,
V1 V2 647.1 K) and hence, it is first to get liquefied.

T1 T2
63. N2 and O2 have Tc values much below 0 C and
T  V 273.15  2V1 their Pc values are high. Consequently,
T2 = 1 2  = 546.30 K
V1 V1 liquefaction of O2 and N2 (and air) requires
T2 = 546.30 K = 546.30  273.15 = 273.15 C compression and cooling.

37. V1 = V0 71. The different molecules of a gas move with

T1 = 273 K different velocities at any instant and hence
T2 = 10 C = 10 + 273 = 283 K have different kinetic energies.
V1 V2

T1 T2 Critical Thinking
T2  V1  283  1. In solids, particles cannot move freely as they
V2 =   V0
T1  273  occupy fixed positions.
T1 300 1 P 1 7. Strength of ion-dipole interaction depends on
40.   and P2 = 2P1 i.e., 1  charge and size of the ion. Smaller the size of
T2 600 2 P2 2
the ion, stronger is the interaction. Cations being
P1 T1
  smaller in size than anions, Na+ – H2O interaction
P2 T2
will be stronger than Cl– – H2O interaction.
33
 

Chapter 06: Redox Reactions

Option (D): 3. x –2
The sum of E0 values 0.92 – 1.09 = –0.17 V Fe3O4
is negative, therefore, reaction is not The oxidation state of Fe is
spontaneous. 3x + 4(–2) = 0
 3x – 8 = 0
41. (I) Cl2 has larger positive value of E0 than
8
Br2. Thus, Cl2 is stronger oxidizing agent  x=+
than Br2. 3
(II) Br2 has larger positive value of E0 than I2. 4. MnO 4
Thus, Br2 is stronger oxidizing agent than
 x + (2  4) = –1 or x = +7
I2.
5. PO 34 SO 24  Cr2O 72 
42. Ferrous ions (Fe+2) and ferric ions (Fe+3) have
net charge of +2 and +3 respectively. x – 8 = 3 x – 8 = 2 2x – 14 = 2
x = 3 + 8 x = 2 + 8 2x = 2 + 14
0 0 +1 1
43. 2Li + H2  2LiH x = +5 x = +6 2x = 12
Here, H2 acts as an oxidizing agent since the x = +6
oxidation number of Li increases from 0 to + 1
and that of H decreases from 0 to 1. 6. Let the oxidation state of N be x.
x 1
N2H4  2x + 4(+1) = 0
44. (A) H2SO4 + 2NaOH  Na2SO4 + 2H2O
This is a neutralization reaction.  2x = 4
0 0
 x = 2
x 1
(B) 2O3  3O2 NH3  x + 3(+1) = 0
Oxidation number of O in both O3 and O2  x = 3
is zero, therefore, it is not a redox x 1

reaction. N3H  3x + 1 = 0
0 0 +22  x = 1/3
x 1 2 1
(C) 2N2 + O2  2NO NH 2O H  x + 2(+1)  2 + 1
Here oxidation number of N increases  x = 1
from 0 in N2 to + 2 in NO and that of O
 Nitrogen in N3H exhibits highest oxidation
decreases from 0 in O2 to  2 in NO state.
therefore, it is a redox reaction.
(D) H2O(l)  H2O(g) 7. The oxidation state of N in the following
Only state of matter changes and hence compounds can be given as,
there is no change in oxidation number. HNO3 : + 1 + x + 3(2) = 0
Thus, among given options only  x = +5
option(C) represents redox reaction. NO : x  2 = 0
 x = +2
45. The oxidation numbers of the elements in their
NH4Cl : x + 4(+1) – 1 = 0
compounds are as follows:
 x = –3
N :  3,  2, + 1 to + 5
N2 : x = 0
O :  1,  1/2, + 2  The ordering of compounds according to the
C :  4, + 2, + 4 decreasing order of the oxidation state of
Cl :  1, + 1, + 3, + 4, + 5, + 6, + 7 nitrogen will be HNO3, NO, N2, NH4Cl.
Thus, Cl exhibit highest oxidation number of +7
among the given options. +4 –1 +1 –1 +6 –1 0
8. (A) XeF4 + O2F2  XeF6 + O2
+2 +5 +2 +5
Competitive Thinking (B) XeF2 + PF5 [XeF]+ PF6

1. Oxidation number of alkali metal, i.e., K is (C) +6 –1 +1 –2 +6 –2 –1 +1 –1

XeF6 + H2O  XeOF4 + 2HF
always +1.
(D) +6 –1 +1 –2 +6 –2 –1 +1 –1
x 
 XeF6 + 2H2O  XeO2F2 + 4HF
2.  AuCl4 
The reaction in option (A) is an example of a
x + 4(–1) = –1 redox reaction since xenon undergoes oxidation
 x = +3 and oxygen undergoes reduction.

25
 
Chapter 10: States of Matter: Gaseous and
Liquid States
V1 V HBr = 1 + 80 = 81
34. = 2
T1 T2 HI = 1 + 127 = 128
T1V2 2V  HI has the greatest molecular mass and least
 T2 = = 300 K  = 600 K volume.
V1 V
 T2 = 600 K = (600  273) C = 327 C 42. V = 44.8 L, n = 2 mol, T = 540 K,
R = 0.0821 L atm mol1 K1
35. At constant pressure, according to Charles’ law
PV = nRT
V1 V2
= 2 mol  0.0821 L atm mol1 K 1  540 K
T1 T2  P=
44.8 L
Let, V1 = x = 1.98 atm  2 atm
 V2 = x + 0.1x = 1.1x
x 1.1x 43. n = 2 mol, P = 3  105 Nm2,
Now, =
T1 T2 T = 300 K, R = 8.314 J K1 mol1
 T2 = 1.1 T1 PV = nRT
1.1 T1  T1 2 mol  8.314 J K 1mol1  300 K
Percentage increase =  100  V=
T1 3  105 N m 2
= 10% 2 mol  8.314 N m K 1 mol 1  300 K
=
Hence, at constant pressure, 10% increase in 3  105 N m 2
volume results into 10% increase in temperature. = 0.0166 m3 = 16.6 dm3

36. T1 = 273 C = 273 + 273 K = 546 K 44. P = 760 mm of Hg = 1 atm

T2 = 0 C = 273 + 0 C = 273 K T = 27 C = 273 + 27 = 300 K
P1 = 1 atm 2 1
n=  mol
According to Gay-Lussac’s law 32 16
P1 P2 PV = nRT
=
T1 T2 1
mol  0.0821 L atm mol1 K 1  300 K
P1T2 1 atm × 273K 1 V= 16
 P2 = = = atm 1 atm
T1 546K 2
= 1.54  1.5 L
37. Volume and number of moles being constant,
45. Molecular weight of C4H10
P P1
Gay-Lussac’s law can be given as, = = (412) + (101)
T T1
= 48 + 10 = 58 g mol–1
P P1 1
 = n= mol
T 2T 58
 P1 = 2P P = 1 atm
38. The given graph represents Gay Lussac’s law, T = 350 K
which holds good at constant volume and nRT
V=
constant number of moles. Different graphs P
plotted at constant volumes are called isochores.  1 
 mol   0.0821 L atm mol1K 1  350 K
= 
58 
40. In the identical vessels at constant temperature
and pressure, the volume and hence, their 1 atm
number of moles will be same. = 0.495 L = 495 cm3
 The number of moles of hydrogen gas will be ( 1 L = 1 dm3 = 1000 cm3)
equal to the number of moles of argon.
Hydrogen being diatomic and argon being 16 1
46. Number of moles of O2 = = mol
monoatomic, the number of atoms of argon is 32 2
half that of hydrogen. 3
Number of moles of H2 = mol
2
41. Pressure and temperature being constant,
3 1
Volume  number of moles Total number of moles =  = 2 mol
1 2 2
Also, Volume  V =
molecular mass 1 1
nRT 2 mol  0.0821 L atm mol K  273 K
Molecular mass of =
P 1 atm
HF = 1 + 19 = 20
HCl = 1 + 35.5 = 36.5 = 44.8 litres = 44800 mL
35
 

MHT-CET Triumph Chemistry (Hints)

47. 760 mm of Hg = 1 atm n A 2P  2V T n 2
  ; A
PV = nRT, n = nB 2T PV nB 1
PV 1 atm  145 L Since, number of molecules is directly
= = 5.8  6 mol
RT 0.0821 L atm mol1 K 1  300 K proportional to number of moles
1 mole of H2 gas weighs 2 g n A number of moleculesof A 2
6 mol  2 g  
 6 moles of H2 gas weighs = = 12 g n B number of moleculesof B 1
1mol
52. T2 = 2T1
48. Ideal gas equation, 1
PV = nRT P2 = P1
2
mass given mass of idealgas P1V1 P2 V2
V= = 
density(d) d T1 T2
given mass V2 P1T2 2
Number of moles, ‘n’ =   2  4
M V1 P2T1 1
given mass given mass
P = RT  There will be four-fold increase in the volume
d M
of the gas.
P RT PM
  d =
d M RT P1V1 P2 V2
53. 
T1 T2
d1 1
49.  P1 = 1 atm P2 = 0.5 atm
d2 2
T1 = 27 C = 300 K T2 = 23 C = 250 K
V2 1 1
  ( d  ) V1 = 12000 L
V1 2 V P1 T2 1 atm 250 K
T1 2  V2 =   V1 =   12000 L
 P2 T1 0.5 atm 300K
T2 1 = 20000 L
P1V1 P2 V2
 P1V1 T2 P 2T
T1 T2 54. V2 = . =  2 litres  = 2 litres
T1 P2 2P T
P1 V2 T1 1 2
   = 
P2 V1 T2 2 1 55. Density of a gas increases with decrease in
P1 1 temperature and increase in pressure.

P2 1 56. P1 = P, V1 = V, T1 = 273 + 75 = 348 K
 Ratio of pressure = 1 : 1 85
P2 = 2P, V2 =
50. PV = nRT 100
P  V 2P  85V
 V  nT 
m
T  
M 348 T2  100
m 348 K  2  85
( P and R are constant and n = ) T2 
M 100
V1 m1T1  T2 = 591.6 K = 318.6 C  319 C

V2 m 2T2 57. According to Dalton’s law, the partial pressure
T1 V1 m 2 d 2 of a gas in a mixture of gases is obtained by
   
T2 m1 V2 d1 multiplying the total pressure of mixture by
300K 0.75d mole fraction of that gas.

T2 d 58. From Dalton’s law of partial pressure,
300 Partial pressure of O2
T2  = 400 K
0.75 = Mole fraction of O2 × Total pressure of mixture
4
51. According to ideal gas equation, =  1 atm
1 4
PV
PV = nRT, n  = 0.8 atm
RT
P1V1 28 g
59. n N2 = = 1 mol
nA RT1 n A P1V1 T2 28g mol 1
 ;  
nB P2 V2 nB T1 P2 V2 16 g
n He = = 4 mol
RT2 4 gmol 1

36
 
Chapter 10: States of Matter: Gaseous and
Liquid States

Now, x N 2 =
n N2
=
1mol
=
1 77. C(s) + H2O(l)  CO(g) + H2(g)
n N 2 + n He 1 + 4  mol 5 1 mole of C gives 1 mole of CO and 1 mole of H2
1 i.e., 12 g of C gives 2 moles of product gases
P N2 = xN2 × PTotal = × 25 bar = 5 bar  48 g of C will give 8 moles of product gases
5
At STP, 1 mole of gas occupies 22.4 L of volume
60. Pressure of the gas is due to the collision of gas  At STP, 8 mole of gas will have volume
molecules with the walls of the container. = 22.4 L  8 = 179.2 L
62. Molecules of a real gas are not perfectly elastic.
PV Competitive Thinking
63. Z=
nRT 1. The graph of PV versus P at constant
For an ideal gas, Z = 1 temperature is straight line parallel to x-axis.
Hence, the slope is zero.
PV
64. Z=
nRT
PV
Z<1  <1
nRT PV (T constant)
nRT
V< P
P
RT 2. P1V1 = P2V2 
Vm < (V = Vm when n = 1 mole)
P 105 kPa  22.4 dm3 = 210 kPa  V2
0.0821  273 105 kPa × 22.4 dm3
Vm < V2 = = 11.2 dm3
1 210 kPa
Vm < 22.4 litres
3. 5.6 L at S.T.P. weighs 7.5 g.
66. 50 C and 73 atm represent a condition for CO2 7.5g  22.4 L
above its Tc. Therefore, under this condition  22.4 L at S.T.P weighs = 30 g
5.6 L
CO2 exists only as single phase i.e., gas state.
 Molar mass of gas = 30 g/mol
67. Higher the pressure to which a liquid is exposed, Hence, the gas is NO.
higher will be its boiling point. The pressure to
which water is exposed is maximum in the 4. PV = nRT
pressure cooker and minimum in the evacuated w æç RT ÷ö
V= ç ÷
vessel. Therefore, boiling point of water is M çè P ÷ø
highest in a pressure cooker and lowest in an 1.8 g 0.083 bar L K –1mol –1 ´ 647 K
evacuated vessel. = ´
18 g mol-1 1 bar
71. Molecules on the surface of liquid experience = 5.37 L
attractive forces towards the interior of the
5. PV = nRT
liquid.
nRT  m  R  T
74. P.V = constant at constant temperature. As P= = 
V M V
temperature changes, the value of constant also 1 1
changes.  6  8.314 J K mol  402 K
= mol  
 16.05  0.03 m3
75. At a particular temperature, there are always = 41647.7 Pa = 41648 Pa
elastic collisions taking place between the gas
molecules. During collisions, redistribution of 6. d1 = 5.46 g dm–3, T1 = 27 C = 300 K, P1 = 4
kinetic energy and velocity of molecules takes bar, T2 = 273 K, P2 = 1.01 bar, d2 = ?
place. Thus, all gas molecules do not possess d1 T1 d 2 T2

same velocity. P1 P2
76. Intermolecular forces of attraction keep the d1 T1 P2 5.46  300  1.01
 d2 = 
molecules together. Intramolecular forces of P1 T2 4  273
attraction hold the constituent atoms of the 1654.38
molecule intact in the molecule. This is due to = = 1.5 g cm–3
1092
formation of chemical bonds between the atoms
of the molecule. So, intermolecular force of 7. PV = nRT
attraction are much smaller than the M M
d=  P = nRT
intramolecular force of attraction. V d

37
 

MHT-CET Triumph Chemistry (Hints)

For 1 mole, WNe 10
nNe =  = 0.5 mol
PM M Ne 20
 d=
RT n H 2 + nNe = 0.25 + 0.5 = 0.75
P
As M and R are constant, d  n H2 0.25
T xH 2 = = = 0.33
n H 2 + n Ne 0.75
P
ratio is highest for 4 atm and 500 K. n Ne 0.5
T xNe = = = 0.67
 Density of carbon monoxide is maximum at n H 2 + n Ne 0.75
4 atm and 500 K. p H 2 = xH 2 PT = 0.33  2.4 = 0.8 bar
8. For given conditions, pNe = xNe PT = 0.67  2.4 = 1.6 bar
PV = RT ( n = 1) (P = 2 atm) Vreal
16. Z=

RT Videal
 V=
P Since volume is lesser than an ideal gas volume,
V
When pressure is Z < 1. For Z < 1, attractive forces are dominant.
R
constant, the slope is T  17. A gas can be liquefied by successive cooling to
P
temperature lower than its critical temperature
R and by applying pressure higher than its critical
 slope = X =
P pressure i.e., T < Tc and P > Pc.
 R = X(lit mol1 K1)  P(atm) ( P = 2 atm)
18. The gas with highest critical temperature will
 R = 2X lit atm mol1 K1 liquefy first.

9.
P1V1 P2V2
 20. Unit of surface tension = N m1 = kg s2
T1 T2 Viscosity is measured in terms of viscosity coefficient.
T1 = 15 C = 288 K Unit of viscosity coefficient = N s m2
P1 = 1.5 bar = kg m1 s1
T2 = 25 C = 298 K
22. Charles’ law: V  T at constant pressure and mass.
P2 = 1.0 bar
V = KT
V2 P1T2 1.5  298
   1.55 V
V1 T1P2 288  1.0  = K (where K is a constant)
T
V2 = 1.55 V1  1.6 V1 ln V = ln K + ln T ….(i)
w 2.303 log V = 2.303 log K + 2.303 log T
PH2 n H2 2  log V = log K + log T
10.  xH2  
PTotal n H2  n ethane w w Taking derivative of equation (i)

2 30 d  ln V  d  ln T 
=0+
w dT dt
15w 15w 15
 2   = d  ln V  1
30w  2w 15w  w 16 w 16 =
dT T
60
wRT
11. Combining ideal gas equation and Dalton’s law 23. PV = nRT =
M
of partial pressure,
 wRT 
RT  log P + log V = log  
Ptotal = ntotal  M 
V
R  1000  wRT 
 200 = (0.5 + x) ×  log V = – log P +log  
10  M 
200  10 This is straight line equation with intercept,
 0.5  x
R  1000  wRT 
log  
On solving,  M 
4 R  wRT   wRT 
x= From the intercept, log 
2R  < log  
 M 1   M2 
12. WH2 = 0.5 g, WNe = 10 g, PT = 2.4 bar wRT wRT
 
WH 2 0.5 M1 M2
n H2 =  = 0.25 mol
M H2 2  M1 > M2
38
 
Chapter 10: States of Matter: Gaseous and
Liquid States
24. Initial number of moles = Final number of 2Pi  T1T2 
moles  Pf =  
T1  T1  T2 
Pi  V Pi  V Pf V Pf V
    T2 
RT1 RT1 RT1 RT2 = 2Pi  
 P  V  Pf V  1 1   T1  T2 
2 i    
 RT1  R  T1 T2 
25. Unit of surface tension = N m1 = kg s2
2Pi  T  T2  = ML0T–2
 Pf  1 
T1  T1T2 

Hints to Evaluation Test

PM V1 V2
2. Density = 10. 
RT T1 T2
1  45 V1  T2 300 cm3  310 K
 Density =  2 g/L V2 = = = 310 cm3
0.0821  273 T1 300 K

3. V1 = 300 c.c.  Volume of air expelled = V2  V1 = 310  300

= 10 cm3
T1 = 27 C = 300 K
P1 = 620 mm = 62 cm P1V1 P2V2
12. 
P2 = 640 mm = 64 cm n1T1 n 2T2
T2 = 47 C = 320 K T1 = 300 K m1 = 2 g
P1V1 P2V2 P1 = 1 atm m2 = 1 g

T1 T2 P2 = 0.75 atm V1 = V2 = 1 L
m
P1 T2 n=
V2 =   V1 M
P2 T1
 gas is same, molecular mass = M
62 cm 320 K
=   300 c.c. n1 m1
64 cm 300 K 
V2 = 310 c.c. n 2 m2
P2 V2 n1 P V m
5. The density of an ideal gas is given as T2 =    T1 = 2  2  1  T1
P1 V1 n 2 P1 V1 m 2
PM
d= 0.75 1 2
RT =    300 = 450 K
1 1 1
1
∴ d (∵P, M, R = constant) 15. 1 mol NH3 at STP = 22.4 dm3
T
= 22400 cm3
m 5.6
6. PV = nRT ∴ PV = RT ⸫ 5.6 cm3 of NH3 = = 2.5  10–4 mol
M 22400
PVM 1 atm  8.21 L  32 g mol1
∴ m= =
RT 0.0821 L atm mol1K 1  200 K
= 16 g
7. At constant volume
P1 T1

P2 T2
P1T2
∴ P2 =
T1
800 mmHg  300 2 K
=
300 K
= 400 mmHg
8. P1V1 = P2V2
P1V1 1 atm  20 L
P2 =  = 0.5 atm
V2 40 L

39
 
Textbook
MHT-CET
Chapter No.Triumph Chemistry (Hints)

11 Adsorption and Colloids

Hints

39.
Classical Thinking
Substance Name of colloidal system
6. Rate of adsorption is dependent on temperature Foam rubber Solid sol
and pressure.
Milk Emulsion
12. The extent of adsorption is large at low Paint Sol
temperature and decreases as the temperature is
raised. Cheese Gel

14. Adsorption of hydrogen on glass is endothermic 40. Mist is a colloidal dispersion of liquid in gas.
because hydrogen dissociates.
44. ‘Hydro’ means ‘water’ and ‘philic’ means
16. Particle size of adsorbent will affect the amount ‘loving’. Hence, water-loving colloids are called
of adsorption as adsorption is a surface
hydrophilic colloids.
phenomenon. Finely divided substances are
good adsorbents as they provide large surface 52. The colloidal particles undergo ceaseless,
area. random motion in all directions over a large
18. Freundlich’s adsorption isotherm is given by: area. This motion of dispersed phase particles is
x m 1 called Brownian motion.
= kP1/n or =
m x kP1/ n 57. Coagulation power  charge on the ion.
where x = mass of gas adsorbed Hence, Sn4+ has the maximum coagulation
m = mass of adsorbent power among the given options.
P = equilibrium pressure
k and n are constants that depend on the nature 59. Milk which consists of particles of liquid fat
of adsorbate and adsorbent and temperature. dispersed in water.
23. Catalyst and reactants exist in the same phase in 63. Enzyme catalysis is an important type of
homogeneous catalysis. homogeneous catalysis.
24. Finely divided metals like Ni, Pd or Pt are used
as catalyst during hydrogenation of unsaturated Critical Thinking
vegetable oils.
1. The material or substance present in the bulk, on
25. SO2 and O2 are gases whereas V2O5 is a solid,
the surface of which adsorption takes place is
hence the reaction in option D is a
called adsorbent and the adsorbed substance is
heterogeneous catalysis.
known as adsorbate. Thus, during the adsorption
27. Ethanol acts as an inhibitor by suppressing the of carbon dioxide by activated charcoal,
formation of carbonyl chloride from chloroform molecules of carbon dioxide are adsorbate while
due to oxidation with air. adsorbent is activated charcoal.
4CHCl3 + 3O2  4COCl2 + 2H2O + 2Cl2 3. Chemisorption is highly specific and occurs
Chloroform Carbonyl only when chemical bond formation is possible
chloride between adsorbent and adsorbate.

30.
Ag/ Al2 O3
2C2H4(g) + O2(g)  2 CH2–CH2 4. Critical temperature  Ease of liquefaction of a
O gas  Extent of adsorption of the gas.
Ethylene oxide Nitrogen gas has the lowest critical temperature
(126 K) among the given gases and thus is
37. Dilute sulphuric acid is a true solution while difficult to liquefy. Hence, it is adsorbed in
others are colloids. minimum amount by activated charcoal.
40
 

Chapter 11: Adsorption and Colloids

5. The substances which provide large surface area 16. CO(g) + 3H2(g) 
Ni
 CH4(g) + H2O(g)
for a given mass are much effective as Cu / ZnO  Cr2 O3
CO(g) + 2H2(g)   CH3OH(g)
adsorbents and adsorb appreciable volumes of
X is methane (an alkane) and Y is methanol (an
gases. Finely divided substances, rough
alcohol).
surfaces, colloidal substances, etc. are good
adsorbents because they provide large surface 17. In zeolites, some silicon atoms in the three
area for a given mass. dimensional network of silicates are replaced by
Therefore, nickel metal sheet having smooth aluminium atoms.
surface is a less effective adsorbent compared to
nickel metal sheet having rough surface. 18. Blood is a colloidal dispersion of plasma
proteins and antibodies in water. However,
6. The extent of adsorption of a gas on a solid blood is also a suspension of blood cells and
surface increases with pressure of the gas at platelets in water.
constant temperature. Initially the adsorption
increases rapidly, however, as the pressure 20. Once lyophobic sols are precipitated, the
increases the surface of adsorbent becomes precipitate cannot be reconverted into sols by
covered by gas molecules. Now, the adsorption simple addition of dispersion medium. Hence,
becomes independent of pressure of the gas. the lyophobic sols are called irreversible sols.
Thus, the adsorption of a gas on a solid surface 24. Though a small quantity of an electrolyte is
varies with pressure of the gas as: necessary for the stability of colloidal solution,
Fast  slow  independent of pressure. large quantity of electrolyte may result in
coagulation. So, during peptization process
x 1
7. Freundlich adsorption isotherm is  kP n small amount of electrolyte (peptizing agent) is
m used.
Taking the logarithm of both sides of the
x 1 25. Colour of colloidal solution depends on the
equation, log  log k  log P wavelength of light scattered by dispersed
m n
The equation is the straight line equation of the particles.
form y = mx + c. Hence, Freundlich adsorption 26. When light passes through true solution
x containing solute particles not larger than 1 nm,
isotherm gives a straight line on plotting log
m the path of the light through the solution cannot
vs log P. be detected. However, if the light passes
through colloidal dispersion, because of the
8. In the low pressure range at constant
scattering of light by the colloidal particles, the
temperature, the extent of adsorption is directly
path of the light through the colloidal dispersion
proportional to the pressure of the gas.
becomes visible. This phenomenon of scattering
However, as the pressure increases and becomes
of light by colloidal particles and making the
higher, the extent of adsorption becomes
path of the light visible through the dispersion is
independent of pressure because the surface of
referred to as Tyndall effect.
adsorbent is almost fully covered by the
adsorbed gaseous molecules. This relation is 30. During electrophoresis, positively charged
correctly shown by graph of Freundlich colloidal particles move towards cathode while
equation which is as follows: negatively charged colloidal particles migrate to
anode.


31. Dispersion medium and disperse phase are two

x phases of colloid. These phases can be solid,
liquid or gas (except gas in gas which is not a
m
colloid). Colloids can be electrolysed by using
P  electrophoresis method and colloids can be
hydrophobic and hydrophilic in nature.
12. Heterogeneous catalysts are used in catalytic
converters in automobiles to reduce toxic 32. Lyophilic colloids possess solvent-loving nature
emissions and pollution by automobiles. These and thus a thin layer of dispersion medium is
catalysts are poisoned by the adsorption of Pb. formed around colloidal particles.
For this reason, automobiles with catalytic
converters require unleaded petrol. 33. The positive particles of one sol are attracted by
the negative particles of the second sol. This is
14. Inhibitors slow down the rate of reaction. followed by mutual coagulation of both the sols.
41
 

MHT-CET Triumph Chemistry (Hints)

34. According to Schulze-Hardy rules, the ions 7 Freundlich adsorption isotherm is given as:
having opposite charge to sol particles cause x
coagulation and greater the valency of = kP1/n where, n > 1.
m
oppositely charged ion, more is the coagulating 1
power, i.e., PO 43  SO 4 2   NO 3  . So, 0 < < 1
n
x
35. In oil in water emulsion, the continuous phase is Hence, = kP0.3 is the correct choice.
m
water.
9. According to the Freundlich adsorption
isotherm:
Competitive Thinking x 1
∝ Pn
m
1. Multilayer of adsorbate is formed on the
adsorbent during physical adsorption. x 1
 log = log k + log P
m n
2. The magnitude of Hadsorption is low during the This corresponds to the equation of a straight
physisorption process, however it has negative line: y = mx + c
value as the process is exothermic. 1 2
 Slope of the line (m) is equal to =
n 3
3. x 2
 ∝ P3
Gas NH3 O2 N2 H2 m
Critical 10. Zeolites are shape-selective catalysts whose
406 154 126 33
Temperature (K) catalytic activity depends on the size of the
cavities, pores and apertures in their structure.
On the basis of critical temperatures of these 13. Sulphur sol is formed by the aggregation of S8
gases, NH3, having highest critical temperature, molecules within colloidal dimensions.
will undergo maximum adsorption.
15. Gold sol consists of particles which are formed
4. The general form of Freundlich adsorption by the aggregation of many gold atoms. Hence,
isotherm may be also represented as: gold sol is an example of multimolecular
x 1 colloid.
log = log k + log P
m n 18. Statement (iii) is incorrect because the process
x of removing a dissolved substance from a
This will give a straight line on plotting log colloidal solution by means of diffusion through
m
versus log P with intercept as log k. a suitable membrane is called dialysis.
20. According to Hardy-Schulze rule, higher the
5. Freundlich adsorption isotherm is charge (greater the valency) of the coagulating
x 1 ion, more is its coagulating power
 kP n ……. (k, n are constants.)
m (PO34  SO 24   Cl  ) .
x 1
 log = log k + log P 22. According to Hardy-Schulze rule, for the
m n
coagulation of a negatively charged colloid,
Comparing with general form : y = mx + c greater the charge on the cation, greater will be
1 its coagulating power and less will be the
 = slope amount of electrolyte required.
n
Electrolyte Cation Charge on cation
6. The general form of Freundlich adsorption
NaNO3 Na+ +1
isotherm may be also represented as:
Ba(NO3)2 Ba2+ +2
x 1
log = log k + log P Al(NO3)3 Al3+ +3
m n
Comparing with general form : y = mx + c Thus, the amount of electrolyte required to
1 coagulate a given amount of negatively charged
The slope of the line is equal to and the AgI colloidal solution will be in the order:
n
intercept is equal to log k. NaNO3 > Ba(NO3)2 > Al(NO3)3
42
 

Chapter 11: Adsorption and Colloids

Hints to Evaluation Test

1. Coagulation is brought about by the oppositely

charged ions. According to Hardy-Schulze rule,
coagulating power is directly proportional to
charge on the ion. Hence, minimum amount of
AlCl3 will be needed for the coagulation of
negatively charged suspension of clay in water.
3. Heterogeneous catalysis can be explained by the
adsorption theory, as the catalyst exists in a
different phase from the reactants.
11. The physical adsorption may be easily reversed
by lowering the pressure of the gas or by raising
the temperature of the surface.
12. As temperature increases at a constant pressure
‘P’, the amount of gas adsorbed decrease.
15. Ni
CO(g) + 3H2(g)   CH4(g) + H2O(g)
Carbon Methane
monoxide

43
 Textbook
Chapter No.

14 Basic Principles of Organic Chemistry

Hints

11. Tropone (Option C) is a homocyclic non-

Classical Thinking benzenoid aromatic compound.
4. The given compound CH3CH2CH2CH2CH3 has O
five carbon atoms.
Therefore, its bond-line formula is 15. Given compound has  C  O  functional group
2 4 i.e., ester group. Hence, the compound is an
1 5 ester.
3
5. The correct bond line formula for the compound O O
is:
16. CH3CH2CNH2 has the functional group  CNH2
CH=CHCHO
i.e., amido group.
O Hence, the class of compound to which this
≡
compound belongs is amides.
18. Members of the homologous series show similar
6. Fischer projection/cross formula is more chemical properties while physical properties
commonly used in carbohydrate chemistry. show a gradual change with increase in the
molecular mass of the member.
7. Option (A): Fischer projection/cross formula
Option (B): Wedge formula 19. Structural formula of the second higher
Option (C): Newman projection formula homologue is obtained by adding two −CH2−
Option (D): Sawhorse formula units to methane.
CH4   CH3 – CH2 – CH3
add two
8. The cyclic organic compounds which have a  CH2  units
ring made up of only carbon atoms are called as 2nd Higher homologue
carbocyclic or homocyclic compounds. (C3H8)

9. Compound Structure 21. Addition of two −CH2− units to propyl chloride

(C3H7Cl) will give pentyl chloride (C5H11Cl).
Naphthalene Thus, pentyl chloride is a second higher
homologue of propyl chloride.

NH2 22. The members of homologous series differ by

CH2 units and they have same functional
Aniline group. Among the given pairs, only the
compounds in option (A) differ by CH2 unit
and have same functional group. Hence, they
represent a homologous series.
OH
23. Tertiary carbon (3) is bonded to three other
Phenol
carbon atoms.
1
H CH3
CH3  CH  CH3 1 3 2 4 1
Isobutane H3C  C  CH2  C  CH3
CH3 1 CH 1CH
3 3
10. Non-benzenoid compounds contain an aromatic Thus, there is only one tertiary carbon atom in
ring other than benzene. the given compound.
44
 

Chapter 14: Basic Principles of Organic Chemistry

CH3 CH3 Option (B): OH H

25. CH3  CH  CH  CH3 H3C  C  C  CH2  CH3

1 2 3 4 1 2 3 4 5

The IUPAC name of the compound is H CH3

2,3-dimethylbutane. 3-Methylpentan-2-ol

26. The longest continuous chain of carbon atoms in Option (C): CH3
the structure is selected as the parent chain and
the substituted carbon atoms should carry the H3C  CH  CH2  CH2  CH2  OH
5 4 3 2 1
lowest possible numbers.
4-Methylpentan-1-ol
CH3 CH3
Option (D): CH3
CH3  C  CH  CH2  CH2  CH3
1 2 3 4 5 6 H3C  CH2  CH2  CH  CH2  OH
CH3 5 4 3 2 1
2-Methylpentan-1-ol
The compound given in option C is
2,2,3-trimethylhexane. 31. O O
1 2 3 4 OR H3C – CH2 – C – H
27. CH2 = CH  CH  CH3 3 2 1
The functional group present is CHO. So, the
CH3 compound is an aldehyde. The parent alkane is
propane. Aldehydes are named as alkanal. So,
3-Methylbut-1-ene
the name of the compound is propanal.
28. 3
6 5 4
1 32. CH3
2
H3C  CH  CH2  C  CH3
5 4 3 2 1
4-Ethylhex-1-en-5-yne
OH OH
29. The IUPAC name of the compound is
Compound IUPAC nomenclature 2-methylpentane-2,4-diol.
6
5 34. CH3CH2CH(CH3)CHO: 2-Methylbutanal
1
(A) 1,4-Dimethylcyclohexane 37. In stereoisomerism, different compounds have
4 2
3 the same structural formula but different relative
arrangement of groups / atoms in space.
6
5 1 39. Position isomers have same functional group at
(B) 1,3-Dimethylcyclohexane different positions on the parent chain.
4 2
3 CH3  CH2  CH = CH2 CH3  CH = CH  CH3
6 But-1-ene But-2-ene
5 (C4H8) (C4H8)
(C) 1 1,2-Dimethylcyclohexane
4 2 42. Homolytic cleavage of a covalent bond gives
3 two neutral species both carrying one unpaired
6 electron.
5 1
(D) 1,1-Dimethylcyclohexane 43. Homolytic cleavage of C−C bond in ethane:
4 2 U.V.Light
H3C – CH3    CH3 + CH3
3 Ethane Methyl free
radicals
30. Option (A): OH CH3 44. The organic reactions which proceed by free
radical formation are known as nonpolar reactions.
H3C  C  CH2  C  CH3
1 2 3 4 5 45. The carbon atom of methyl free radical with an
H H unpaired electron is sp2 hybridized and has
4-Methylpentan-2-ol planar trigonal geometry.
45
 

MHT-CET Triumph Chemistry (Hints)

46. Heterolysis of carbon-chlorine bond produces 5. Option (A): Sawhorse formula of propane
one cation and one anion. Option (B): Sawhorse formula of ethane
 C  Cl 
Heterolytic
bond fission
 C  Cl Option (C): Newman projections of ethane
Cation Anion Option (D): Newman projections of propane
In C  Cl bond, as chlorine atom is more
electronegative than carbon atom, the electron 6. In wedge formula, a solid wedge is used to
pair is retained by chlorine atom on fission. represent a bond projecting up from the paper
53. Alkyl group shows +I effect while COOH towards the viewer.
groups shows –I effect. Space filling model emphasizes on relative size
of each atom. Frame work model emphasizes
54. Resonance forms are shown with double-headed the skeletal pattern of bonds ignoring size of
arrow between them. atoms.
55. The energy of the resonance hybrid is lower
7. Homocyclic compounds:
than that of any of the contributing resonance
structures. H2C CH2 CH3
57. When the transfer of electrons is away from an
atom or substituent group attached to the
conjugated system, it is termed as positive H2C CH2 O
resonance effect. Cyclobutane Tropone Toluene
NH2 group shows positive resonance effect
Heterocyclic compound:
while COOH, CHO and CN groups show
negative resonance effect. CH
58. Cyclohexane does not contain lone pair of HC CH
electrons which can take part in resonating
structures. HC CH
N
60. There are three hyperconjugation structures in Pyridine
ethyl cation.
8. Pyridine (option D) is a heterocyclic aromatic
H H H+ H H H H H (heteroaromatic) compound.

H  C  C+ HC=C H+ C = C HC=C 9. Both are heterocyclic compounds. The

heteroatom present in both the compounds is
H H H H H H H nitrogen.
Ethyl cation I II III

N N
Critical Thinking Pyridine
(Heterocyclic H
1. In complete structural formula, all the bonds aromatic) Piperidine
between the atoms are represented using a dash (Heterocyclic
non-aromatic)
(). A single bond is represented by a single
dash (–), a double bond by double dash (=) and
10. The compound has molecular formula
a triple bond by triple dash (). C6H5O2N. It has six carbon atoms in a ring
4. system with alternating single and double
bonds. This indicates that the structure has an
OR aromatic benzene ring. The compound also has
HO an NO2 group as a substituent. Hence, its
structure will be
H CH3 CH3
NO2
HO  CH2  C  C  CH2  C  CH3

CH3 H H
There are four methyl (CH3) groups in the Thus, the given compound ‘X’ is homocyclic
given structure. and aromatic.
46
 

Chapter 14: Basic Principles of Organic Chemistry

11. 19. The priority is given to COOH group and then
Class of the compound General formula to C = O group.
Ketones R C R
O
O 5 4|| 3 2 1
Acid anhydrides H3C  C  CH  CH  COOH
R C O C R | |
Cl Br
O O
Esters 2-Bromo-3-chloro-4-oxopentanoic acid
R C OR
1 2 3 4 5
O 20. CH3  CH  C  CH2  CH3
Ethers R – O – R
12. H3C  C  CH3 has a keto group. I O
The name of the compound is 2-iodopentan-3-
O one.
Hence, it belongs to the family of ketones. 23. (A) Functional isomers:
The compounds in option (A), (C) and (D) have
aldehyde functional group and hence, they CH3  CH2  COOH CH3COOCH3
belong to the family of aldehydes. Propanoic acid Methyl ethanoate
(B) Position isomers:
14. Homologues differ by CH2 unit. The
molecular weight of CH2 is 12 + (2  1) = 14. CH3  CH  CHO HO  CH2  CH2  CHO
Therefore, homologues differ in their molecular OH 3-Hydroxypropanal
weights by 14 units. 2-Hydroxypropanal
16. The general molecular formula of given
(C) Functional isomers:
homologues series is, CnH2n – 2 [from given
homologues]. Thus, X must be alkyne. CH2OH OH
C5H8 is a second higher homologue of CH3
compound X. Thus,
remove
C5H8 two
C3H4
 CH 2  units Benzyl alcohol o-Cresol
C2H2 is a first lower homologue of compound X.
(D) Metamers:
Thus, C2H2   C3H4
add one
 CH2  unit
CH3 C2H5
Therefore, compound X is propyne (C3H4). C3H7  N C2H5  N
17. A quaternary carbon atom is bonded to four CH3 CH3
Dimethylpropylamine Diethylmethylamine
other carbon atoms.
CH3 Quaternary carbon atom
24. Free radicals are stabilized by electron-donating
1 3 4 effect of alkyl groups.
H3C 2C  CH2  CH3 Higher the number of alkyl substituents, higher
is the stability of the free radical. Hence, the
CH3 stability of given free radicals decreases in the
18. If the substituent is further branched, it is named order.
as substituted alkyl group, by numbering the  
(CH 3 )3C > (CH 3 ) 2CH > CH 3CH 2 > CH3
 

carbon atom of this group attached to the parent

3 Free 2 Free 1 Free Methyl free
chain as 1. The name of such a substituent is
radical radical radical radical
enclosed in brackets to avoid confusion with the
numbering of parent chain. 25. Methyl free radical contains an odd electron i.e.,
unpaired electron, hence paramagnetic in nature.
CH3 CH3
28. Nucleophiles Electrophiles
CH3CH2CH2CHCH2CHCH2 C CH3
9 8 7 6 5 4 3 2 1 H2O, NH3, CN, OH BF3, H+, AlCl3, NO2
1 CHCH3 CH3
Thus, the series that contains only nucleophiles
H3C–CH2 is NH3, H2O and OH.
3 2
The IUPAC name is 2,2,6-trimethyl-4- 29. Alkyl groups such as CH(CH3)2 shows +I
(1-methylpropyl)nonane. effect.

47
 

MHT-CET Triumph Chemistry (Hints)

31. The resonance structure with the lowest energy 11. O
is a major resonance contributor.
32. The structure does not have lone pair of CH2 – CH2 – C – OH
3 2 1
electrons or  electrons that are required for
resonance. Hence, resonance effect is not
3-Phenylpropanoic acid
present in this structure.

12. CHO
Competitive Thinking 1
NO2
1. 2
3
4
OCH3
4-Methoxy-2-nitrobenzaldehyde
O
Tropone
13. A. n-Butane and isobutane are chain isomers.
It is a homocyclic non-benzenoid compound. B. Dimethyl ether and ethanol are functional
3. C6H10O2N is the successive member of the group isomers.
homologous series of C5H8O2N as they differ C. Ethanoic acid (CH3COOH) and methyl
from each other in molecular formula by a methanoate (HCOOCH3) are functional
methylene ( CH2 ) group. group isomers.
Also, in homologous series, the members differ
14. α-Hydrogen at bridge carbon never participate
only in the number of C and H atoms. The in tautomerism. Thus, only (III) exhibits
number of hetero atoms remains the same. tautomerism.
Only in option (D), the number of O and
N-atoms are same as in the compound given in O OH


question.
Thus, option (D) is the correct answer. Enol form
H
5. The given molecule can also be written as
follows: 15. The structure of enolic form is,
1 2 3 4 5 6 7 H H
H3C  CH  CH = CH  CH = CH  CH  CH3
H
8 9 C C O
CH3 CH2  CH3 H C C H H
2,7-Dimethylnona-3,5-diene
OH OCCH
6. The functional group in the molecule is keto
group. In ketones, the final ‘-e’ from the parent H H
alkane name is dropped and the suffix ‘-one’ is
17. The positive inductive (+I) effect stabilises the
added to give the base name.
free radical. Therefore, the free radicals
CH3  CO  CH2  CH2  CH3 containing more number of electron donating
1 2 3 4 5 substituents like alkyl groups are more stable.
The IUPAC name of the compound is
H H CH3 CH3
pentan-2-one.
8. For compounds having functional groups along H  C < H3C  C < H3C  C < H3C  C
with multiple bonds order of preference will be
as follows: H H H CH3
Functional group > Double bond > Triple bond Methyl 1 2 3
> Side chain
O 18. More the number of the alkyl groups, greater
O will be the dispersal of the positive charge on
H C 2 the carbon atom due to the +I (electron
1 3 4 releasing) effect, and thereby greater will be the
5 stability. Hence, the most stable carbocation
6

3-Keto-2-methylhex-4-enal formed from the given compounds is  H 3C 3 C .

48
 

Chapter 14: Basic Principles of Organic Chemistry

24. Resonance effect is observed in a conjugated 27. In alkyl free radicals, the carbon atom having
system of  electrons. In option (B), lone pair the unpaired electron is sp2 hybridised. For
on ‘N’ atom is not in conjugation with carbon- hyperconjugation the -carbon atom with
carbon  bond. Hence, resonance effect is not respect to sp2 hybridised carbon atom should
observed in the structure given in option (B). have at least one hydrogen atom. Among the
given structures, only (III) has an -hydrogen
25. +
O  CH3 O  CH3 atom.


CH3
In other structures,  bond is not in conjugation H -H atom
with lone pairs of electrons. Hence, in these Hence, hyperconjugation occurs in structure
molecules lone pairs are not delocalized. (III).
26. The resonance structures of pyrrole are: 28. Stability of carbocations depends upon the
extent of hyperconjugation effect which in turn
4 3 4 4 3

3 depends on the number of hyperconjugation
5 2 + 2  + 2 structures possible.
N1 5 N1 5 N1   
H H H CH3  CH – CH2  CH2 – CH3
has maximum (five) -H and thus has five
3 hyperconjugation structures. Hence, it is the
4 3 4
most stable carbocation among the given.
5 + 2 5 + 
N1 N1 2 29.  NO2 group is an electron withdrawing group
H H and it exhibits I effect. This I effect decreases
with increase in distance. In option (C), as the
The electron density is maximum on 2nd and 5th
C-atom with positive charge is at a maximum
carbon atoms as these carbon atoms are closer to
distance, so I effect is minimum and hence, it
the electronegative N-atom.
is the most stable carbocation.

Hints to Evaluation Test

1. The bond line formula for 1,1,1-trichloroethane 4. CH3  CH  CH2  CH  CH3

4 3 2 1
can be represented as:
5 CH2 OH
Cl
6 CH3
Cl
The IUPAC name of the compound is
Cl 4-methylhexan-2-ol.
2. Benzenoid aromatic compounds contain at least 6. BCl3 is an electron-deficient species and hence,
one benzene ring in the structure. Thus, aniline
it is an electrophile. CN, ROH and NH3 are
is a benzenoid aromatic compound. Pyrrole is a
electron-rich species and hence, these are
non-benzenoid aromatic compound.
nucleophiles.

3. Electromeric effect arises due to the mobility of 7. The polarizability/ electromeric electronic effect
electrons in double or triple bonds, i.e., it is occurs in a substrate due to approach of the
possible only in a -bonded compound. Among attacking reagent hence it is a temporary effect.
the given options, only ethyne has  bonds and 10. Benzenoid compounds contain at least one
can undergo electromeric effect. benzene ring.
49
 

MHT-CET Triumph Chemistry (Hints)

12. Hyperconjugation involves the delocalization of
electrons due to overlap between a  bond and
an empty p-orbital. However, it occurs only if 
bond and empty p-orbital have proper
orientation.
13.
(A) 1 (B) 1
CH3 CH3
1 3
CH3 – C – H 2
CH2
1 CH3 CH3 – CH2 – C – H
1 2 3

CH2
2
CH3
1

(C) 1
(D)
1
CH3 CH3
4 2 3 1
CH3 – C – CH2 – CH – CH3 CH3 – C – CH3
1 1 4 1
CH3 CH3 CH3
1 1
Thus, the structure given in option (C) contains
primary, secondary, tertiary and quaternary
carbon atoms together.
14. The priority is first given to CHO group and
then OH group. So, the base name is derived
from CHO group and the OH group is named
as the substituent.
5 4 3 2 1
CH3  CH  CH2  CH  CHO

OH CH3
The IUPAC name of the compound is
4-hydroxy-2-methylpentanal.
15. Higher the number of electron donating groups
attached to the carbon carrying positive charge,
higher will be the stability.

50
 
Textbook
Chapter No. Chapter 15: Hydrocarbons

15 Hydrocarbons

Hints

Classical Thinking
4. The alkanes in which at least one carbon atom is bonded to more than two other carbon atoms are known as
branched chain alkanes.
CH4 CH3 – CH3 CH3 – CH2 – CH3
Methane Ethane Propane
Methane, ethane and propane cannot form branched chain alkanes. Hence, the minimum number of carbon
atoms necessary for a hydrocarbon to form a branched structure is 4 i.e., butane onwards alkanes can form
branched chain alkanes.
6. General molecular formula of alkanes is CnH2n+2.
In butane, 4 carbon atoms are present therefore, n = 4. Substituting the value of n in the general formula of
alkanes, we get the molecular formula of butane as C4H10.
7. Hexane has 5 isomers.

Hexane 2-Methylpentane 3-Methylpentane

2,2-Dimethylbutane
2,3-Dimethylbutane

Ni
10. CH3  C  CH + 2H2 
 high temp and high pressure 
 CH3CH2CH3
Propyne Propane
‘A’

11. CH3(CH2)2  I + 2[H] 

Zn / HCl
CH3 – CH2–CH3 + HI
Propyl Nascent Propane
iodide hydrogen (A)

13. CH3  CH2  Br + 2Na + Br  CH2  CH3 

dry ether
 CH3  CH2  CH2  CH3 + 2NaBr


Ethyl bromide Sodium Ethyl bromide n-Butane Sodium bromide

metal

14. For straight chain alkanes melting points increases with an increase in the number of carbon atoms.
Therefore the increasing order of the melting points of given compounds is,
Propane < n-Butane < n-Pentane < n-Hexane.
15. First four alkanes are gases and alkanes having carbon atoms in the range from 5 to 17 are liquids at room
temperature.
18. Chlorine reacts with methane in sunlight or U.V. light (or on heating) to give a mixture of four different
alkyl halides. When all the four H-atoms of methane are substituted by Cl-atoms, the end product formed
will be tetrachloromethane (carbon tetrachloride).
51
 
Chapter 10: States of Matter: Gaseous and
Liquid States

Now, x N 2 =
n N2
=
1mol
=
1 77. C(s) + H2O(l)  CO(g) + H2(g)
n N 2 + n He 1 + 4  mol 5 1 mole of C gives 1 mole of CO and 1 mole of H2
1 i.e., 12 g of C gives 2 moles of product gases
P N2 = xN2 × PTotal = × 25 bar = 5 bar  48 g of C will give 8 moles of product gases
5
At STP, 1 mole of gas occupies 22.4 L of volume
60. Pressure of the gas is due to the collision of gas  At STP, 8 mole of gas will have volume
molecules with the walls of the container. = 22.4 L  8 = 179.2 L
62. Molecules of a real gas are not perfectly elastic.
PV Competitive Thinking
63. Z=
nRT 1. The graph of PV versus P at constant
For an ideal gas, Z = 1 temperature is straight line parallel to x-axis.
Hence, the slope is zero.
PV
64. Z=
nRT
PV
Z<1  <1
nRT PV (T constant)
nRT
V< P
P
RT 2. P1V1 = P2V2 
Vm < (V = Vm when n = 1 mole)
P 105 kPa  22.4 dm3 = 210 kPa  V2
0.0821  273 105 kPa × 22.4 dm3
Vm < V2 = = 11.2 dm3
1 210 kPa
Vm < 22.4 litres
3. 5.6 L at S.T.P. weighs 7.5 g.
66. 50 C and 73 atm represent a condition for CO2 7.5g  22.4 L
above its Tc. Therefore, under this condition  22.4 L at S.T.P weighs = 30 g
5.6 L
CO2 exists only as single phase i.e., gas state.
 Molar mass of gas = 30 g/mol
67. Higher the pressure to which a liquid is exposed, Hence, the gas is NO.
higher will be its boiling point. The pressure to
which water is exposed is maximum in the 4. PV = nRT
pressure cooker and minimum in the evacuated w æç RT ÷ö
V= ç ÷
vessel. Therefore, boiling point of water is M çè P ÷ø
highest in a pressure cooker and lowest in an 1.8 g 0.083 bar L K –1mol –1 ´ 647 K
evacuated vessel. = ´
18 g mol-1 1 bar
71. Molecules on the surface of liquid experience = 5.37 L
attractive forces towards the interior of the
5. PV = nRT
liquid.
nRT  m  R  T
74. P.V = constant at constant temperature. As P= = 
V M V
temperature changes, the value of constant also 1 1
changes.  6  8.314 J K mol  402 K
= mol  
 16.05  0.03 m3
75. At a particular temperature, there are always = 41647.7 Pa = 41648 Pa
elastic collisions taking place between the gas
molecules. During collisions, redistribution of 6. d1 = 5.46 g dm–3, T1 = 27 C = 300 K, P1 = 4
kinetic energy and velocity of molecules takes bar, T2 = 273 K, P2 = 1.01 bar, d2 = ?
place. Thus, all gas molecules do not possess d1 T1 d 2 T2

same velocity. P1 P2
76. Intermolecular forces of attraction keep the d1 T1 P2 5.46  300  1.01
 d2 = 
molecules together. Intramolecular forces of P1 T2 4  273
attraction hold the constituent atoms of the 1654.38
molecule intact in the molecule. This is due to = = 1.5 g cm–3
1092
formation of chemical bonds between the atoms
of the molecule. So, intermolecular force of 7. PV = nRT
attraction are much smaller than the M M
d=  P = nRT
intramolecular force of attraction. V d

37
 

Chapter 15: Hydrocarbons

41. Ethylene dibromide when heated with zinc ethylene is obtained.
Br  CH2  CH2  Br + Zn 
alcohol
 CH2 = CH2 + ZnBr2


1,2-Dibromoethane Ethene
(Ethylene dibromide) (Ethylene)

45. Cl
|
CH3  C = CH  CH3 + HCl 
Markovniko v's rule
 CH3  C  CH2  CH3
| |
CH3 CH3
2-Methylbut-2-ene 2-Chloro-2-methylbutane

47. Reaction of HBr with propene in the presence of organic peroxide follows anti-Markovnikov’s addition and
gives n-propyl bromide as the major product.
CH3  CH = CH2  HBr
 CH3  CH2  CH2  Br
Peroxide

Propene n-Propyl bromide

48. CH3 – CH = CH2 + H–OSO3H  H  OH

H3C – CH – CH3  
 H3C  CH  CH3 + H2SO4
Propene (cold and conc.)
| |
(Propylene) Sulphuric OSO3H OH
acid Isopropyl hydrogen sulphate Propan-2-ol
(Isopropyl alcohol)
(Major product)

H O H
50.
C C
H2C = CH2 + O3  H H 
Zn / H 2 O

 2HCHO + ZnO
Ethene or Ethylene Formaldehyde
O O ‘B’

Ethylene ozonide
‘A’
52.
H H
H
6H3C  C = C  H + H  B 
THF
solvent
 2(CH3  CH2  CH2)3B
Propene H
2
Diborane

H3C  CH2  CH2

H3C  CH2  CH2  B 
3 HO - OH
NaOH
 3CH3  CH2  CH2  OH + B(OH)3
H3C  CH2  CH2 3 Propan-1-ol
(n-Propyl alcohol)
Tri-n-propylborane

53. Dilute alkaline KMnO4 is an oxidising agent and is known as Baeyer’s reagent. This reagent oxidizes
alkenes in the presence of water at low temperature to form dihydric alcohols, also called alkane diols,
vicinal glycols or 1,2-diols. In this reaction, KMnO4 is used up, hence the purple colour of potassium
permanganate disappears i.e., decolourisation of KMnO4 solution takes place.
54. CH2 = CH2 + H2O + [O] 
alkaline KMnO4
HO  CH2  CH2  OH
Ethylene Ethylene glycol
(Ethene) (Ethane-1,2-diol)

55. CH3CH = CH2 + H2O + (O) 

alkaline KMnO4
CH3  CH  CH2
Propene
OH OH
Propylene glycol

53
 

MHT-CET Triumph Chemistry (Hints)

For 1 mole, WNe 10
nNe =  = 0.5 mol
PM M Ne 20
 d=
RT n H 2 + nNe = 0.25 + 0.5 = 0.75
P
As M and R are constant, d  n H2 0.25
T xH 2 = = = 0.33
n H 2 + n Ne 0.75
P
ratio is highest for 4 atm and 500 K. n Ne 0.5
T xNe = = = 0.67
 Density of carbon monoxide is maximum at n H 2 + n Ne 0.75
4 atm and 500 K. p H 2 = xH 2 PT = 0.33  2.4 = 0.8 bar
8. For given conditions, pNe = xNe PT = 0.67  2.4 = 1.6 bar
PV = RT ( n = 1) (P = 2 atm) Vreal
16. Z=

RT Videal
 V=
P Since volume is lesser than an ideal gas volume,
V
When pressure is Z < 1. For Z < 1, attractive forces are dominant.
R
constant, the slope is T  17. A gas can be liquefied by successive cooling to
P
temperature lower than its critical temperature
R and by applying pressure higher than its critical
 slope = X =
P pressure i.e., T < Tc and P > Pc.
 R = X(lit mol1 K1)  P(atm) ( P = 2 atm)
18. The gas with highest critical temperature will
 R = 2X lit atm mol1 K1 liquefy first.

9.
P1V1 P2V2
 20. Unit of surface tension = N m1 = kg s2
T1 T2 Viscosity is measured in terms of viscosity coefficient.
T1 = 15 C = 288 K Unit of viscosity coefficient = N s m2
P1 = 1.5 bar = kg m1 s1
T2 = 25 C = 298 K
22. Charles’ law: V  T at constant pressure and mass.
P2 = 1.0 bar
V = KT
V2 P1T2 1.5  298
   1.55 V
V1 T1P2 288  1.0  = K (where K is a constant)
T
V2 = 1.55 V1  1.6 V1 ln V = ln K + ln T ….(i)
w 2.303 log V = 2.303 log K + 2.303 log T
PH2 n H2 2  log V = log K + log T
10.  xH2  
PTotal n H2  n ethane w w Taking derivative of equation (i)

2 30 d  ln V  d  ln T 
=0+
w dT dt
15w 15w 15
 2   = d  ln V  1
30w  2w 15w  w 16 w 16 =
dT T
60
wRT
11. Combining ideal gas equation and Dalton’s law 23. PV = nRT =
M
of partial pressure,
 wRT 
RT  log P + log V = log  
Ptotal = ntotal  M 
V
R  1000  wRT 
 200 = (0.5 + x) ×  log V = – log P +log  
10  M 
200  10 This is straight line equation with intercept,
 0.5  x
R  1000  wRT 
log  
On solving,  M 
4 R  wRT   wRT 
x= From the intercept, log 
2R  < log  
 M 1   M2 
12. WH2 = 0.5 g, WNe = 10 g, PT = 2.4 bar wRT wRT
 
WH 2 0.5 M1 M2
n H2 =  = 0.25 mol
M H2 2  M1 > M2
38
 

Chapter 15: Hydrocarbons

83. In benzene, all the six carbon–carbon bonds are of same length due to resonance. In but-2-ene and
but-1-ene, all the carbon–carbon bonds are not of the same length because there are single and double bonds
in their structure.
H H

H3C  C = C  CH3 H2C = CH  CH2  CH3

But-2-ene But-1-ene
In prop-1-yne, there is a single and a triple bond and hence, it does not have the carbon-carbon bonds of the
same length.
HC  C  CH3
Prop-1-yne

85.

Anthracene
There are 7 bonds in anthracene, so the number of  electrons is 14.
86. Compound given in option (B) is aromatic since it has 6 electrons and hence, obeys Huckel rule of
aromaticity.
H
CH H C
87. HC CH H

Red hot iron tube
873 K
C C
+
HC CH C C
CH H H
C
Ethyne
(Acetylene) H
Benzene

88. When anhydrous sodium benzoate is heated with soda lime, it undergoes decarboxylation and gives benzene.
O
C  ONa

CaO
+ NaOH 

 + Na2CO3

Benzene
Sodium benzoate

90. The electrophile involved in the chlorination of benzene in the presence of anhydrous AlCl3 is Cl+.
It is generated as follows:
 Cl+ + [AlCl4]
Cl  Cl + AlCl3 
Cl
91. Cl
Cl
anhydrous AlCl3
+ 6Cl2 + 6HCl
Cl Cl
Benzene Cl
Hexachlorobenzene

93. When benzene is heated with a mixture of conc. HNO3 and conc. H2SO4, nitration reaction takes place.
NO2

conc. H 2SO 4 , 
+ HNO3 
Nitration

Conc.
Benzene Nitrobenzene
55
 

MHT-CET Triumph Chemistry (Hints)

96. AlCl3 is a Lewis acid which helps in formation of electrophile in the Friedel-Craft’s reaction.
In Friedel-Craft’s alkylation, the electrophile generated is R+ (carbocation) while in Friedel-Craft’s
acylation, the electrophile generated is R  C+ (acylium ion).
 R + + [AlCl4]
R  Cl + AlCl3  O
 R  C + + [AlCl4]
R  C  Cl + AlCl3 

O O
97. The base or nucleophile in the electrophilic substitution reactions is as follows:
Chlorination/Friedel-Craft’s
Alkylation or acylation : [AlCl4]
Bromination : [FeBr4]
Nitration : [HSO4]
99. The electron density in the aromatic ring in nitrobenzene decreases at ortho (o-) and para (p-) positions (as
shown in the resonating structures), due to the strong electron withdrawing resonance effect of NO2 group.
  O
O O O O O O O O O
N N N N N

+ +

+
II I III IV V
104. CH3CH = CH2 
HBr
 CH3CH(Br)CH3 
alc.KOH
 CH3CH = CH2 
O3
CH3CHO + HCHO
Zn.H 2 O
Propene 2-Bromopropane Propene Acetaldehyde Formaldehyde
(A) (B) (C)
105. Since, the given compound is an alkyne (CnH2n  2), the molecular weight is given as follows:
Molecular weight = (12  n) + [1  (2n  2)]
where, n = integer indicating number of carbon atoms
12 = atomic weight of carbon, 1 = atomic weight of hydrogen
180 = 12n + 2n  2
182 = 14n
182
n= = 13
14
 n = 13
 The alkyne with molecular weight of 180 is C13H24.
106. Disubstituted benzene derivatives are given common names using prefixes ortho (o-), meta (m-) or para (p-)
depending on the relative positions of the substituents.
A
1 A
6 2 Substituents in 1, 2 positions  ortho (o-)
5 3
4
A
1
6 2
Substituents in 1, 3 positions  meta (m-)
5
3
4 A
A
1
6 2
Substituents in 1, 4 positions  para (p-)
5 3
4
A
Thus, if two substituents are on the adjacent carbon atoms (1, 2 positions) in a disubstituted benzene, then
the compound is named using prefix ortho.
56
 

Chapter 15: Hydrocarbons

Critical Thinking
1. General molecular formula of alkanes is CnH2n+2.
In the alkane with 17 carbon atoms, n = 17. Substituting the value of n in the general formula of alkanes, we
get the molecular formula as C17H36.
2. Since, the given compound is saturated hydrocarbon therefore, comparing the formula with general
molecular formula of alkanes CnH2n+2 we get,
2n + 2 = 14
2n = 12
 n=6
4. Butane and 2-methylpropane are structural isomers.
CH3  CH2  CH2  CH3 and CH3  CH  CH3

Butane CH3
2-Methylpropane
6. Hexane (C6H14) has following isomers.
CH3 CH3

CH3 – CH2 – CH2 – CH2 – CH2 – CH3 CH3 – CH – CH2 – CH2 – CH3 CH3 – CH2 – CH – CH2 – CH3
n-Hexane 2-Methylpentane 3-Methylpentane
(C6H14) (C6H14) (C6H14)

CH3 CH3

CH3 – C – CH2 – CH3 CH3 – C – CH2 – CH2 – CH3

CH3 CH3
2,2-Dimethylbutane 2,2-Dimethylpentane
(C6H14) (C7H16)

Except 2,2-dimethylpentane which is an isomer of heptane (as it contains seven C-atoms), all others are
isomers of hexane.
8. Unsaturated hydrocarbons like alkenes (CnH2n) and alkynes (CnH2n–2) on catalytic reduction by H2 gas over
Ni catalyst at high temperature and pressure, form the corresponding alkanes (CnH2n+2).
9. In the presence of platinum (Pt) or palladium (Pd) catalyst at room temperature, ethene adds up one mole of
hydrogen gas to give ethane.
CH2 = CH2 + H2  Pt or Pd
 CH3  CH3
Ethene Ethane

10. In Wurtz reaction, the reagent used is sodium metal in dry ether (Na/dry ether).
R  X + 2Na + X R  
dry ether

 R  R + 2NaX
Alkyl Sodium Alkyl Alkane
halide metal halide

11. CH3CH2CH2Br + 2Na + BrCH2CH2CH3 

dry ether

 CH3CH2CH2CH2CH2CH3 + 2NaBr
1-Bromopropane Sodium 1-Bromopropane n-Hexane
metal
The reactants in the options (A), (B) and (D) will give n-hexane along with other alkanes. Only option (C)
i.e., CH3CH2CH2Br will yield pure n-hexane.
12. CH3  Mg  I + H  OH 
Dry ether
 CH3  H + MgI(OH)
13. Methyl iodide on reduction forms methane.
CH3  I + 2[H]  Zn, dil. HCl
CH4 + HI
Methyl iodide Methane

57
 

MHT-CET Triumph Chemistry (Hints)

Methyl iodide reacts with sodium metal in dry ether to form ethane (C2H6).
CH3  I + 2Na + I  CH3  

dry ether
 CH3  CH3 + 2NaI
Methyl iodide Sodium Methyl iodide Ethane
(Iodomethane) metal (Iodomethane)

14. When ethyl iodide and propyl iodide react with Na in the presence of ether they form mixture of three alkanes
viz., butane, pentane and hexane.
C2H5I + 2Na + C3H7I  Dry ether

 C5H12 + 2NaI
Ethyl Sodium n-Propyl Pentane Sodium
iodide metal iodide iodide

C2H5I + 2Na + C2H5I 

Dry ether

 C4H10 + 2NaI
Ethyl Sodium Ethyl Butane Sodium
iodide metal iodide iodide

C3H7I + 2Na + C3H7I 

Dry ether

 C6H14 + 2NaI
n-Propyl Sodium n-Propyl Hexane Sodium
iodide metal iodide iodide

15. Alkyl halides undergo Wurtz reaction to give higher alkanes having double the number of carbon atoms as
compared to the reactant (alkyl halide).
CH4, being an alkane that has only one carbon atom, cannot be prepared by Wurtz reaction.
16. In alkanes, the boiling point depends on molecular mass and extent of branching. Greater the molecular
mass, higher is the boiling point. Hence, among the given options, n-hexane has maximum boiling point.
17. In isomeric alkanes, as branching increases, surface area decreases and hence intermolecular forces become
weak resulting in lowering of boiling point.
CH3

(A) CH3  CH2  CH2  CH2  CH3 (B) CH3  CH  CH2  CH3
(C5H12) n-Pentane (C5H12) Isopentane
CH3

(C) CH3  C  CH3

CH3
(C5H12) Neopentane
Among the given options, neopentane has the most number of branches (i.e., two methyl groups), hence it
has the lowest boiling point.
18. Photochemical chlorination of alkane takes place by free radical mechanism involving homolysis of Cl – Cl
bond. The Cl  Cl bond being weaker than C  H bond is broken easily.
h
Cl  Cl  2Cl
Chlorine Chlorine
molecule free radical

21. Alkanes on heating at higher temperature in absence of air decompose to lower alkanes, alkenes and
hydrogen.
CH3CH2CH2CH3  Cracking
 CH4 + CH3  CH = CH2
n-Butane Methane Propene

23. Lower liquid alkanes are used as solvent.

25. H3C CH3 H3C H

C=C C=C
H H H CH3
cis-But-2-ene trans-But-2-ene

58
 

Chapter 15: Hydrocarbons

26. 3-Methylpent-2-ene exhibits cis-trans isomerism as follows:
1 4 5 4 5
H3C
2 3
CH2CH3 CH2CH3
H 2 3
C=C C=C
1
H CH3 H3C CH3
trans-isomer cis-isomer

27. Structural isomers of C5H10 can be represented as follows:

CH3  CH2  CH2  CH = CH2
Pent-1-ene

CH3  CH = CH  CH2 – CH3

Pent-2-ene

CH3 CH3 CH3

| |
H3C  C = CH  CH3 H2C = C  CH2  CH3 CH3  CH  CH = CH2
2-Methylbut-2-ene 2-Methylbut-1-ene 3-Methylbut-1-ene

28. The order of reactivity of alkyl halides towards dehydrohalogenation reaction is 3 > 2 > 1 and
iodides > bromides > chlorides.
Thus, among given options, alkyl halide given in option (D) is tertiary butyl iodide and will be most reactive
towards dehydrohalogenation reaction.
29. CH3 CH3 CH3

CH3  C  CH2  CH3 

alc. KOH

 CH2 = C  CH2  CH3 + H3C  C = CH  CH3

Cl
2-Chloro-2-methylbutane 2-Methylbut-1-ene 2-Methylbut-2-ene

30. The ease of dehydration of alcohols is in the order 3 > 2 > 1. Thus, 1 alcohols require high temperature
conditions as compared to 2 alcohols.
33. Branched alkenes have lower boiling points than straight chain alkenes.
35. Markovnikov's rule: When an unsymmetrical reagent is added to an unsymmetrical alkene, the negative part
(X-) of the reagent gets attached to the carbon atom which carries less number of hydrogen atoms.
36. Markovnikov’s rule governs the addition of unsymmetrical reagents to unsymmetrical alkenes. Br2 and Cl2
are symmetrical reagents while C2H4 is a symmetrical alkene. Moreover, in option (D), C3H8, an alkane will
undergo substitution reaction. Thus, among the given options, the Markovnikov’s rule is best applicable to
the reaction between C3H6 and HBr.
37. Reaction of HBr with but-1-ene in the presence of organic peroxide follows anti-Markovnikov’s addition
and gives 1-bromobutane as the major product.
(C6 H5CO) 2 O 2
CH3  CH2  CH = CH2 + HBr 
Benzoyl peroxide
 CH3  CH2  CH2  CH2Br
But-1-ene 1-Bromobutane

38. In the presence of peroxides, only the addition of HBr to an unsymmetrical alkene does not occur according
to Markovnikov’s rule.
39. H3C O CH3
O
C C
(CH3)2C = C(CH3)2 + O3  CH3 
Zn / H2 O

 2CH3  C  CH3 + ZnO
H3C Propanone
2,3-Dimethylbut-2-ene
O O

59
 

MHT-CET Triumph Chemistry (Hints)

H O H
40. CH3  CH = CH  CH3 + O3  C C 
Zn / H 2 O

 2CH3CHO + ZnO
But-2-ene H3C CH3 Ethanal
(Acetaldehyde)
O O ‘B’

-Butylene ozonide
‘A’

41. CH3CHCH3 

alc.KOH
 CH3  CH = CH2 + H2O + [O] 
alkaline KMnO4
CH3  CH  CH2
Propylene OH OH
Br (Propene)
2-Bromopropane Propylene glycol
(Propane-1,2-diol)
Product ‘B’
43. CH2 = CH  C  CH: But-1-en-3-yne
44. HO  H + C  C + H  OH  H  C  C  H + Ca(OH)2
Acetylene
Ca
Calcium
carbide

45. Dehydrobromination of alkyl bromides occurs smoothly with alcoholic KOH. However, the intermediate
compound i.e., vinyl bromide is less reactive and stronger base like NaNH2 in liquid NH3 is required in the
second step.
Br H
Br
Br is also represented as H  C  C  H

H Br
Br H
H  C  C  H 
KOH(alc.), 
 HBr
 CH2 = CH  Br 
NaNH 2
 HBr
HCCH
Vinyl bromide Acetylene
H Br (Bromoethene)
Ethylene dibromide
(1,2-Dibromoethane)

46.
H H H H
Na + NH 
H3C  C  C  H + KOH 
 KCl
H3C  C = C  Cl  2  H C C≡ CH
 NaCl 3
(Alcoholic)  H2O 1-Chloropropene  NH3
Propyne
Cl Cl
1,2-Dichloropropane

47. Alkynes are less dense than water.

48. In hybridized state, the electronegativity of carbon atom increases with the increase in its percentage of
s character. In ethyne, carbon atom is sp hybridized, hence it has 50% s character. sp hybridized carbon atom
in ethyne (acetylene) can attract the shared electron pair to a greater extent as compared to sp2 hybridized
carbon atom in ethene (ethylene) and sp3 hybridized carbon atom in ethane. Therefore, hydrogen atom can
be easily liberated as proton from ethyne. Hence, acetylenic hydrogens are acidic.

49. CH3  C  C  H LiNH 2


 NH
 CH3  C  C Li+
3

Methyl acetylene Lithium methyl acetylide

‘A’

60
 

Chapter 15: Hydrocarbons

50. H  C  C  H 
HBr
 [CH2 = CH  Br] 
HBr
 CH3  CH  Br

Acetylene Vinyl bromide Br

Ethylidene dibromide
(1,1-Dibromoethane)
I
51.
CH3  CH2  C  C  H + HCl  CH3  CH2  C = CH2 
HI
 CH3  CH2  C  CH3

Cl Cl
But-1-yne 2-Chlorobut-1-ene 2-Chloro-2-iodobutane
‘B’ ‘C’
52. Propyne reacts with hydrogen bromide to give propylidene dibromide (2,2-Dibromopropane).
Br

CH3  C  CH 
HBr
 [CH3  C(Br) = CH2] 
HBr
 CH3  C  CH3

Br
Propyne 2-Bromopropene 2,2-Dibromopropane
55. Methyl acetate, ethyl acetate and chloroform do not resemble benzene but have a pleasant odour. Anthracene
resembles benzene and do not have pleasant odour.
57. Aromatic compounds (despite the presence of unsaturation) do not undergo addition reactions easily
compared to aliphatic compounds. Hence, aromatic compounds do not decolourise dilute aqueous potassium
permanganate solution as compared to the alkenes and alkynes. Among the given options, only benzene is an
aromatic compound while others are unsaturated aliphatic compounds.
60. Benzene is a planar molecule, in which each carbon atom is sp2 hybridized and the C  C  C bond angles
are 120. The six  electrons are delocalized above and below the plane of the ring.

61. have 8 delocalised  electrons (6  electrons of the 3 double bonds and 2 unshared electrons on the
negatively charged carbon).


62.
Planar/non-planar Delocalisation of  Huckel rule
Compound
ring electrons (4n + 2) electron
(A) 4  e
Planar Complete
Rule not obeyed.

(B) 10  e
Planar Complete
Rule obeyed.

COOH
(C) 6  e
Planar Complete
Rule obeyed.

(D)
14  e
Planar Complete
Rule obeyed.

63. Benzene can be prepared by reduction of phenol. This is carried out by passing vapours of phenol over
heated zinc dust.
OH


+ Zn   + ZnO
Phenol Benzene

61
 

Chapter 11: Adsorption and Colloids

5. The substances which provide large surface area 16. CO(g) + 3H2(g) 
Ni
 CH4(g) + H2O(g)
for a given mass are much effective as Cu / ZnO  Cr2 O3
CO(g) + 2H2(g)   CH3OH(g)
adsorbents and adsorb appreciable volumes of
X is methane (an alkane) and Y is methanol (an
gases. Finely divided substances, rough
alcohol).
surfaces, colloidal substances, etc. are good
adsorbents because they provide large surface 17. In zeolites, some silicon atoms in the three
area for a given mass. dimensional network of silicates are replaced by
Therefore, nickel metal sheet having smooth aluminium atoms.
surface is a less effective adsorbent compared to
nickel metal sheet having rough surface. 18. Blood is a colloidal dispersion of plasma
proteins and antibodies in water. However,
6. The extent of adsorption of a gas on a solid blood is also a suspension of blood cells and
surface increases with pressure of the gas at platelets in water.
constant temperature. Initially the adsorption
increases rapidly, however, as the pressure 20. Once lyophobic sols are precipitated, the
increases the surface of adsorbent becomes precipitate cannot be reconverted into sols by
covered by gas molecules. Now, the adsorption simple addition of dispersion medium. Hence,
becomes independent of pressure of the gas. the lyophobic sols are called irreversible sols.
Thus, the adsorption of a gas on a solid surface 24. Though a small quantity of an electrolyte is
varies with pressure of the gas as: necessary for the stability of colloidal solution,
Fast  slow  independent of pressure. large quantity of electrolyte may result in
coagulation. So, during peptization process
x 1
7. Freundlich adsorption isotherm is  kP n small amount of electrolyte (peptizing agent) is
m used.
Taking the logarithm of both sides of the
x 1 25. Colour of colloidal solution depends on the
equation, log  log k  log P wavelength of light scattered by dispersed
m n
The equation is the straight line equation of the particles.
form y = mx + c. Hence, Freundlich adsorption 26. When light passes through true solution
x containing solute particles not larger than 1 nm,
isotherm gives a straight line on plotting log
m the path of the light through the solution cannot
vs log P. be detected. However, if the light passes
through colloidal dispersion, because of the
8. In the low pressure range at constant
scattering of light by the colloidal particles, the
temperature, the extent of adsorption is directly
path of the light through the colloidal dispersion
proportional to the pressure of the gas.
becomes visible. This phenomenon of scattering
However, as the pressure increases and becomes
of light by colloidal particles and making the
higher, the extent of adsorption becomes
path of the light visible through the dispersion is
independent of pressure because the surface of
referred to as Tyndall effect.
adsorbent is almost fully covered by the
adsorbed gaseous molecules. This relation is 30. During electrophoresis, positively charged
correctly shown by graph of Freundlich colloidal particles move towards cathode while
equation which is as follows: negatively charged colloidal particles migrate to
anode.


31. Dispersion medium and disperse phase are two

x phases of colloid. These phases can be solid,
liquid or gas (except gas in gas which is not a
m
colloid). Colloids can be electrolysed by using
P  electrophoresis method and colloids can be
hydrophobic and hydrophilic in nature.
12. Heterogeneous catalysts are used in catalytic
converters in automobiles to reduce toxic 32. Lyophilic colloids possess solvent-loving nature
emissions and pollution by automobiles. These and thus a thin layer of dispersion medium is
catalysts are poisoned by the adsorption of Pb. formed around colloidal particles.
For this reason, automobiles with catalytic
converters require unleaded petrol. 33. The positive particles of one sol are attracted by
the negative particles of the second sol. This is
14. Inhibitors slow down the rate of reaction. followed by mutual coagulation of both the sols.
41
 

Chapter 15: Hydrocarbons

73. CH3 group is a ring activating group which shows electron-donating inductive effect while Cl and NO2
are electron-withdrawing deactivating groups. Among Cl and NO2 groups, Cl has electron-donating
resonance effect while NO2 has electron-withdrawing resonance effect. Therefore, Cl is moderately
deactivating group while NO2 is strongly deactivating group.
74. CN, COCH3 and CHO groups are meta directing while Br is ortho, para directing.

75. CH3  CH2  CH2  OH 

60% H 2 SO 4
373 K
 CH3  CH = CH2 
HBr
 CH3  CH  CH3
Propanol Propene
Br
Isopropyl bromide
(Major product)

76. Catalytic hydrogenation of alkynes using H2/Pt catalyst cannot be stopped at alkene stage, but continues
further to form corresponding alkane. However, by using catalysts like palladised charcoal deactivated
partially with quinoline or sulphur compound, Lindlar’s reagent, etc., the reaction can be stopped at alkenes
stage.
77. Dehydration is an example of 1,2-elimination reaction while halogenation and hydrohalogenation are
examples of electrophilic addition reactions.
79. Alkynes and alkenes being more polar, have slightly higher boiling points than corresponding alkanes.
Among the isomeric alkanes, the normal isomer has a higher boiling point than the branched chain isomer.
Hence, among the given options, isobutane has the minimum boiling point.
80. Numbering of an enyne chain starts from the end nearer to the first multiple bond, whether double or triple.
Ties are broken in favour of the double bond. Hence, the numbering will be from left to right.
1 2 3 4 5 6
CH2 = CH  CH2  CH2  C  CH
sp2 sp3
81. In ethyne, both the carbon atoms are sp hybridized, hence they have 50% s character. In hybridized state, the
electronegativity of carbon increases with the increase in its percentage of s character. Hence, sp hybridized
carbon atom in ethyne (acetylene) can attract the shared electron pair to a greater extent as compared to sp2
hybridized carbon atom in ethene (ethylene) and sp3 hybridized carbon atom in ethane. This makes ethyne
the most reactive hydrocarbon among the given options.
82. Since, the compound is a hydrocarbon with molecular weight 26. It must be an alkyne (CnH2n2).
H Br
H  C  C  H + Br2  Bromine Water
C=C
Acetylene (dil.) Br H
(Ethyne ) Acetylene dibromide
[Alkyne] (trans-1,2-Dibromoethene)
‘X’ [Dibromide derivative product]

Br Br Br
H
H  C  C  H + Br2  C=C 
Br2
HCCH
Acetylene H
(Ethyne ) Br Br Br
[Alkyne] Acetylene dibromide Acetylene tetrabromide
‘X’ (trans-1,2-Dibromoethene) (1,1,2,2-Tetrabromoethane)
[Tetrabromide derivative product]

83. CH2 = CH  C  CH
But-1-en-3-yne
There are four CH sigma bonds, three CC sigma bonds and three CC pi bonds in the given molecule.
Thus there are in all seven sigma bonds and three pi bonds in but-1-en-3-yne.
63
 

MHT-CET Triumph Chemistry (Hints)

CH3

84. CaC2 H2 O

 Ca (OH)2
 HCC–H 
Hot iron
tube
CH3 Cl
Anhydrous AlCl3

 HCl

Calcium Acetylene Benzene Toluene

carbide (P) (Q) (R)

85. CH3 SO3H

H2C CH3

Cr2 O3 , 773 K
10  20 atm
 
Fuming H2SO4
373 K

H2C CH2
Benzene Benzenesulphonic
CH2 (Y) acid
(Z)
n-Hexane

Competitive Thinking
2. CH3  CH2  CH2  Cl + 2Na + CH3  CH2  CH2  Cl 
dry ether
 CH3  (CH2)4  CH3 + 2NaCl
(Wurtz reaction)

n-Propyl chloride n-Propyl chloride n-Hexane

3. For isomeric alkanes, straight chain isomers have higher boiling points than branched chain isomers.
5. All H-atoms in neopentane are equivalent and hence, neopentane gives only one mono-chloro compound.
CH3 CH3

CH3  C  CH3 + Cl2 

UV light
 CH3 – C – CH2 – Cl + HCl

CH3 CH3
Neopentane 1-Chloro-2,2-dimethylpropane

7. CH3  CH 2 4 CH3 

V2 O5
773 K, 10  20 atm


n-Hexane (Dehydrogenation) Benzene

7 1
8. Me Me Me CH3 CH3
H3C 6 2
CH CH
OR 5 3
Me CH 4 CH
5,6-Dimethylhept-2-ene CH3 CH2
5,6-Dimethylhept-2-ene

9. H3C CH3 H3C H

C=C C=C
H H H CH3
cis-But-2-ene trans-But-2-ene

10. The compounds in which each of the doubly bonded carbon atoms is attached to two different atoms or
groups show geometrical isomerism.

CH2 CH3 CH2 H

C C C C

H H H CH3

cis-1-phenylbut-2-ene trans-1-phenylbut-2-ene

64
 

Chapter 15: Hydrocarbons

13. 
 Birch reduction  
Na / liq.NH3

But-2-yne trans-But-2-ene
14. The reaction involves electrophilic addition to a carbon-carbon double bond resulting in a stable carbocation.
CH2 CH3 CH3
+ Cl

+ H+  
Cl


1-Chloro-1-methylcyclohexane

CH3 CH3 CH3

+ Cl

+ H+  
Cl


1-Chloro-1-methylcyclohexane

15.

H2C  CH = CH2 + HBr 

Peroxide
 H2C  CH2  CH2  Br
3-Phenylpropene 1-Bromo-3-phenylpropane

CH3 CH3 CH3

+ Rearrangement
H   H3C – C – CH – CH3
16. H3C – C – CH = CH2  H3C – C – CH – CH3 Methylshift
+
CH3 CH3 CH3
2° carbocation 3° carbocation
(Less stable) (More stable)

OH– OH–

CH3 CH3

H3C – C – CH – CH3 H3C – C – CH – CH3

CH3 OH OH CH3
(B) (A)
(Minor) (Major)
17.
H O O
Zn /H 2 O
CH3  C = C  CH3 + O3  CH3  C  O  C  CH3   CH3  C = O + O = C  CH3 + ZnO


CH3 CH3 H CH3 H

2-Methylbut-2-ene Ozonide Propanone Ethanal

18. Option (A) (Me2C = CHMe), contains one disubstituted (Me2C =) and one monosubstituted (= CHMe)
C-atom. Thus, it will form both aldehyde and ketone on ozonolysis.
O H
Me2C C – Me
Me2C = CHMe 
 O3 / CH 2 Cl2
196  200K

Zn / H 2 O
 Me2C = O + CH3CHO
2-Methylbut-2-ene O O Acetone Acetaldehyde
(Ketone) (Aldehyde)
Ozonide

65
 

MHT-CET Triumph Chemistry (Hints)

19. H H H CH3 O

C = C – C = C – CH2 – CH3 

O3 / CH 2 Cl2 /196K
Zn / H 2 O
 CHO + CHO – CHO + CH3 – C – CH2 – CH3
Ethyl methyl
Cyclohexanal Glyoxal
1-Cyclohexyl-4-methylhexa-1,3-diene ketone

20. So, ‘A’ is (CH3)2C = CH – CH3.

CH3 CH3 CH3
CH3 – C = CH – CH3 + HCl  CH3 – C – CH2 –CH3  CH3 – C – CH2 –CH3
+
2-Methylbut-2-ene
Cl
2-Chloro-2-methylbutane
21. For an aldehyde, general formula can be written as CnH2nO.
In the reaction, an aldehyde having molecular mass of 44 u is formed.
i.e., (n  C) + (2n  H) + O = 44
(n  12) + (2n  1) + 16 = 44 (substituting atomic mass)
12n + 2n = 28
14n = 28
n=2
 the aldehyde formed is C2H4O i.e., CH3CHO.
 The symmetrical alkene that on ozonolysis gives two moles of acetaldehyde is but-2-ene.
H O H
CH3  CH = CH  CH3 + O3  C C 
Zn / H2 O

 2CH3CHO + ZnO
But-2-ene H3C CH3 Ethanal
(Acetaldehyde)
O O

-Butylene ozonide
22. The alkene which on ozonolysis will give the above compound is,
CH3
CH3 O
ozonolysis
¾¾¾¾  OHC – C – CH2 – CH2 – C – CH3

H
CH3
23. H3C  CH2  C  C  CH3
Correct IUPAC name: Pent-2-yne
24. The possible alkynes are:
CH3

CH3  CH2  CH2 C  CH CH3  CH2  C  C  CH3 CH3  CH  C  CH

Pent-1-yne Pent-2-yne 3-Methylbut-1-yne
25.
 +
H  C  C  H 
NaNH 2 / liq.NH3
 H  C  C Na 
CH3 CH 2 Br
H C  C  CH2  CH3 + NaBr
Ethyne But-1-yne
(X)
NaNH2/liq.NH3

NaBr + CH3  CH2  C  C  CH2  CH3 

CH3 CH 2 Br +
NaC  C  CH2  CH3
Hex-3-yne
(Y)

66
 

Chapter 15: Hydrocarbons

26. The hydrogen atoms attached to the triply bonded carbon atoms in alkynes are acidic in nature.
Acetylene (H  C  C  H) reacts with strong base such sodamide (NaNH2) to give sodium acetylide.
H  C  C  H + Na  NH 2  H  C  CNa+ + NH3
Acetylene Sodamide Monosodium Ammonia
acetylide
H  C  CNa+ + Na  NH 2  Na+C  CNa+ + NH3
Monosodium Disodium Ammonia
acetylide acetylide

27. When acetylene is passed into dilute sulphuric acid containing Hg 2 ions (1% mercuric sulphate), the
product formed is acetaldehyde.
H  C  C  H + H  OH  40% H 2SO 4
 [CH2 = CH  OH] 
tautomerism
  CH3  CHO

1% HgSO4
Acetylene Vinyl alcohol Acetaldehyde
(Enol)
28. When propyne is treated with aqueous H2SO4 in presence of HgSO4, the major product is propanone.

H3C  C  CH + H  OH   H3C  C = CH2  H3C  C  CH3

tautomerism
40% H 2SO4
 
 
1% HgSO4

Methyl acetylene OH O
(Propyne) Acetone
Prop-1-en-2-ol (Propanone)

29. CH3  CH2  C  CH + H  OH 

2 4
 [CH3  CH2  CH = CH  OH]
40% H SO
1% HgSO4

But-l-yne
Tautomerism

CH3  CH2  CH2  CHO

Butanal

OH O
30. H3C – C  CH 
H 2 O, H 2SO 4
H3C – C = CH2  H3C – C – CH3
HgSO 4
Propyne  Markovnikov’s
addition  Intermediate Product
(enol form) (Propanone)
(A) (B)
31. The COOH group is given priority over NH2 and OH groups. So, the carbon atom bearing COOH
group is considered to be at position 1. The carbon atoms of the ring are numbered so as to assign the lowest
locant to the substituents.
OH
4
3 5

6
H2N 2
1
COOH
The IUPAC name of the given compound is 2-amino-4-hydroxybenzoic acid.
33. According to Huckel rule, any cyclic, planar and conjugated compound containing (4n+2) electrons, where
n = 0, 1, 2, 3, etc. is aromatic.
(4n+2) = 6  n = 1; aromatic compound

(4n+2) = 4  n = 1 2 ; not aromatic

+

(4n+2) = 4  n = 1 2 ; not aromatic

O
67
 

MHT-CET Triumph Chemistry (Hints)

H H

5
(4n + 2) = 12 n= ; not aromatic
2

H H

34. Cyclopentadienyl anion does not contain a benzene ring. Hence, it is a

non-benzenoid. But it contains 6 electrons and 6 is a Huckel number,
so cyclopentadienyl anion is aromatic in nature.

Cyclopentadienyl anion
6-electrons (n = 1)
36. Structures ii, v and vi have 8, 4 and 4 electrons respectively. Thus, they do not obey Huckel rule, i.e.,
(4n + 2) electron rule and are non-aromatic.

37. Imidazole contains 6 electrons and therefore, obeys the Huckel’s rule, where n = 1. Thus,
N N – H aromatic.
+ +

Cyclobutenyl dication contains 2 electrons (n = 0) and it is planar. 2-electrons are in resonance or

delocalisation with two positive charges. Thus, aromatic.
38. Molecules in option (A), (B) and (C) are aromatic and are stabilized by resonance. Molecule in option (D) is
non-aromatic and hence, it is least stabilized by resonance.
39. The product is,
H
H3C CH3

H H
CH3
It contains 21 sigma () bonds.
42. In the nitration of benzene with conc. HNO3 and conc. H2SO4, the required electrophile NO2+ is generated
by the reaction of HNO3 with H2SO4. The electrophile NO2+ attacks the benzene ring forming nitrobenzene.
HO  NO2 +  2[HSO4] + H3O+ + NO2+
2H2SO4 
Nitric acid Sulphuric acid

44. NO2 group is meta directing, so the electrophilic attack (during bromination) occurs at the meta position.
NO2 NO2


conc.HNO3
conc.H 2SO 4
 
Br2
FeBr3


Br
Benzene Nitrobenzene
m-Bromonitrobenzene
‘A’
‘B’
45. The active species i.e., electrophile in the benzene sulphonation is SO3.
46. In Friedel Craft’s alkylation reaction, R+ is the electrophile and it is generated by using the catalyst AlCl3.
 R+ + [AlCl4]
R  Cl + AlCl3 

47. In Friedel-Crafts alkylation, alkyl halide provides the required electrophile (i.e., carbocation). Hence, among
the given options, isopropyl chloride is the most suitable halide component.
49. Nitrobenzene will not undergo Friedel-Craft’s reaction easily because of the presence of
electron-withdrawing NO2 group that deactivates the aromatic ring.

68
 

Chapter 15: Hydrocarbons

50. CH2  CH3 CH2  CH3

+ 3H2  Ni
458 K to 473 K


Ethylbenzene Ethylcyclohexane

51. Deactivating groups are generally meta directing groups. Reaction of benzene with l-chloropropane and
anhydrous AlCl3 gives isopropylbenzene (cumene).
According to Huckel rule, for cyclohexadiene (4n+2) = 4
Cyclohexadiene  n = 1/2

53. Conformers of ethane (eclipsed, staggered, gauche) have difference in dihedral angle, energy and stability
but their bond lengths and bond angles do not change.
54. Homologues differ by CH2 unit. Hence, fourth higher homologue of ethane (C2H6) will have additional four
CH2 units i.e., C2H6 + (CH2)4 = C6H14, which is the molecular formula of hexane. Thus, the fourth higher
homologue of ethane is hexane.
55. Neopentane contains four primary (1°) and one quaternary (4°) C-atoms. It is represented as,
1
CH3
1 4 1
H3C – C – CH3

CH3
1
Neopentane

56. The C  H and C  C single bonds are the  bonds. The C = C double bond consists of one  bond and one
 bond. H
  H H
H C  H H 
    
H     
     C H
H C   
 
 
H  H H H
 C  C 
H H H  H
H

Thus, the given molecule contains four  bonds which consists of eight -bond electrons.
57. 
CH3  CH = CH2 
KMnO4 / OH
CH3  CH  CH2
273 K

Propylene
OH OH
(Propene) Propane1,2diol

58. In acetylene/ethyne molecule, the sp hybrid orbital of one carbon atom overlaps axially with sp hybrid
orbital of other carbon atom to form one sigma bond whereas the unhybridized 2py and 2pz orbitals of each
of these carbon atoms overlap laterally to form two pi bonds. Thus, the C  C bond in ethyne consists of one
sigma bond and two pi bonds.
59. HC  C  C = CH2

H
(C4H4)

69
 

MHT-CET Triumph Chemistry (Hints)

60. π
σ σ σ
H C C H
π
3 and 2 bonds

61. H H H

H–CC–C=C–C–H
1 2 3 4 5
H
10  and 3  bonds

62. sp2 sp2 sp sp

CH2 = CH– C  CH

63. CH4 + Br2  h

Substitution   CH3Br
Methane Methyl
‘A’ bromide

 Wurtz reaction   CH3  CH3 + 2NaBr

CH3Br + 2Na + CH3Br dry ether

Methyl Methyl Ethane

bromide bromide (Gaseous
hydroccarbon)
65.
Compound Hybridisation of carbon atom(s)
CO2 sp
Ethane sp3
Ethyne sp
Ethene sp2
Ethanol sp3
Thus, the compound having same hybridization as its combustion product (CO2) is ethyne.
66. In biphenyl, all the carbon atoms are sp2 hybridised having trigonal planar geometry. Hence, all the atoms
will lie in the same plane i.e., all the atoms are coplanar.
67. Lower the heat of hydrogenation (i.e., enthalpy of hydrogenation), more stable is the compound.
Compound (I) is aromatic. Hence, it is more stable than compounds (II) and (III).
Compound (II) has conjugated double bonds. Hence, it is more stable than compound (III).
Thus, the stability decreases in the order: (I) > (II) > (III)
Therefore, the enthalpy of hydrogenation decreases in the order: (III) > (II) > (I)

Hints to Evaluation Test

1. Alkanes are insoluble in water.

2. Since, the given compound is an alkane (CnH2n+2) with molecular weight 170.
Therefore, (12  n) + 1(2n + 2) = 170
Where n = integer indicating number of carbon atoms in a molecule
12 = atomic weight of carbon
1 = atomic weight of hydrogen
 12n + 2n + 2 = 170
 14n = 168
168
 n= = 12
14
 The molecular formula of the given alkane is C12H26.
70
 

Chapter 15: Hydrocarbons

3. In alkanes, boiling point depends on molecular mass. Greater the molecular mass, higher will be the boiling
point. For isomeric alkanes, boiling points of branched chain alkanes as compared to straight chain alkanes
are lower. Hence, among given options n-octane has maximum boiling point.
4. C2H5I + 2Na + C3H7I 
Dry ether

 C5H12 + 2NaI
Ethyl Sodium n-Propyl Pentane Sodium
iodide metal iodide iodide

C2H5I + 2Na + C2H5I 

Dry ether

 C4H10 + 2NaI
Ethyl Sodium Ethyl Butane Sodium
iodide metal iodide iodide

C3H7I + 2Na + C3H7I 

Dry ether

 C6H14 + 2NaI
n-Propyl Sodium n-Propyl Hexane Sodium
iodide metal iodide iodide

Thus, n-propane is not formed when a mixture of ethyl iodide and n-propyl iodide is subjected to Wurtz reaction.
5.
CH3  CH2  CH2  CH3 + Br2 
UV Light
 CH3  CH  CH2  CH3 + CH3  CH2  CH2  Br
n-Butane 1-Bromobutane
Br
(Minor product)
2-Bromobutane
(Major product)

6. C2H4 
HBr
 C2H5Br 
alc.KOH

 C2H4
Ethene Ethyl bromide Ethene
‘A’ ‘A’

7. In a reaction, if half of the double bond is broken and two new bonds are formed, this is a case of addition.
eg.
Br
C = C  
2
CC
(Alkene) Br Br
(Addition product)
8. When ethylene reacts with bromine, it forms ethylene dibromide.
H2C = CH2 + Br2  H2C  CH2
Ethylene Bromine
Br Br
Ethylene dibromide
(X)

9. Replacing the Oatoms of the carbonyl compounds by double bond, the alkene formed is:
CH3 CH3
CH3 CH3
C =O+O=C  CH3  C = C  CH2  CH3
CH3 C2H5 2,3-Dimethylpent-2-ene
Acetone Ethyl methyl ketone

10. CaC2 + 2H2O 

 C2H2 + Ca(OH)2
Calcium Ethyne
carbide (X)
H H
40% H 2SO4
H  C  C  H + H  OH 
1% H 2SO 4
 HC=CH Tautomerism

 
 H  C  C H
Ethyne
(X) O  H O H
Vinyl alcohol Ethanal
sp2 sp3 sp 2
11. CH3  CH  CH  CH 2  CH  CH  C  CH
sp3 sp 2 sp 2 sp sp

Molecular formula: C8H10

71
 

MHT-CET Triumph Chemistry (Hints)

12. But-1-yne (CH3  CH2 – C  CH) being a terminal alkyne has an acidic hydrogen and hence reacts with
LiNH2 to evolve H2 gas. However, but-2-yne (CH3 – C  C – CH3) does not react with LiNH2.
4 3 2 1
13. CH3  CH2  C  CH
But-1-yne

In the given molecule, C2 un dergoes sp hybridisation which has 50% each of s-character and p-character.

15. The number of -bonds in benzene is 12. The number of -bonds in benzene is 3. Hence, the ratio of  and
12
-bonds is = 4.
3

16. COOH COOH


Monochlorination


Cl
Benzoic acid
m-Chlorobenzoic acid

In Benzoic acid, the –COOH group is meta directing group. Chlorobenzene and phenol will not undergo
meta substitution on monochlorination because Cl and OH groups are ortho, para directing. Ethoxyethane
will not undergo meta substitution reaction since it is not an aromatic compound.

17. The COOH group is meta directing and the NHCOCH3 group is ortho, para directing.
COOH COOH


conc. HNO3
conc.H 2SO 4 , 

NO2
NHCOCH3 NHCOCH3
(P)

19. 6 5 4 3 2 1
HC  C  CH2  CH2 – CH – CHO
OH
2-Hydroxhex-5-yn-1-al

20. Reaction of HBr with 2-methylpropene in the presence of organic peroxide follows anti-Markovnikov’s
addition and gives 1-bromo-2-methylpropane as the major product.
CH3  C = CH2 + HBr 
Anti  Markovniko v's rule
Peroxide
CH3  CH  CH2Br
| |
CH3 CH3
2-Methylpropene 1-Bromo-2-methylpropane

72
 
Textbook
Chapter No. Chapter 01: 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
Contribution
Atom/ion Location 18. For bcc unit cell, n = 2.
to a unit cell
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  10 23 
3
49.
Contribution = 5.2 g / cm3
Atom/ion Location
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  10 23 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  10 23
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.
73
 

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 Contribution
Atom/ion Location
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
only   of these holes are occupied.
2
Body-centred unit cell, r =
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
a3 Number of cation B = n  
3 3
Number of atoms in 100 g
4  100 
= 8 3
= 4  1025 Ratio of cation A : cation B : Oxide ions
10  (10 ) n n
= : : n = 1: 1 : 3
3 3
33. a = 3 Å = 3  10–8 cm,
The formula of the solid is ABO3.
Density of the element = 8 g cm–3,
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 =
 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
Contributi  Mass of fcc unit cell of silver = 4m
Atom/ion Location 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
 Density of silver (Ag) =
Formula Cu4Ag3Au a3

74
 

MHT-CET Triumph Chemistry (Hints)

31. The resonance structure with the lowest energy 11. O
is a major resonance contributor.
32. The structure does not have lone pair of CH2 – CH2 – C – OH
3 2 1
electrons or  electrons that are required for
resonance. Hence, resonance effect is not
3-Phenylpropanoic acid
present in this structure.

12. CHO
Competitive Thinking 1
NO2
1. 2
3
4
OCH3
4-Methoxy-2-nitrobenzaldehyde
O
Tropone
13. A. n-Butane and isobutane are chain isomers.
It is a homocyclic non-benzenoid compound. B. Dimethyl ether and ethanol are functional
3. C6H10O2N is the successive member of the group isomers.
homologous series of C5H8O2N as they differ C. Ethanoic acid (CH3COOH) and methyl
from each other in molecular formula by a methanoate (HCOOCH3) are functional
methylene ( CH2 ) group. group isomers.
Also, in homologous series, the members differ
14. α-Hydrogen at bridge carbon never participate
only in the number of C and H atoms. The in tautomerism. Thus, only (III) exhibits
number of hetero atoms remains the same. tautomerism.
Only in option (D), the number of O and
N-atoms are same as in the compound given in O OH


question.
Thus, option (D) is the correct answer. Enol form
H
5. The given molecule can also be written as
follows: 15. The structure of enolic form is,
1 2 3 4 5 6 7 H H
H3C  CH  CH = CH  CH = CH  CH  CH3
H
8 9 C C O
CH3 CH2  CH3 H C C H H
2,7-Dimethylnona-3,5-diene
OH OCCH
6. The functional group in the molecule is keto
group. In ketones, the final ‘-e’ from the parent H H
alkane name is dropped and the suffix ‘-one’ is
17. The positive inductive (+I) effect stabilises the
added to give the base name.
free radical. Therefore, the free radicals
CH3  CO  CH2  CH2  CH3 containing more number of electron donating
1 2 3 4 5 substituents like alkyl groups are more stable.
The IUPAC name of the compound is
H H CH3 CH3
pentan-2-one.
8. For compounds having functional groups along H  C < H3C  C < H3C  C < H3C  C
with multiple bonds order of preference will be
as follows: H H H CH3
Functional group > Double bond > Triple bond Methyl 1 2 3
> Side chain
O 18. More the number of the alkyl groups, greater
O will be the dispersal of the positive charge on
H C 2 the carbon atom due to the +I (electron
1 3 4 releasing) effect, and thereby greater will be the
5 stability. Hence, the most stable carbocation
6

3-Keto-2-methylhex-4-enal formed from the given compounds is  H 3C 3 C .

48
 

MHT-CET Triumph Chemistry (Hints)

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.

76
 

Chapter 14: Basic Principles of Organic Chemistry

24. Resonance effect is observed in a conjugated 27. In alkyl free radicals, the carbon atom having
system of  electrons. In option (B), lone pair the unpaired electron is sp2 hybridised. For
on ‘N’ atom is not in conjugation with carbon- hyperconjugation the -carbon atom with
carbon  bond. Hence, resonance effect is not respect to sp2 hybridised carbon atom should
observed in the structure given in option (B). have at least one hydrogen atom. Among the
given structures, only (III) has an -hydrogen
25. +
O  CH3 O  CH3 atom.


CH3
In other structures,  bond is not in conjugation H -H atom
with lone pairs of electrons. Hence, in these Hence, hyperconjugation occurs in structure
molecules lone pairs are not delocalized. (III).
26. The resonance structures of pyrrole are: 28. Stability of carbocations depends upon the
extent of hyperconjugation effect which in turn
4 3 4 4 3

3 depends on the number of hyperconjugation
5 2 + 2  + 2 structures possible.
N1 5 N1 5 N1   
H H H CH3  CH – CH2  CH2 – CH3
has maximum (five) -H and thus has five
3 hyperconjugation structures. Hence, it is the
4 3 4
most stable carbocation among the given.
5 + 2 5 + 
N1 N1 2 29.  NO2 group is an electron withdrawing group
H H and it exhibits I effect. This I effect decreases
with increase in distance. In option (C), as the
The electron density is maximum on 2nd and 5th
C-atom with positive charge is at a maximum
carbon atoms as these carbon atoms are closer to
distance, so I effect is minimum and hence, it
the electronegative N-atom.
is the most stable carbocation.

Hints to Evaluation Test

1. The bond line formula for 1,1,1-trichloroethane 4. CH3  CH  CH2  CH  CH3

4 3 2 1
can be represented as:
5 CH2 OH
Cl
6 CH3
Cl
The IUPAC name of the compound is
Cl 4-methylhexan-2-ol.
2. Benzenoid aromatic compounds contain at least 6. BCl3 is an electron-deficient species and hence,
one benzene ring in the structure. Thus, aniline
it is an electrophile. CN, ROH and NH3 are
is a benzenoid aromatic compound. Pyrrole is a
electron-rich species and hence, these are
non-benzenoid aromatic compound.
nucleophiles.

3. Electromeric effect arises due to the mobility of 7. The polarizability/ electromeric electronic effect
electrons in double or triple bonds, i.e., it is occurs in a substrate due to approach of the
possible only in a -bonded compound. Among attacking reagent hence it is a temporary effect.
the given options, only ethyne has  bonds and 10. Benzenoid compounds contain at least one
can undergo electromeric effect. benzene ring.
49
 
Textbook
Std. XII:No.
Chapter 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.  = iMRT = i W2 RT
M 2V
condensation is an exothermic process. Hence,
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
P10 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
0.184 point increases and vice-versa.
m= = 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  is the osmotic pressure of a dilute solution
when forming a solution.
then, V = nRT where n = moles of solute
6. Sugar dissolves in water because the dissolution
nRT
 = of sugar in water is due to intermolecular
V hydrogen bonding between sugar and water.
1
 at constant T :   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 :   T and of the gas over the solution.
V = constant if T and n are constant
12. Gases like NH3 and CO2 react with water as
 The incorrect statement is   V when T is
follows:
constant.
 NH 4 + OH–
NH3 + H2O 
46. Na3PO4 gives a maximum of four ions, thus, it
 H2CO3
CO2 + H2O 
will show highest van’t Hoff factor.
78
 

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
P10  P1 760  750 10 1
17. P1 = P x10 x2 = 0
  =
1 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
78  W1 = 1.58 g/cm3  100 cm3 = 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
 =
P  P1
0
P 640 39.08× M 2
1
= 0 = x2
P10 P1  M2 = 69.5 g mol1
79
 

MHT-CET Triumph Chemistry (Hints)

P10  P1 W ×M K b  W2  1000 3.9  0.5143  1000
29. = 2 1 39. M2 = =
P10
W1 × M 2 Tb  W1 0.323  35
3000  2985 5  18 = 177.42 g/mol
 =
3000 100  M 2
K b  W2  1000 0.52  6  1000
 M2 = 180 g mol1 40. M2 = = = 60 g mol1
Tb  W1 0.52  100
P10  P1 W ×M
30. 0
= 2 1 41. Tf = Kf m = 1.86  0.05 = 0.093 K
P1 W1 × M 2
 Freezing point = (273  0.093) K = 272.907 K
10 2  78

750 78  M 2 342
42. Tf = Kf  m = 1.86  = 1.86 K = 1.86 C
2  78  750 342
 M2 = = 150 g mol1
10  78 Tf = Freezing point of solvent
P10  P1 W ×M  Freezing point of solution
31. = 2 1
P10 W1 × M 2  Freezing point of solution
0.3 20  18 = Freezing point of solvent – Tf
=
17.54 100  M 2 = (0 – 1.86)C = – 1.86 C
20  18  17.54
M2 = = 210.48  210.5 g mol1 1000 K f  W2
100  0.3 43. M2 =
Tf  W1
 0.1  M 2  Tf  W1
33. Tb = Kb  m = 0.513   1000  W2 =
 200  1000  K f
= 0.2565 C
 Tb = (100 + 0.256) C = 100.256 C. 60  0.186  500 6 5 30
W2 = = = =3g
1.86  1000 10 10
X
34. Tb = Kb  m = X  0.2 =   C
5 Tf  W1  M 2
44. W2 =
 Boiling point of the solution = Boiling point of 1000  K f
X 1.05  100  9000
pure solvent + Tb = (A + ) C = = 192.86 g  193 g
5 1000  4.9
35. For 0.1 molal solution : Tb = (100.16 – 100) C
= 0.16 C. 45. Tf = 0.93 K
Solvent is same in both solutions, hence, Kb is K f  W2  1000 1.86  6  1000
M2 = =
constant. Tf  W1 0.93  100
Tb = Kb  m
= 120 g mol1
(DTb )1 m1
 =  Molar mass of x = 120 g mol1
(DTb )2 m 2
(D Tb )1 ´ m 2 0.16 ´ 0.5 46. Tf = 273 – 272.07 = 0.93 K
(Tb)2 = = = 0.8 C
m1 0.1 K f  W2  1000 1.86  6.8  1000
M2 = =
 for 0.5 molal solution : Tb = 0.8 C Tf  W1 0.93  100
Hence, boiling point of glucose solution = 136 g mol1
= (100 + 0.8) C
= 100.8 C. K f  1000  W2 5.1  1000  4.8
47. M2 = =
1000K b W2 1000  0.52  3
Tf  W1  5.5  4.48  60
36. M2 =  = 15.0 g/mol 5.1  4.8
Tb W1 0.52  200 = 3
= 400 g mol1
1.02  60  10
1000K b W2 1000  2.16  0.11
37. M2 =  K f  1000  W2
Tb W1 0.1  15 48. M2 =
Tf  W1
= 158.40 g mol1  158 g mol1
1.86  1000  0.1
=
38.
K  W2  1000 2.53 10  1000
M2 = b =
 273.15  272.813  21.7
Tb  W1 1 100 1.86  0.1
–1 = = 25.4 g/mol
= 253 g mol 0.337  21.7  10 3

80
 

Chapter 02: Solutions

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 0.186 K  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
 = 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+ + SO24  = 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
450 1000
properties increases.
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. =MRT 67. i=
colligative propertyof nonelectrolyte solution
 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.
 = MRT  The reaction is KCl  K+ + Cl–
W2 RT 3  0.0821 288 1 mole of KCl dissociates to form 2 mole
= = = 6.57 atm particles.
M2V 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.
81
 

MHT-CET Triumph Chemistry (Hints)

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  0.61  41
 x1 = = 0.50
1 0 0 50
(1–) 2  Ptoluene = y2 P
 i = (1 – ) +  + 2 = 1 + 2 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
WB = x2 = =
Tb = Kb ; 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 mass of 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

82
 

Chapter 02: Solutions

9. Vapour pressure of pure acetone P10 = 185 torr  PH2O = xH2 O PH0 2 O
Vapour pressure of solution, P1 = 183 torr 9.9
Molar mass of solvent i.e., acetone  PH2O =  760 mm (considering at boiling
10
(CH3COCH3), M1 = 58 g mol–1 point of water)
P10  P1 W ×M  PH2O = 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
M2 =  185
 Boiling point of pure solvent (water)
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
 P  3.00 = 1.2 P  3.624
1
0
1
0
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
18 ΔTf = Kf.m
 Mole fraction of water xH2O  =
nA
nA  nB
ΔTf = Kf  number of moles of solute
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

83
 

Chapter 15: Hydrocarbons

41. Ethylene dibromide when heated with zinc ethylene is obtained.
Br  CH2  CH2  Br + Zn 
alcohol
 CH2 = CH2 + ZnBr2


1,2-Dibromoethane Ethene
(Ethylene dibromide) (Ethylene)

45. Cl
|
CH3  C = CH  CH3 + HCl 
Markovniko v's rule
 CH3  C  CH2  CH3
| |
CH3 CH3
2-Methylbut-2-ene 2-Chloro-2-methylbutane

47. Reaction of HBr with propene in the presence of organic peroxide follows anti-Markovnikov’s addition and
gives n-propyl bromide as the major product.
CH3  CH = CH2  HBr
 CH3  CH2  CH2  Br
Peroxide

Propene n-Propyl bromide

48. CH3 – CH = CH2 + H–OSO3H  H  OH

H3C – CH – CH3  
 H3C  CH  CH3 + H2SO4
Propene (cold and conc.)
| |
(Propylene) Sulphuric OSO3H OH
acid Isopropyl hydrogen sulphate Propan-2-ol
(Isopropyl alcohol)
(Major product)

H O H
50.
C C
H2C = CH2 + O3  H H 
Zn / H 2 O

 2HCHO + ZnO
Ethene or Ethylene Formaldehyde
O O ‘B’

Ethylene ozonide
‘A’
52.
H H
H
6H3C  C = C  H + H  B 
THF
solvent
 2(CH3  CH2  CH2)3B
Propene H
2
Diborane

H3C  CH2  CH2

H3C  CH2  CH2  B 
3 HO - OH
NaOH
 3CH3  CH2  CH2  OH + B(OH)3
H3C  CH2  CH2 3 Propan-1-ol
(n-Propyl alcohol)
Tri-n-propylborane

53. Dilute alkaline KMnO4 is an oxidising agent and is known as Baeyer’s reagent. This reagent oxidizes
alkenes in the presence of water at low temperature to form dihydric alcohols, also called alkane diols,
vicinal glycols or 1,2-diols. In this reaction, KMnO4 is used up, hence the purple colour of potassium
permanganate disappears i.e., decolourisation of KMnO4 solution takes place.
54. CH2 = CH2 + H2O + [O] 
alkaline KMnO4
HO  CH2  CH2  OH
Ethylene Ethylene glycol
(Ethene) (Ethane-1,2-diol)

55. CH3CH = CH2 + H2O + (O) 

alkaline KMnO4
CH3  CH  CH2
Propene
OH OH
Propylene glycol

53
 

Chapter 02: Solutions

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.  
0.45 = i  60  5.12  i = 0.527
If several gases are present, then the solubility 0.02 
of any gas may be evaluated by using P as  
 
partial pressure of that gas in the mixture. 
From given graph it is gas-A i.e., 0.527 = 1    = 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. = 
n 1 P10 M 2 W1
i 1 W2M1P10
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
M2 = 62 g mol –1 31.757 100

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 moles of thesolute ∆Tf = Kf.m
But molality =
mass of 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.  (CH3COOH)2
2CH3COOH  d 1 MB
 
x=2 M m 1000
M M  MB 0.218 0.218  60
i = 1    1  i = 1    1 
1 1
 d= + = +
x  2  m 1000 0.222 1000
 = 0.982 + 0.013
i = 1
2 = 0.995  0.993 g mL1
85
 

MHT-CET Triumph Chemistry (Hints)

Hints to Evaluation Test

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. V = 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
M2 = 4
= 1.68  105 g mol1 P
= x2 =
M2
= 180
5.2  10 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 2 T
14. = 2
Vapour pressure lowering 1 T1
25  78  180 546  2.5
= P10  P1 = = 4.1 mm Hg 2 =
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 Msolute  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

86
 

Chapter 02: Solutions

W2 RT
18. = 
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

87
 

MHT-CET Triumph Chemistry (Hints)

96. AlCl3 is a Lewis acid which helps in formation of electrophile in the Friedel-Craft’s reaction.
In Friedel-Craft’s alkylation, the electrophile generated is R+ (carbocation) while in Friedel-Craft’s
acylation, the electrophile generated is R  C+ (acylium ion).
 R + + [AlCl4]
R  Cl + AlCl3  O
 R  C + + [AlCl4]
R  C  Cl + AlCl3 

O O
97. The base or nucleophile in the electrophilic substitution reactions is as follows:
Chlorination/Friedel-Craft’s
Alkylation or acylation : [AlCl4]
Bromination : [FeBr4]
Nitration : [HSO4]
99. The electron density in the aromatic ring in nitrobenzene decreases at ortho (o-) and para (p-) positions (as
shown in the resonating structures), due to the strong electron withdrawing resonance effect of NO2 group.
  O
O O O O O O O O O
N N N N N

+ +

+
II I III IV V
104. CH3CH = CH2 
HBr
 CH3CH(Br)CH3 
alc.KOH
 CH3CH = CH2 
O3
CH3CHO + HCHO
Zn.H 2 O
Propene 2-Bromopropane Propene Acetaldehyde Formaldehyde
(A) (B) (C)
105. Since, the given compound is an alkyne (CnH2n  2), the molecular weight is given as follows:
Molecular weight = (12  n) + [1  (2n  2)]
where, n = integer indicating number of carbon atoms
12 = atomic weight of carbon, 1 = atomic weight of hydrogen
180 = 12n + 2n  2
182 = 14n
182
n= = 13
14
 n = 13
 The alkyne with molecular weight of 180 is C13H24.
106. Disubstituted benzene derivatives are given common names using prefixes ortho (o-), meta (m-) or para (p-)
depending on the relative positions of the substituents.
A
1 A
6 2 Substituents in 1, 2 positions  ortho (o-)
5 3
4
A
1
6 2
Substituents in 1, 3 positions  meta (m-)
5
3
4 A
A
1
6 2
Substituents in 1, 4 positions  para (p-)
5 3
4
A
Thus, if two substituents are on the adjacent carbon atoms (1, 2 positions) in a disubstituted benzene, then
the compound is named using prefix ortho.
56
 

Chapter 03: 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.  = 0.001 % = 10–5
46. The solubility of a sparingly soluble compound Ka = 2c = (10–5)2  0.1 = 1.0  10–11
decreases with the presence of a common ion in 8.  = 4.0% = 4  10–2
solution.
Ka = 2c = (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 = 2c
i.e., 1000 cm3 of acidic solution will contain 10 Ka 1.8  105
13  c=  2 = 0.045 M
moles of H+ ions. 2  0.02
 1 cm3 of solution will contain 10–16 moles of H+
ions. 10. Ka = α12c1 = α 22c 2
 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 =   100
endothermic reaction.
1.3
 = = 1.3  10–2
100 12. pH = – log10[H+]
+
Equilibrium concentration of H ions  1 millimolar = 1  10–3 M
=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,
4. In forward reaction, HCO3 donates proton while [H+] = 2  0.05 = 0.1 M
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.
89
 

Chapter 15: Hydrocarbons

26. 3-Methylpent-2-ene exhibits cis-trans isomerism as follows:
1 4 5 4 5
H3C
2 3
CH2CH3 CH2CH3
H 2 3
C=C C=C
1
H CH3 H3C CH3
trans-isomer cis-isomer

27. Structural isomers of C5H10 can be represented as follows:

CH3  CH2  CH2  CH = CH2
Pent-1-ene

CH3  CH = CH  CH2 – CH3

Pent-2-ene

CH3 CH3 CH3

| |
H3C  C = CH  CH3 H2C = C  CH2  CH3 CH3  CH  CH = CH2
2-Methylbut-2-ene 2-Methylbut-1-ene 3-Methylbut-1-ene

28. The order of reactivity of alkyl halides towards dehydrohalogenation reaction is 3 > 2 > 1 and
iodides > bromides > chlorides.
Thus, among given options, alkyl halide given in option (D) is tertiary butyl iodide and will be most reactive
towards dehydrohalogenation reaction.
29. CH3 CH3 CH3

CH3  C  CH2  CH3 

alc. KOH

 CH2 = C  CH2  CH3 + H3C  C = CH  CH3

Cl
2-Chloro-2-methylbutane 2-Methylbut-1-ene 2-Methylbut-2-ene

30. The ease of dehydration of alcohols is in the order 3 > 2 > 1. Thus, 1 alcohols require high temperature
conditions as compared to 2 alcohols.
33. Branched alkenes have lower boiling points than straight chain alkenes.
35. Markovnikov's rule: When an unsymmetrical reagent is added to an unsymmetrical alkene, the negative part
(X-) of the reagent gets attached to the carbon atom which carries less number of hydrogen atoms.
36. Markovnikov’s rule governs the addition of unsymmetrical reagents to unsymmetrical alkenes. Br2 and Cl2
are symmetrical reagents while C2H4 is a symmetrical alkene. Moreover, in option (D), C3H8, an alkane will
undergo substitution reaction. Thus, among the given options, the Markovnikov’s rule is best applicable to
the reaction between C3H6 and HBr.
37. Reaction of HBr with but-1-ene in the presence of organic peroxide follows anti-Markovnikov’s addition
and gives 1-bromobutane as the major product.
(C6 H5CO) 2 O 2
CH3  CH2  CH = CH2 + HBr 
Benzoyl peroxide
 CH3  CH2  CH2  CH2Br
But-1-ene 1-Bromobutane

38. In the presence of peroxides, only the addition of HBr to an unsymmetrical alkene does not occur according
to Markovnikov’s rule.
39. H3C O CH3
O
C C
(CH3)2C = C(CH3)2 + O3  CH3 
Zn / H2 O

 2CH3  C  CH3 + ZnO
H3C Propanone
2,3-Dimethylbut-2-ene
O O

59
 

Chapter 03: Ionic Equilibria

28. For CaSO4, 36.
2
CaSO4(s)  Ca (aq)


+ 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.  3Ca + 2PO
Ca3(PO4)2(s)  3
4
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3aq  + 3OHaq 
Cr(OH)3(s)  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
31
K sp 2.7  10 1. The conjugate acid and base differ with respect
 S= 4  4  4 1032 = 108
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 -H
Acid ¾¾¾
+
 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). HSO 4 H2SO4 S O 24 

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+] =  c = c
c Total volume = 0.06 + 0.04 = 0.1 L
2  103
= Ka  c  [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  c2 (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
91
 

MHT-CET Triumph Chemistry (Hints)

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
+  NH4OH(aq) + H (aq)
NH 4(aq) + H2O(l)  

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   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,
 H+aq  + Qaq 
HQ(aq)  Ksp = xx.yy.Sx + y
K sp
[H+] = c  Sx + y =
xx.y y
[H  ] 103
 = = = 0.01 1
c 0.1  K  x+ y
 S =  x sp y 
Ka = 2c [ (1  )  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 
 H (aq)
HA(aq)   
 A (aq)
 [H+] =  c 20.  3Ca2+ + 2PO34
Ca3(PO4)2 
 H   1  105 3S 2S
 =   = 1  104
c 0.1 Ksp = [Ca2+]3 [ PO34 ]2 = [3S]3 [2S]2 = 108 S5
 Percent of degree of dissociation
21.  2A3 aq   3X2aq 
A2X3(s) 
=   100 = 1  104  100
= 1  102 % x = 2, y = 3
Ka = 2c = (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
92
 

Chapter 03: Ionic Equilibria

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–
12
S= 3 = 3 = 3
2.5  10 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.  2Ag  C2O 4 aq 
Ag2C2O4(s)  
 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2+aq
Ca(OH)2(S)  + 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 (aq)
Ba(OH)2(s)  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+] = [OH  ]   0.01  5  103 M 1
2 2 3  0.62  4
=   10
Ksp = [Ba2+] [OH]2  27 
= 5  103 M  (0.01)2 M2 = 0.389  103 mol dm3
= 5  107 M3 Thus, the molar solubility of MY in water is
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 Kb 1.7 109
=  = 1.3  104
given options). C 0.10
28. AgCl(s) 


Ag (aq) 
+ Cl(aq)  Percent dissociation =   100
Concentration = 1.3  104  100 = 0.013 %
S S + 0.1
(M)  Percentage of pyridine that forms pyridinium
+  ion in the given solution = 0.013 %
Ksp = [Ag ] [Cl ]
93
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MHT-CET Triumph Chemistry (Hints)

64. It is insoluble in water. It forms upper layer when mixed with water.
65. When benzene is heated with chlorine in the presence of sunlight, benzene hexachloride (C6H6Cl6) is formed.
H Cl
H H
Cl Cl
+ 3Cl2 
 bright sunlight
H
Cl
H Cl
Benzene
Cl H
Benzene hexachloride
(BHC)
66. Benzene reacts with H2 in the presence of Ni catalyst to give cyclohexane which is an alicyclic compound.
H / Ni
2
453  473 K


Benzene Cyclohexane
(Aromatic compound) (Alicyclic compound)

67. Benzene triozonide obtained from the reaction of benzene with ozone is highly unstable and explosive. It
undergoes hydrolysis with water in the presence of zinc to form three molecules of glyoxal, a dialdehyde.
O
O O
O CHO
+ 3O3  O 
Zn / H 2 O
 3| + 3H2O2
Hydrolysis
O O O CHO Hydrogen
Benzene Ozone Glyoxal peroxide
O
Benzene triozonide

68. When benzene is treated with limited amount of Cl2 in the presence of anhydrous AlCl3 in dark, substitution
of a hydrogen atom of benzene molecule by a chlorine atom occurs. The reaction mechanism involves
electrophilic substitution.
O

69. For introducing CH3 – C  group in the benzene ring, Friedel-Craft’s acylation reaction is used.
O
H C  CH3
O
+ CH3  C  Cl Anhydrous AlCl3
  + HCl


Benzene Acetyl chloride Acetophenone

70. In Friedel-Craft’s alkylation reaction, a hydrogen atom of the aromatic ring is substituted by an alkyl group
(R). The reaction involves treatment of the aromatic compound with an alkyl halide in the presence of
anhydrous AlCl3 to form alkyl substituted product.
In Friedel-Craft’s acylation reaction, a hydrogen atom of the aromatic ring is substituted by an acyl group (R
 CO ). The reaction involves treatment of the aromatic compound with acyl halide or acid anhydride in
the presence of anhydrous AlCl3 to form acyl substituted product.
The reaction of benzene with ethyl chloride forming ethyl benzene is a Friedel-Craft’s reaction.
C6H6 + C2H5Cl 
AlCl3
 C6H5C2H5 + HCl
Benzene Ethyl benzene

72. In an electrophilic substitution reactions such as sulphonation, the substituent that makes the aromatic ring
more reactive is called an activating group and the one that makes the aromatic ring less reactive is called a
deactivating group. CH3 is an activating group while Cl, NO2 and COOH are deactivating groups.
Hence, among the given options, toluene is most reactive towards sulphonation.
62
 
Textbook
Chapter No. Chapter 4: Chemical Thermodynamics

04 Chemical Thermodynamics

Hints

30. Enthalpy change that occurs when one mole of a

Classical Thinking solid is converted into liquid without change in
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
95
 

MHT-CET Triumph Chemistry (Hints)

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 dm 3 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
P2
than liquids and hence, entropy of the system
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,
P1
i. H = + ve (i.e., enthalpy increases) Wmax = 2.303 nRT log10
P2
ii. G =  ve (i.e., free energy decreases)
= 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

96
 

MHT-CET Triumph Chemistry (Hints)

19. H H H CH3 O

C = C – C = C – CH2 – CH3 

O3 / CH 2 Cl2 /196K
Zn / H 2 O
 CHO + CHO – CHO + CH3 – C – CH2 – CH3
Ethyl methyl
Cyclohexanal Glyoxal
1-Cyclohexyl-4-methylhexa-1,3-diene ketone

20. So, ‘A’ is (CH3)2C = CH – CH3.

CH3 CH3 CH3
CH3 – C = CH – CH3 + HCl  CH3 – C – CH2 –CH3  CH3 – C – CH2 –CH3
+
2-Methylbut-2-ene
Cl
2-Chloro-2-methylbutane
21. For an aldehyde, general formula can be written as CnH2nO.
In the reaction, an aldehyde having molecular mass of 44 u is formed.
i.e., (n  C) + (2n  H) + O = 44
(n  12) + (2n  1) + 16 = 44 (substituting atomic mass)
12n + 2n = 28
14n = 28
n=2
 the aldehyde formed is C2H4O i.e., CH3CHO.
 The symmetrical alkene that on ozonolysis gives two moles of acetaldehyde is but-2-ene.
H O H
CH3  CH = CH  CH3 + O3  C C 
Zn / H2 O

 2CH3CHO + ZnO
But-2-ene H3C CH3 Ethanal
(Acetaldehyde)
O O

-Butylene ozonide
22. The alkene which on ozonolysis will give the above compound is,
CH3
CH3 O
ozonolysis
¾¾¾¾  OHC – C – CH2 – CH2 – C – CH3

H
CH3
23. H3C  CH2  C  C  CH3
Correct IUPAC name: Pent-2-yne
24. The possible alkynes are:
CH3

CH3  CH2  CH2 C  CH CH3  CH2  C  C  CH3 CH3  CH  C  CH

Pent-1-yne Pent-2-yne 3-Methylbut-1-yne
25.
 +
H  C  C  H 
NaNH 2 / liq.NH3
 H  C  C Na 
CH3 CH 2 Br
H C  C  CH2  CH3 + NaBr
Ethyne But-1-yne
(X)
NaNH2/liq.NH3

NaBr + CH3  CH2  C  C  CH2  CH3 

CH3 CH 2 Br +
NaC  C  CH2  CH3
Hex-3-yne
(Y)

66
 

MHT-CET Triumph Chemistry (Hints)

46. The reaction for the combustion can be given as 57. 2C2H6(g) + 7O2(g)  4CO2(g) + 6H2O(l) ;
15
C6H5COOH(s) + O2(g)  7CO2(g) + 3H2O(l) rH° = – 3119 kJ
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
2x = – 1574 – 1716 + 3119 = – 171
H = 321.30 +     300  R
1

 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) – Δf H(CO) + Δ f H(O2 ) 

= [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

98
 

Chapter 15: Hydrocarbons

26. The hydrogen atoms attached to the triply bonded carbon atoms in alkynes are acidic in nature.
Acetylene (H  C  C  H) reacts with strong base such sodamide (NaNH2) to give sodium acetylide.
H  C  C  H + Na  NH 2  H  C  CNa+ + NH3
Acetylene Sodamide Monosodium Ammonia
acetylide
H  C  CNa+ + Na  NH 2  Na+C  CNa+ + NH3
Monosodium Disodium Ammonia
acetylide acetylide

27. When acetylene is passed into dilute sulphuric acid containing Hg 2 ions (1% mercuric sulphate), the
product formed is acetaldehyde.
H  C  C  H + H  OH  40% H 2SO 4
 [CH2 = CH  OH] 
tautomerism
  CH3  CHO

1% HgSO4
Acetylene Vinyl alcohol Acetaldehyde
(Enol)
28. When propyne is treated with aqueous H2SO4 in presence of HgSO4, the major product is propanone.

H3C  C  CH + H  OH   H3C  C = CH2  H3C  C  CH3

tautomerism
40% H 2SO4
 
 
1% HgSO4

Methyl acetylene OH O
(Propyne) Acetone
Prop-1-en-2-ol (Propanone)

29. CH3  CH2  C  CH + H  OH 

2 4
 [CH3  CH2  CH = CH  OH]
40% H SO
1% HgSO4

But-l-yne
Tautomerism

CH3  CH2  CH2  CHO

Butanal

OH O
30. H3C – C  CH 
H 2 O, H 2SO 4
H3C – C = CH2  H3C – C – CH3
HgSO 4
Propyne  Markovnikov’s
addition  Intermediate Product
(enol form) (Propanone)
(A) (B)
31. The COOH group is given priority over NH2 and OH groups. So, the carbon atom bearing COOH
group is considered to be at position 1. The carbon atoms of the ring are numbered so as to assign the lowest
locant to the substituents.
OH
4
3 5

6
H2N 2
1
COOH
The IUPAC name of the given compound is 2-amino-4-hydroxybenzoic acid.
33. According to Huckel rule, any cyclic, planar and conjugated compound containing (4n+2) electrons, where
n = 0, 1, 2, 3, etc. is aromatic.
(4n+2) = 6  n = 1; aromatic compound

(4n+2) = 4  n = 1 2 ; not aromatic

+

(4n+2) = 4  n = 1 2 ; not aromatic

O
67
 

MHT-CET Triumph Chemistry (Hints)

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 
= –2.303  1  8.314  302  (–0.6989) 9. In an adiabatic process, there is no exchange of
= 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
100
 

Chapter 04: Chemical Thermodynamics

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 = H(reactant bonds) – 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 = fH(products) – 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

101
 

MHT-CET Triumph Chemistry (Hints)

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
102
 

MHT-CET Triumph Chemistry (Hints)

60. π
σ σ σ
H C C H
π
3 and 2 bonds

61. H H H

H–CC–C=C–C–H
1 2 3 4 5
H
10  and 3  bonds

62. sp2 sp2 sp sp

CH2 = CH– C  CH

63. CH4 + Br2  h

Substitution   CH3Br
Methane Methyl
‘A’ bromide

 Wurtz reaction   CH3  CH3 + 2NaBr

CH3Br + 2Na + CH3Br dry ether

Methyl Methyl Ethane

bromide bromide (Gaseous
hydroccarbon)
65.
Compound Hybridisation of carbon atom(s)
CO2 sp
Ethane sp3
Ethyne sp
Ethene sp2
Ethanol sp3
Thus, the compound having same hybridization as its combustion product (CO2) is ethyne.
66. In biphenyl, all the carbon atoms are sp2 hybridised having trigonal planar geometry. Hence, all the atoms
will lie in the same plane i.e., all the atoms are coplanar.
67. Lower the heat of hydrogenation (i.e., enthalpy of hydrogenation), more stable is the compound.
Compound (I) is aromatic. Hence, it is more stable than compounds (II) and (III).
Compound (II) has conjugated double bonds. Hence, it is more stable than compound (III).
Thus, the stability decreases in the order: (I) > (II) > (III)
Therefore, the enthalpy of hydrogenation decreases in the order: (III) > (II) > (I)

Hints to Evaluation Test

1. Alkanes are insoluble in water.

2. Since, the given compound is an alkane (CnH2n+2) with molecular weight 170.
Therefore, (12  n) + 1(2n + 2) = 170
Where n = integer indicating number of carbon atoms in a molecule
12 = atomic weight of carbon
1 = atomic weight of hydrogen
 12n + 2n + 2 = 170
 14n = 168
168
 n= = 12
14
 The molecular formula of the given alkane is C12H26.
70
 

Chapter 15: Hydrocarbons

3. In alkanes, boiling point depends on molecular mass. Greater the molecular mass, higher will be the boiling
point. For isomeric alkanes, boiling points of branched chain alkanes as compared to straight chain alkanes
are lower. Hence, among given options n-octane has maximum boiling point.
4. C2H5I + 2Na + C3H7I 
Dry ether

 C5H12 + 2NaI
Ethyl Sodium n-Propyl Pentane Sodium
iodide metal iodide iodide

C2H5I + 2Na + C2H5I 

Dry ether

 C4H10 + 2NaI
Ethyl Sodium Ethyl Butane Sodium
iodide metal iodide iodide

C3H7I + 2Na + C3H7I 

Dry ether

 C6H14 + 2NaI
n-Propyl Sodium n-Propyl Hexane Sodium
iodide metal iodide iodide

Thus, n-propane is not formed when a mixture of ethyl iodide and n-propyl iodide is subjected to Wurtz reaction.
5.
CH3  CH2  CH2  CH3 + Br2 
UV Light
 CH3  CH  CH2  CH3 + CH3  CH2  CH2  Br
n-Butane 1-Bromobutane
Br
(Minor product)
2-Bromobutane
(Major product)

6. C2H4 
HBr
 C2H5Br 
alc.KOH

 C2H4
Ethene Ethyl bromide Ethene
‘A’ ‘A’

7. In a reaction, if half of the double bond is broken and two new bonds are formed, this is a case of addition.
eg.
Br
C = C  
2
CC
(Alkene) Br Br
(Addition product)
8. When ethylene reacts with bromine, it forms ethylene dibromide.
H2C = CH2 + Br2  H2C  CH2
Ethylene Bromine
Br Br
Ethylene dibromide
(X)

9. Replacing the Oatoms of the carbonyl compounds by double bond, the alkene formed is:
CH3 CH3
CH3 CH3
C =O+O=C  CH3  C = C  CH2  CH3
CH3 C2H5 2,3-Dimethylpent-2-ene
Acetone Ethyl methyl ketone

10. CaC2 + 2H2O 

 C2H2 + Ca(OH)2
Calcium Ethyne
carbide (X)
H H
40% H 2SO4
H  C  C  H + H  OH 
1% H 2SO 4
 HC=CH Tautomerism

 
 H  C  C H
Ethyne
(X) O  H O H
Vinyl alcohol Ethanal
sp2 sp3 sp 2
11. CH3  CH  CH  CH 2  CH  CH  C  CH
sp3 sp 2 sp 2 sp sp

Molecular formula: C8H10

71
 
Textbook
Chapter No. Chapter 5: Electrochemistry

05 Electrochemistry

Hints

 Moles of copper deposited on passing of

Classical Thinking 9650 coulombs
9650
= = 0.05 moles
1000k 2  96500
9. Molar conductivity,  =
C
24. At cathode:
1000  6.3  102
= Ni2+ + 2e–  Ni
0.1
 2F will deposit 1 mole of Ni.
= 630 ohm1 cm2 mol1 0.1  1
 0.1 F will deposit = = 0.05 mol Ni
1 2
10. Molar conductivity  ,
Molarity
25. Fe3+ + 3e  Fe
Lower the concentration, higher will be molar  3 F will deposit 1 mole (i.e., 56 g) of Fe
conductivity. So, molar conductivity will be 0.6  56
maximum for 0.001 M HCl solution. So, 0.6 F will deposit = = 11.2 g
3
11. The expression for the variation of the molar
26. 
Ag (aq)  e   Ag(s)
conductivity () of strong electrolytes with
concentration (c) is  = 0  a C 1 Faraday i.e., 96500 C will deposit 108 g of
where ‘a’ is constant and ‘0’ is the molar Ag.
conductivity at zero concentration or infinite  9650 C will deposit 10.8 g of Ag
dilution. 27. Cu2+ + 2e  Cu
14. 0 (NaBr) = 0 (NaCl) + 0 (KBr) – 0 (KCl) To deposit 1 mole of Cu, 2 F i.e.,
= 126 + 152  150 = 128 S cm2 mol1 2  96500 coulombs of electricity is required.
 Coulombs of electricity is required
 50 = 2  96500 C = 193000 C
15. α= c = = 0.2
0 250 = 1.93  105 C
 = 0.2  100 = 20 % 28. Salt bridge prevents the mixing of the two
16. Cell constant = k  R solutions in the half cells.
= 0.002765  400 = 1.106 m1 30. Zn(s) + 2Ag  (1 M)  Zn 2  (1 M) + 2Ag(s)
21. The charge of one mole electrons is The two half cell reactions are:
96500 coulombs (C). It is referred to as one Zn(s)  Zn 2  (1 M) + 2e
faraday (1 F). [ Ag  (1 M) + e  Ag(s)]  2
3+
22. The balanced equation for the reduction of Cr Therefore, Zn is oxidised and acts as negative
to Cr is Cr3aq  + 3e–  Cr(s) electrode (anode) whereas, Ag+ ions are reduced
The equation shows that 1 mole of Cr3+ is and acts as positive electrode (cathode).
reduced to Cr by 3 moles of electrons. Hence the cell representation is
For reduction of 5 moles of Cr3+, 15 moles of Zn(s) | Zn2+ (1 M) || Ag+ (1 M) | Ag(s)
electrons will be required. 31. The electrode potential and the cell potential
23. In CuSO4 solution, the reduction reaction of Cu depend on concentrations of solutions, pressures
can be given as, of gases and the temperature.
Cu2+ + 2e  Cu 32. According to IUPAC convention, standard
 To deposit 1 mole of Cu, 2 F i.e., potential of an electrode is taken as the standard
2  96500 coulombs of electricity is required. reduction potential.
105
 

MHT-CET Triumph Chemistry (Hints)

33. Since, Cu2+ undergoes reduction it is cathodic 6. ∧0 (CaCl2) = λ0Ca2+ + 2λ0Cl
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  50 S cm2 mol1
electrodes. The standard potential of this α= c = = 0.125
0 400 S cm2 mol1
electrode has arbitrarily been taken as zero.

41. For hydrogen gas electrode, Haq | H2 (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 PH 0.0592 PH = 46 ohm1 cm2 mol1
EH2  EoH2  log10 2 2   log10 2 2
2 H  2 H  9. Depending upon the type of electrochemical cell,
o anode and the cathode may be positive or
(since EH2 = 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 1000  2.428  10  3

c= = = 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

106
 

Chapter 05: Electrochemistry

13. When molten metal chloride undergoes 19. Eocell  Eocathode  Eoanode = EoCo  EoMn
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  Cl 2 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 
2 PCl2
= 96.15 g mol1
2
14. 2H+ + 2e  H2 0.0592 Cl   Mg 2  
log10   
o
= Ecell –
molesof product 1 2 1
(mole ratio)1 = 
=
molesof e 2 o 0.0592
= Ecell – log10 [Cl–]2 [Mg2+]
Ca2+ + 2e  Ca 2
molesof product 1
(mole ratio)2 = =
molesof e 2 21. Eocell  Eocathode  Eoanode
W1 W2
= EAg  ESn  0.800V  0.136 V = 0.936 V
o o

 mole ratio 1  M1  mole ratio 2  M 2
W1 2 1 The cell potential is given by
  0.0592 V [Sn 2 ]
W2 40 20 Ecell = Eocell  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 = Eoel  log
=  mole ratio Hg 2  :  mole ratio Hg 2  : n [Zn 2  ]
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 2
Zn(s) + Cu (aq)  Zn (aq)
2
 Cu (s)
cathode (+) at extreme right.
At 298 K,
2 2
18. Cu (s) | Cu (aq) 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.

107
 

MHT-CET Triumph Chemistry (Hints)

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  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) = 0m (CH3COO–) + 0m (H+)
electrochemical series are oxidizing agents.
  0m (CH3COOH)
30. Lower is the reduction potential, greater is the 1 0
=  m (CH3COOK) +
0
reducing power. Hence, the increasing order of  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 oanode = –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 () =
nF [Reactant] 0
At equilibrium, Ecell = 0 150
= = 0.3
2.303 RT [Product] 500
 E ocell  log10
nF [Reactant]  2c
Dissociation constant of HF (Ka) =
0.06 [Sn 2  ] 1 
 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 ,
= – 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  = 70 m1
ii. For given 0.5 M solution,
Competitive Thinking Resistance (R) = 280 
Specific conductance (k)
a
2. G=k cell constant 70 m 1
l =  = 0.25 S m1
R 280 
 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
108
 

Chapter 05: Electrochemistry

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
109
 

MHT-CET Triumph Chemistry (Hints)

 At cathode; Cu2+ + 2e  Cu W1 18

2 moles of electron give 1 mole of Cu. 1
2
 58.5 13  27
0.01
 0.01 mole of electron will give = = 0.005 W1 
18 58.5
  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
Au 3  |Au
of mass of Al, Ag, Mg deposited will be
1 1 1 E = 0.15 V
Sn 4  |Sn 2 
: : =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
W1 W2
2Ag  2Ag+ + 2e (Oxidation at anode)
 Zn+2 + 2e  Zn (Reduction at cathode)
 mole ratio 1  M1  mole ratio 2  M 2
8 W2
 2Ag + Zn+2  2Ag+ + Zn
1
 32 1  108
4 (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
Ecell =  1.562  log10
Aluminium chloride : AlCl3 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  M1  mole ratio 2  M 2 = 1.562 + 0.0296 =  1.5324 V
110
 

Chapter 01: Solid State

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  r 3  r
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 × 10 23 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
   NA 
1 20. Closest distance in fcc = 2r
 2  6.94 g mol1 3
 a= 3 1  2 2a
 0.530 g cm  6.02  10 mol 
23
=
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 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
M= 10   200  10 
 10 3

4
–1
= 27 g mol 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 x
Number of unit cells in x g of metal =
4r 4r  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
Z bcc ×M  4r 
N0 ×  27
dbcc N 0 ×a 3  3 = = 1.0  1024 unit cells
= = 4×M 27  10  24
dfcc Zfcc ×M
N 0 ×a 3  4r 
3
23.
N 0 ×  Contribution
 2 Atom/ion Location
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)
= r
3 Ratio A : B = 1 : 5/2 = 2 : 5
In fcc unit cell, there are 4 atoms present. Formula A2B5
75
 

MHT-CET Triumph Chemistry (Hints)

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),
60. From the electrochemical series of standard
7.5F + 2.4F = 5.1F
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. ΔG° = nFEcell = –RT ln K
o  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 mole of electron will give =
0.01
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) 2
 SO 4(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

112
 

Chapter 05: Electrochemistry

Hints to Evaluation Test

l 1.5cm  E  E
2. Cell constant = = = 2.0 cm–1 Zn 2  / Zn Mg 2  / Mg
a 0.75cm 2
Zn cannot reduce Mg2+. Mg and Zn will reduce
5. The balanced equation for the reduction of Zn2+ Fe but not oxidise Fe since their E values are
to Zn is lesser than Fe.
–
Zn 2aq  + 2e  Zn(s) 13. Electrolytic conductivity of a solution decreases
The equation shows that 1 mole of Zn is 2+ with decrease in concentration of solution.
reduced to Zn by 2 moles of electrons (i.e., 2 F). 17. Cell constant = k  R
Therefore, for 3 moles of Zn2+, 6 F of electricity = 0.00141 Ω–1 cm–1 × 604 Ω
will be required. = 0.8515 cm–1
6. More negative the reduction potential, higher 18. Zn + Fe2+  Zn2+ + Fe
will be the reducing property. Since Zn has  Zn 2  
0.0592
more negative reduction potential than the other E = E  log10
given options, Zn will be the strongest reducing 2  Fe 2  
agent. 0.0592  Zn 2  
E = E + log10
Cell constant 0.5 2  Fe 2  
9. k= = = 1  102
R 50 0.0592 102
1000  = 0.2905 + log10 3
 = 2 10
C = 0.32 V
1000  1  102 At equilibrium,
 = = 10 ohm1 cm2 mol–1
1 0.0592
 E = log10 K = 0.0296 log10 K
2
10. Oxidation state of X and Y are X3+ and Y2+
0.32
respectively.  log10 K =
0.0296
X3+ + 3e–  X 0.32
molesof product 1  K = 10 0.0296
(mole ratio)1 = =
molesof e 3
19. Oxidation at anode:
Y2+ + 2e–  Y Cd(s)  Cd2+ + 2e–
molesof product 1 Reduction at cathode:
(mole ratio)1 = =
molesof e 
2 Sn2+ + 2e–  Sn(s)
M1 1 Eocell  Eocathode  Eoanode
 (Given)
M2 2
Eocell = ESn
o
 ECd
o
= – 0.136 – (–0.403) = 0.267 V.
W1 W2
 ΔG = – nF Ecell
o
 mole ratio 1  M1  mole ratio 2  M 2
n=2
W1  mole ratio 1  M1 13 1 1
    ΔG = 2 mole   96500 C / mol e   0.267 V
W2  mole ratio 2  M 2 12 2 3
= – 51531 V C = – 51531 J = – 51.53 kJ

11. Eocell  Eocathode  Eoanode 20. Cu 2aq  + 2e–  Cu(s)

Eocell  EoAu  EoCd = (1.500 V) – (–0.403 V) 1 mol

Mole ratio =
= 1.903 V 2 mol e
I  A  × t s 
W=  mole ratio × MCu
12. E
Zn 2  / Zn
= 0.76 V 96500  C / mole  
E
Mg 2  / Mg
= 2.37 V = 2 × 965 × 60 × 1  63.5 = 38.1 g
96500 2
E 2
Fe / Fe
= 0.44 V
E  E  E 2
Mg 2  / Mg Zn 2  / Zn Fe / Fe
2+
 Zn will reduce Fe
113
 
Textbook
MHT-CET
Chapter No.Triumph Chemistry (Hints)

06 Chemical Kinetics

Hints

0.125 Ms–1 = k  2.0 M  (0.4 M)2

Classical Thinking 0.125M / s
 k= = 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[NH3 ] =
rate =    (1  10 3 mol L1 ) 2
dt 3 dt 2 dt
1 d[H 2 ] 1 d[NH3 ] = 3.25 mol–1 L1 s–1
  
3 dt 2 dt 13. (rate)1 = k [A] [B]
d[NH3 ] 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]
8. Rate of reaction = constant,
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[NO2 ] 2 2 2
rate = – =
2 dt 4 dt
17. Order of a reaction = sum of the exponents of
d[NO2 ]
 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

114
 

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
k[8A]x = 2k[A]x
2.303  4 0.29
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
[A]0  [A]t
defined as the number of reactant molecules 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
k 2 of s1.
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.
115
 

MHT-CET Triumph Chemistry (Hints)

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[O2 ] 1 d[SO2 ] 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[SO2 ] i.e., the rate of formation of B will increase by a
 2.5  10 = – factor of 4.
2 dt
d[SO2 ] 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
6  102
8r = k[2G]x[2H]y ….(ii)
nd
= According to 2 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
  NH 3 
4 = 2y
–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)
116
 

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
P10  P1 760  750 10 1
17. P1 = P x10 x2 = 0
  =
1 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
78  W1 = 1.58 g/cm3  100 cm3 = 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
 =
P  P1
0
P 640 39.08× M 2
1
= 0 = x2
P10 P1  M2 = 69.5 g mol1
79
 

MHT-CET Triumph Chemistry (Hints)

25. Flask I: [A]0 = 1 M 32. Activation energy (Ea) = 60 kJ mol1
= 60  103 J mol1
[A]t = 0.25 M  
1
of originalconcentration 
4
th
 Temperature (T) = 300 K
 2 t1/2 = 8 hrs f = e - E a / RT
t1/2 = 4 hrs Substituting the given value above
æç ö÷
çç - 60 ´103 J mol- 1 ÷÷÷
Flask II: [A]0 = 0.6 M ; [A]t = 0.3 M çç
èç 8.314 J K - 1 m ol- 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   -60 ´ 103
t3 1 log10f =
  8.314 ´ 300 ´ 2.303
4 4
2.303
log10f = 10.445 ≈ −10.4
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  E a / 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 = = e T T

 t= e 2000/ T
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

118
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Chapter 06: Chemical Kinetics

39. Arrhenius equation is given as: d d d[N 2 ]
44. rate = – C6H5 N2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  H2  1 d  NH3 
Rate =   
A = 106 = 1.0  106 s1 dt 3 dt 2 dt
d  N 2  1 d  NH3 
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[NO2 ] d[O2 ]
 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
 [Br  ]
As temperature increases, t1/2 decreases. 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
119
 

MHT-CET Triumph Chemistry (Hints)

8. Rate = k[A]2[B] y

1 =  
1
0.22 = k (1)2(0.25)   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

120
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Chapter 06: Chemical Kinetics

(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 = 2x 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
log
[A]0
Rate1 (R1) = k[2A]x [B]y ....(ii) t [A]t
But rate1(R1) = 2 rate(R)  A]0
log 
2.303 2.303 100 
 t = log = 2 
 x y x y
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)
2.303  20 
 k[4A]x [4B]y = 4k[A]x [B]y t= 2
log10  
10  5 
….[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
121
 

Chapter 02: Solutions

9. Vapour pressure of pure acetone P10 = 185 torr  PH2O = xH2 O PH0 2 O
Vapour pressure of solution, P1 = 183 torr 9.9
Molar mass of solvent i.e., acetone  PH2O =  760 mm (considering at boiling
10
(CH3COCH3), M1 = 58 g mol–1 point of water)
P10  P1 W ×M  PH2O = 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
M2 =  185
 Boiling point of pure solvent (water)
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
 P  3.00 = 1.2 P  3.624
1
0
1
0
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
18 ΔTf = Kf.m
 Mole fraction of water xH2O  =
nA
nA  nB
ΔTf = Kf  number of moles of solute
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

83
 

Chapter 06: Chemical Kinetics

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.
123
 

MHT-CET Triumph Chemistry (Hints)

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 ] 

Hints to Evaluation Test

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
t (a  x) (1.25  10–3) = k2[0.005]y ….(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
 0.25   0.5 
2. k=
2.303 [A]
 log10 0   
t [A]t  1   1 
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.
124
 

Chapter 06: Chemical Kinetics

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
20. Order of a reaction = sum of the exponents of
the concentration terms
3  1 2
 Order of the reaction = +   = = 1.
2  2 2

125
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MHT-CET Triumph Chemistry (Hints)

Hints to Evaluation Test

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. V = 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
M2 = 4
= 1.68  105 g mol1 P
= x2 =
M2
= 180
5.2  10 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 2 T
14. = 2
Vapour pressure lowering 1 T1
25  78  180 546  2.5
= P10  P1 = = 4.1 mm Hg 2 =
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 Msolute  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

86
 

Chapter 07: Elements of Groups 16, 17 and 18

40. 64. HOCl: Hypochlorous acid
Compound Oxidation state of xenon HClO3: Chloric acid
XeF4 +4 HClO2: Chlorous acid
XeF2 +2 HClO4: Perchloric acid
XeO3 +6 65. Oxidation number of ‘Cl’:
XeF6 +6 HOCl: +1 ; HOClO: +3 ;
HOClO2: +5 ; HOClO3: +7
41.
Compound Oxidation state of xenon 66. 2KClO3 
MnO
Δ
 2KCl + 3O2
2

XeOF4 +6 ⸫ 1 mol KClO3 ≡ 1.5 mol O2

XeF4 +4 67. Electronic configuration of O2 is: KK (2s)2
XeO3 +6 *(2s)2 (2pz)2 (2px)2 (2py)2 *(2px)1
XeF6 +6 *(2py)1.
43. On moving down the group 16, the size of the There are two unpaired electrons present in O2.
central atom increases and therefore, its Therefore, dioxygen exhibits paramagnetism in
tendency to form stable covalent bond with spite of having even number of electrons.
hydrogen decreases. As a result, thermal 69. Acidic oxides: N2O5
stability decreases. Basic oxides: BaO
46. Higher the pKa value, weaker is the acid. HF is Amphoteric oxides: Al2O3
the weakest acid among halogen acids, hence, Neutral oxides: N2O
its pKa value will be the highest. 72. Ozone is prepared in the laboratory by passing
silent electric discharge through pure and dry
Hydrides HF HCl HBr HI
oxygen in an apparatus called ozoniser.
pKa 3.2 7.0 9.5 –10.0
74. Ozone oxidizes potassium iodide to iodine and
47. Thermal stability of hydrogen halides decreases reduces hydrogen peroxide to water.
in the order: HF > HCl > HBr > HI.
2KI(aq) + H2O(l) + O3(g)
48. TeO2 acts as an oxidising agent. Potassium Ozone
iodide
51. I2O5 is a very good oxidising agent and used for
 2KOH(aq) + I2(s) + O2(g)
the estimation of carbon monoxide.
Potassium Iodine
53. Stability of halides decreases in the order: hydroxide
fluorides > chlorides > bromides > iodides
H2O2 + O3  H2O + 2O2
55. 2Au + 3Te  Au2Te3 Hydrogen Dioxygen
Gold telluride peroxide

56. Ionic character of halides decreases in the order 75. In laboratory, sulfur dioxide is prepared by
MF > MCl > MBr > MI, where, M is a treating sodium sulfite with dilute sulfuric acid.
monovalent metal.
Na2SO3(aq) + H2SO4(aq)  SO2(g) + Na2SO4(aq) + H2O(l)
57. Sulfur: Both the allotropes (rhombic and Sodium Sulfuric Sulfur Sodium
monoclinic) are non-metallic in nature. sulfite acid (dil) dioxide sulfate
Selenium: One allotrope is metallic (grey form)
and the other is non-metallic (red form) in 77. Sulfur dioxide acts as a reducing agent in the
nature. presence of moisture. Moist sulfur dioxide
Polonium: Both the allotropes (α and β forms) reduces ferric salts into ferrous salts.
are metallic in nature. 2Fe3+ + SO2 + 2H2O
59. Rhombic sulfur is referred to as -sulfur and Ferric Sulfur
ion dioxide
monoclinic sulfur as -sulfur.
62. Thiosulfuric acid (H2S2O3) contains S=S bond.  2Fe2+ + S O 24  + 4H+
Ferrous Sulfate Hydrogen
S ion ion ion

S 79. Sulphuric acid is a strong oxidising agent.

HO
O 83. Chlorine is 2-5 times heavier than air.
OH
127
 

MHT-CET Triumph Chemistry (Hints)

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
NH3 + 3Cl2  NCl3 + 3HCl nature.
10 2 6
Ammonia Chlorine Nitrogen Hydrogen 4. 36Kr: [Ar] 3d 4s 4p
(excess) trichloride chloride 10 2 6
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
its bleaching action. Chlorine is not used to shells.
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
89. Interhalogen compounds have even number of accept electrons. This is because of their stable
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
91. I2 + 3Cl2  2 I Cl3 Element Cl O F He
(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
electrons on central atom X. Compound Oxidation state of xenon
XeOF4 +6
99. Partial hydrolysis of XeF4 yields xenon XeO3 +6
monooxydifluoride (XeOF2). XeF6 +6
80  C
XeF4 + H2O   XeOF2 + 2HF XeF4 +4
Xenon Water Xenon Hydrogen XeF2 +2
tetrafluoride monooxydifluoride fluoride
13. The acidic character of the hydrides increases,
101. XeF4: Square planar ; while thermal stability decreases from H2O to
XeF6: Distorted octahedral H2Te.
XeO3: Trigonal pyramidal ; 14. The acidic character of the hydrides increases
XeOF4: Square pyramidal from H2O to H2Te because the bond
dissociation enthalpy of the H–E bond decreases
102. For filling balloons, a mixture of helium (85%) down the group. (where, E = O, S, Se, Te)
and hydrogen (15 %) is used. Thus, H2Te is most acidic among the given
hydrides and will have lowest value of pKa.
Critical Thinking Hydride H2O H2S H2Se H2Te
2. CuFeS2: Copper pyrites pKa values 14.0 7.0 3.8 2.6
Na3AlF6: Cryolite 15.
3Ca3(PO4)2.CaF2: Fluorapatite Hydrides H2O H2S H2Se H2Te
CaSO4.2H2O: Gypsum b.p. (K) 373 213 232 269

128
 

Chapter 07: Elements of Groups 16, 17 and 18

16. Dipole moment depends upon the 23. Hypochlorous acid, HOCl
electronegativity of the atoms in the molecule.
O
Oxygen is the second most electronegative H Cl
element and the electronegativity decreases
down the group. So, the increasing order of Chlorous acid, HOClO or HClO2
dipole moment will be O
H2Te < H2Se < H2S < H2O. O
H Cl
17. The acidic character of hydrides increases down
the group i.e., from HF to HI. HF is least acidic Chloric acid, HClO3
hence will have the highest pKa value. O
O
18. Bond dissociation enthalpies of halogen H Cl
molecules follow the order: O
Cl – Cl > Br – Br > F – F > I – I. Perchloric acid, HClO4
19. The tetrahalides of group 16 elements undergo O
sp3d hybridisation and possess trigonal O
bipyramidal geometry with one equatorial H Cl O
position occupied by a lone pair of electrons. O
F 24. Out of several oxoacids of halogens, only 4
F have been isolated in pure form. These are HOF,
Se HClO4, HIO3 and H2IO6. All others are stable
F only in aqueous solutions or in the form of their
F salts.
20. (I) S2 molecule has two unpaired electrons in 25. 4HCl + O2 
CuCl
Δ
 2Cl2 + 2H2O
2

the antibonding π* orbitals.

(IV) Grey selenium allotrope is a 26. NO, N2O and CO are examples of neutral
photoconductor used in photocells. oxides.
21. Sulfurous acid, H2SO3 28. (I) Ozone is thermodynamically less stable
than dioxygen.
(IV) Ozone acts as a good bleaching agent due
to its oxidising nature.

S 29. 2NaOH + SO2  Na2SO3 + H2O

HO (X)
HO O
Na2SO3 + H2O + SO2  NaHSO3
(Y)
Disulfuric acid or pyrosulfuric acid, H2S2O7
30. In SO2, O – S – O bond angle is 119.5°.
O O
31. SO3 + H2SO4  H2S2O7
S S
O O O
Sulfur Oleum
OH HO trioxide

32. Concentrated sulphuric acid is a powerful

Thiosulfuric acid, H2S2O3 dehydrating agent due to its strong affinity for
S water. It removes water from a large number of
organic and inorganic compounds.
S conc. H SO
HO C12H22O11 
2 4 12C + 11H2O
O
OH Sucrose Carbon Water

Peroxydisulfuric acid, H2S2O8 33. 2HBr + H2SO4  Br2 + SO2 + H2O

O Hydrobromic Sulphuric Bromine Sulphur Water
O
acid acid dioxide
S S
O O–O O 34. CaF2 + H2SO4  CaSO4 + 2HF
OH OH (Conc.)

129
 

MHT-CET Triumph Chemistry (Hints)

35. I2 + 5Cl2 + 6H2O  2HIO3 + 10HCl 39. 2XeOF4 + SiO2  2XeO2F2 + SiF4
Xenon
Oxidation state of Cl in HCl = –1 dioxydifluoride
Oxidation state of I in HIO3 = +5
40. Mixture of 85 % Ar and 15 % N2 is filled in
36. (A) Structure of XeF6: electric bulb to increase life of filament.

F
F Competitive Thinking
F 2. The abundance of noble gases in dry air is ∼ 1%
Xe
(by volume) with argon as the major constituent.
F F
3. Due to smaller size of fluorine, it shows inter
F electronic repulsion among its electrons. Hence,
electron gain enthalpy of F is less negative than
(B) Structure of XeO3: Cl. The value of electron gain enthalpy becomes
less negative going down the group from Cl.
Thus, chlorine has the highest value of negative
Xe electron gain enthalpy.
O O 4.
O Electron gain F Cl Br I
enthalpy –333 –349 –325 –296
(C) Structure of XeOF4: (kJ mol1)
O The order of the electron gain enthalpies of
F F halogens is Cl > F > Br > I.
Xe Fluorine has unexpectedly low negative value of
electron gain enthalpy due to its small atomic
F F
size.

5. The order of the electron gain enthalpies of

(D) Structure of XeF2:
halogens is Cl > F > Br > I.
F
7. Argon is a monoatomic gas.

Xe 8. Boiling point (in K) of inert gases:

He Ne Ar Kr Xe Rn
F 4.2 27.1 87.2 119.7 165.0 211

10. Thermal stability decreases from H2O to H2Po.

37. XeF4: Square planar
11. All hydrides except H2O possess reducing
F F property as H2O is very stable molecule.
Hdiss(O – H) = 463 kJ mol–1. Therefore, it does
Xe not act as a reducing agent.

F F 13. Among halogens, only chlorine forms the

halous acid like chlorous acid wherein the
chlorine atom is in tripositive oxidation state.
38. XeF6 + H2O  XeOF4 + 2HF O
(P) O
Square pyramidal H Cl

XeF6 + 3H2O  XeO3 + 6HF Chlorous acid

(Q) (Oxidation state of Cl: +3)
Trigonal pyramidal
130
 

Chapter 07: Elements of Groups 16, 17 and 18

14. The acid strength of the halogen oxoacids 27. Interhalogen compounds are more reactive than
increases with the increasing oxidation state of halogens. This is because XX bonds present in
halogen. them are weaker than XX or XX bonds.
Also, the increasing order of charge

delocalization in the anions of oxoacids of 28. MnO2 + 4HCl  MnCl2 + Cl2 + H2O
chlorine is, ClO < ClO 2 < ClO3 < ClO 4 . Manganese Hydrochloric
Manganese Chlorine Water
dichloride (A)
With increase in charge delocalisation, the dioxide acid
stability of the ion increases and the basicity of
the anion decreases. Thus, ClO is the strongest Cl2 + 3F2
573 K
 2ClF3
base and ClO 4 is the weakest base. A weak base Chlorine Fluorine Chlorine trifluoride
(A) (excess) (colourless gas)
has strong conjugate acid and vice versa. Hence,
(B)
HClO (conjugate acid of ClO) is the weakest
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
Uranium
trifluoride hexafluoride monofluoride
order of acid strength is: (D)
(B) (C)
HClO < HClO2 < HClO3 < HClO4.
In the given series of reactions, the gases A, B,
15. SO2, CO2  Acidic oxide
C and D are Cl2, ClF3, UF6 and ClF
BaO  Basic oxide respectively.
N2O  Neutral oxide
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) F F
Potassium Ozone Potassium Iodine Oxygen Br
iodide hydroxide F
F
F
18. Ozone molecule is angular with O  O  O bond
angle as 116.8 ( 117). Both O  O bonds are 32. 1 mol of H2O = 18 g of H2O
identical having bond length 128 pm (i.e., 1.28 Å)
 0.1 mol of H2O = 1.8 g of H2O
[Since, 1 Å = 1010 m and 1 pm = 1012 m].
Molar ratio of XeF6 : H2O = 1 : 1
19. Sulphur dioxide is not a dehydrating agent. 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.
36. Rhombic sulphur and monoclinic sulphur are
2NaOH + Cl2  NaCl + NaOCl polymorphic forms of sulphur, i.e, arrangement
Sodium hydroxide Chlorine Sodium Sodium of molecules is different. However, both the
(Cold and dilute) chloride hypochlorite crystals are made up of S8 molecules.
23. Chlorine reacts with water to form HCl and 37. The valence shell electronic configuration of
HOCl. HOCl gives nascent oxygen which p-block elements is ns2np16, except helium,
results in bleaching action. which has 1s2 configuration. Helium contains
OCl–  [O] + Cl– completed duplet and hence, one molecule of
Hence, the reactive species in chlorine bleach is He consists of only one atom (i.e., it is a
OCl–. monoatomic element).
26. Aqua regia dissolves gold,
38. Generally, acidic oxides are the binary
+5
Au + 4H +
+ NO 
+ 4Cl  compounds of oxygen with nonmetals whereas
3
Gold Nitrate Chloride basic oxides are the binary compounds of
ion ion oxygen with highly electropositive metals.
+2
AuCl4
39. ZnO and Al2O3 are amphoteric oxides.
 + NO + 2H2O
Tetrachlorido- Nitric Water N2O5 is an acidic oxide.
aurate(III) oxide
MgO is a basic oxide.
131
 

MHT-CET Triumph Chemistry (Hints)

40. 42.
Element Nature of oxide Element Type
Calcium Basic (A) Carbon Non-metal
Zinc Amphoteric (B) Neon Noble gas
Carbon Acidic (C) Sodium Alkali metal
Sulphur Acidic (D) Tellurium Metalloid

Hints to Evaluation Test

5. 11. Perchloric acid, HClO4

Compound Oxidation state of xenon Oxidation state of ‘Cl’ = +7
XeOF4 +6
13. Let ‘x’ be the oxidation number of sulphur. S8 is
XeO3 +6 the elemental form of sulphur. Hence, oxidation
XeF6 +6 state is zero.
XeF4 +4 In S2F2, 2x  2 = 0
XeF2 +2  2x = 2
x=1
7. Acidic character of hydrides of group 17
In H2S, 2 + x = 0
elements increases down the group. Thus, HF is
least acidic in nature. x=2

8. Peroxydisulfuric acid, H2S2O8 14. The noble gas which forms maximum number
of compounds is Xe.
O O e.g. XeF2 , XeOF2 . XeF4 , XeOF4 . XeF6 , XeO3 .

S S 18. Most electronegative fluorine shows only –1

O O–O O oxidation state. Chlorine, bromine and iodine
OH OH show –1, +1, +3, +5 and +7 oxidation states.
Chlorine and bromine also exhibit +4 and +6
Thiosulfuric acid, H2S2O3 oxidation states.
S

S
HO
O
OH
Sulfurous acid, H2SO3

S
HO
HO O

Disulfuric acid or pyrosulfuric acid, H2S2O7

O O

S S
O O O
OH HO
9. Acidic oxides: Cl2O7
Amphoteric oxides: Al2O3
Neutral oxides: CO, NO
10. SO2 is highly soluble in water and its solution in
water is called sulfurous acid (H2SO3).

132
 
Textbook Chapter 08: Transition and Inner
Chapter No. 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,  = 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  = 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
133
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MHT-CET Triumph Chemistry (Hints)

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 ()
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
configuration electrons highest for Yb.
Mn2+ 3d5 5 29.
Cu2+ 3d9 1 Outer No. of
2+ 1
Sc 3d 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.
134
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Chapter 08: Transition and Inner
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.
Competitive Thinking
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]4f 5d 6s ; Lu3+  [Xe]4f14
14 1 2 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
configuration electrons
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
3+
Ti 3d1 1 1.73 BM
38. Pre-transition metals do not exhibit ligand field
Co3+ 3d6 4 4.90 BM
effects.
9. Magnetic moment = n(n  2) BM
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
3+
(representative element), Rb is an alkali metal Ti 3d1 1 1.73 BM
and Mo is a transition element. V3+ 3d2 2 2.83 BM
135
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MHT-CET Triumph Chemistry (Hints)

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
 = 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  = n(n  2) BM,
iodide ion is converted into iodate.
Where n = number of unpaired electrons.  
2M nO 4 + H2O + I  2MnO2 + 2OH + IO 3
When n = 2;  = 2(2  2) = 8 = 2.84 BM
 Magnetic moment 2.84 BM is given by Ni2+. 25. In acidic medium:
+ – 2+
M nO 4 + 8H + 5e  Mn + 4H2O
12. Magnetic moment () = n  n  2  BM (i) FeC2O4 ⇒ 1 mol oxalate ion and 1 mol
ferrous ion:
Number Calculated Oxalate ion:
Outer
of value of +
2M nO 4 + 5C 2 O 24  + 16H  2Mn
2+
Ion electronic
unpaired Magnetic
configuration + 8H2O + 10CO2
electrons moment
 2
1 mol C 2 O 4 ≡ mol M nO 4
2
Co3+ 3d6 4 24 BM 5
Cr3+ 3d3 3 15 BM Ferrous ion:
2+ + 2+
Fe3+ 3d5 5 35 BM 2M nO 4 + 10Fe + 16H  2Mn
Ni2+ 3d8 2 + 10Fe3+ + 8H2O
8 BM
3+ 2+
 1 mol Fe2+ ≡ 1 mol M nO 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 C 2 O 24  ≡ 2 mol M nO 4
Mn2+ (3d5) : 5 unpaired electrons 5
Now, 1 mol Fe2(C2O4)3 ≡ 3 mol C 2 O 24 
14. CuSO4 will be absorbing orange-red colour and 6
emits out blue colour.  3 mol C 2 O 24  ≡ mol M nO 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 M nO 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
Ti3+  [Ar] 3d1 = 2161
5 5 5 5
Mn2+  [Ar] 3d5 = 10
Due to absence of unpaired electrons, Sc3+ ion 5
will be colourless. = 2 mol
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Chapter 08: Transition and Inner
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.
Cr2O72 + 14H+ + 6e 2Cr3+ + 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.

Hints to Evaluation Test

5. When H2S gas is passed through acidified 10. In this reaction

K2Cr2O7 solution, it is oxidized to sulphur. MnO4 + 5Fe2+ + 8H+  Mn2+ + 5Fe3+ 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.
137
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Textbook
MHT-CET
Chapter No.Triumph Chemistry (Hints)

09 Coordination Compounds

Hints

Classical Thinking
2. In a complex, metal ion is Lewis acid and ligand is Lewis base.
6.
O O

O=C O O C=O
O=C C=O
H2C CH2 CH2 CH2

N CH2 CH2 N
Ethylenediamine tetraacetate
(EDTA)

7. Ca2+ forms an octahedral complex with just one molecule of EDTA as it has four donor oxygen atoms and
two donor nitrogen atoms in each molecule.
8. Oxalate can bond metal atom through two oxygen atoms
– –
O O
C–C
O O
9. Ammonia, ethylenediamine and water are neutral ligands. Nitrate  NO2  is a negatively charged ligand.
11. Let the oxidation number of Fe be ‘x’. As CN– is a negative ligand, charge on it is –1. Thus, the oxidation
number can be calculated as:
x + 6  (–1) = – 4
 x = +2
12. CO is neutral molecule, hence the oxidation state of central metal atom (Ni) is zero.
14. en is a bidentate ligand. Hence, the coordination number of the central metal ion = 2  number of bidentate
ligands = 2  3 = 6
16. Carnalite is double salt. Its chemical formula is KCl.MgCl2.6H2O.
18. Inner sphere is known as the first sphere or coordination sphere and the outer sphere is known as the second
sphere or the ionization sphere.
19. Secondary valencies and are non ionizable. Number of secondary valencies is equal to the coordination
number. Secondary valencies have a fixed spatial arrangement around the metal ion. Secondary valencies for
a metal ion are satisfied by either by anions or neutral ligands.
21.  [Co(NH3)6]3+ + 3Cl–
[Co(NH3)6]Cl3 

(4 ions)

24. The complex ion carries a net positive charge; hence, a cationic complex. Also, it consists of one type of
ligand only, i.e., H2O. Therefore, it is also a homoleptic complex.

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Chapter 09: 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] and [MA4BC] 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 charge, smaller the
atomic radius, greater will be charge to size ratio and hence, greater 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

139
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MHT-CET Triumph Chemistry (Hints)

46. The reaction for the combustion can be given as 57. 2C2H6(g) + 7O2(g)  4CO2(g) + 6H2O(l) ;
15
C6H5COOH(s) + O2(g)  7CO2(g) + 3H2O(l) rH° = – 3119 kJ
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
2x = – 1574 – 1716 + 3119 = – 171
H = 321.30 +     300  R
1

 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) – Δf H(CO) + Δ f H(O2 ) 

= [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

98
 

Chapter 09: Coordination Compounds

Critical Thinking
1. Ligands, ammonia and chloride are bonded to platinum through coordinate bonds.
3. O O
5 4
O=C O 6 3 O C=O
O=C C=O
1 2
H2C CH2 CH2 CH2

N CH2 CH2 N
Ethylenediamine tetraacetate
(EDTA)
1, 2 are donor N atoms and 3, 4, 5, 6 are donor O atoms.
4. NO 2 is an ambidentate ligand. Hence, either N or O bonds to the central metal atom to form a complex.

6. Let the oxidation state of Fe in be x.

The charge on C2O4 ligands is –2. Thus, the oxidation number can be calculated as:
x + 3(2) = 3
x6=3
x=3
Thus, iron in [Fe(C2O4)3]3 has +3 oxidation state while in K2[Ni(CN)4], K4[Fe(CN)6] and [Cu(NH3)4]2+; the
central metal atom exhibits an oxidation state of +2.
7. The number of donor atoms in the ligand determines the coordination number of metal ion in the complex.
For example, [Co(en)3]3+, wherein, en (ethylenediamine) is a bidentate ligand; hence, total number of donar
atoms is 6. The coordination number of metal ion is 6.
8. Six monodentate ligands are attached to the central metal atom. Hence, the coordination number is 6.
Let the oxidation number of metal be x.
NH3 is neutral molecule, SO4 has charge of –2 and Cl has charge of –1.
 x + 5 (0) + (–2) + (–1) = 0
x = +3
 Coordination number is 6 and oxidation number is +3.
9. [E(en)2(C2O4)]NO2
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 ‘E’ in the complex be ‘x’.
The charges on complex ion, en and C2O42 are +1, 0 and 2, respectively.
Hence, x + 0  2 = +1
x=3
10. In the complex ion [Co(III)(NH3)5Cl]x, charge on the complex ion is
x = 3 + (0  5) + (– 1)
x=3–1=2
Hence, it will combine with that species which has – 2 charge to produce a neutral complex salt. So, it will
combine with 2Cl– to produce [Co(NH3)5Cl]Cl2 complex.
11. Mohr’s salt (FeSO4.(NH4)2SO4.6H2O) is a double salt.
12. The metal ion exercises primary valences towards the negative groups to satisfy its normal charge by the
formation of simple salts. It exercises secondary valences towards the negative ions, neutral molecules or
both to form a coordination sphere.
13. Cl– ions are present in ionization sphere and hence it will get ionized when dissolved in water while the rest
of coordination sphere remains intact. Hence, the solution will give the test of Cl– ions.
141
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MHT-CET Triumph Chemistry (Hints)

14. According to Werner’s theory, most metals exhibit two types of valences:
i. Primary valence ii. Secondary valence
15. Since the isomer gives one mole of AgCl, the isomer will contain one ionizable chlorine atom. So, among
the given options, (C) is the answer.
16. The complex [Co(NH3)5Cl]Cl2 ionizes to give a complex cation and two chloride ions, i.e., total of three
ions.
[Co(NH3)5Cl]Cl2  [Co(NH3)5Cl]2+ + 2Cl–
Ionizable chloride ions react with AgNO3 to give 2 moles of AgCl.
2Cl– + 2AgNO3  2AgCl(s)
28. The complex ion is the anion and bears four negative charges. Thus, iron atom must have an oxidation
number of +2. Hence, the compound is potassium hexacyanoferrate (II) and is commonly called as
potassium ferrocyanide.
30. Atomic number of Pd (Z) = 46
Oxidation state of Pd (X) = 4
Number of electrons donated by ligands (Y) = 12
EAN of Pd 4+ = 46 – 4 + 12
= 54
31. Atomic number of Fe = 26
Each CO ligand donates 2 electrons.
Electrons from xCO ligand is 2x
Charge on the complex = 0
EAN of the central metal ion = 36
EAN = Atomic number of metal (Z) – Number of electrons lost by metal to form the ion (X) + Number of
electrons donated by ligands (Y).
 36 = 26 – 0 + 2x
 x=5
32. In complexes with coordination number 4, geometrical isomerism is shown by complex with formula
MA2B2 and MA2BC. Hence, [Pt(NH3)2(H2O)2]+2 and [Co(NH3)2(H2O)Cl]Cl will show geometrical
isomerism.
In octahedral complex with coordination number 6, complexes of the type M(AA)2B2 show geometrical
isomerism. So, [Co(en)2Cl2]Cl will show geometrical isomerism.
33. Geometric isomers of [PtCl2(en)2]2+:
2+ 2+
Cl Cl
Cl
en Pt en Pt en
en
Cl
cis isomer trans isomer

35. Optical isomers of [Co(en)2(NH3)2]3+ are

en en
NH3 NH3
Co Co
NH3 NH3
en en
d-form l-form

38. The complex is an octahedral complex of the type [M(AA)2ab]n  and hence can exhibit cis-trans isomerism.
SCN and NO2 being ambidentate ligands, enable the complex to show linkage isomerism. The complex can
show ionization isomerism with [Co(en)2(SCN)Br]NO2 and [Co(en)2Br(NO2)]SCN.

142
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Chapter 09: Coordination Compounds

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.
143
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Chapter 04: Chemical Thermodynamics

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 = H(reactant bonds) – 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 = fH(products) – 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

101
 

Chapter 09: Coordination Compounds

62. The formula of the complex is [M(H2O)4Cl2]Cl.
0.1  V = 0.01  200
 V = 20 mL

Competitive Thinking

x 
1.  AuCl 4 
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

145
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MHT-CET Triumph Chemistry (Hints)

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

146
 

Chapter 09: Coordination Compounds

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 e g ) 4Dq(3)  6Dq(1) = 6 Dq
[Fe(H2O)6]3+ 3d5 (t 32g e g2 ) 4Dq(3)  6Dq(2) = 0 Dq
2+
[Co(H2O)6] 3d7 (t 52g e g2 ) 4Dq(5)  6Dq(2) = 8 Dq
3+
[Co(H2O)6] 3d6 (t 42g e g2 ) 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.
147
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MHT-CET Triumph Chemistry (Hints)

For the complexes [Co(CN)6]3 and [CoF6]3, the central metal ion is Co3+ with outer electronic
configuration 3d6. CN is a strong field ligand while F is a weak field ligand. Therefore, [Co(CN)6]3 is
diamagnetic (no unpaired electrons) while [CoF6]3 has magnetic moment of four unpaired electrons.
Thus, among the given complexes, [Fe(H2O)6]3+ has the highest magnetic moment value.
34. Magnetic moment is obtained from number of unpaired electrons. Therefore, complexes having same
number of unpaired electrons will have same magnetic moment. By considering H2O and Cl to be weak
field ligands:
Complex Central metal ion No. of unpaired electrons
[Cr(H2O)6]2+ Cr2+ (3d4) 4
[CoCl4]2 Co2+ (3d7) 3
[Fe(H2O)6]2+ Fe2+ (3d6) 4
[Mn(H2O)6]2+ Mn2+ (3d5) 5
[Cr(H2O)6]2+ and [Fe(H2O)6]2+ have the same magnetic moment.
35. In tetrahedral complexes, the five degenerate d orbitals of metal split into two levels, i.e., lower energy level, eg
and upper energy level, t2g. The eg contains dx2 y2 and dz2 orbitals while t2g contains dxy, dyz and dxz orbitals.
 The correct order for energy of d orbital splitting in [Ni(Cl)4]2– is,
d xy  d yz  d zx > d d
x 2  y2 z2

In  TiF6  , Ti4+ : 3d0, colourless; as there is no unpaired electron

2
37.
In  CoF6  , Co3+ : 3d6, coloured; as there are 4 unpaired electrons
3

In Cu2Cl2, Cu+ : 3d10, colourless; as there is no unpaired electron

In  NiCl4  , Ni2+ : 3d8, coloured; as there are 2 unpaired electrons
2

Thus, among the given options, two species (  TiF6 

2
and Cu2Cl2) are colourless.

38. The strength of ligands is in order en > NH3 > H2O. Greater the strength of ligand, larger is the crystal field
splitting energy; therefore, the wavelength of absorption will be
[Co(en)3]3+ < [Co(NH3)6]3+ < [Co(H2O)6]3+
39. The increasing order of energies of light is
red < yellow < green < blue.
Higher the energy of light absorbed, higher is the ligand strength.
Hence, the increasing order of ligand strength is L1 < L3 < L2 < L4
40. The compound cis-[PtCl2(NH3)2] is also known as cisplatin.
42.
H2O
 H
H2O  Cu2+ O H
O
 H
SO 24  H
. H2O

Covalent bond

Ionic Coordinate Hydrogen

bond covalent bond bond

Weight of complex 2.675

43. Number of moles of complex = = = 0.01 mol
molar mass of complex 267.5
Molar mass of AgCl = 108 + 35.5 = 143.5 g.
Weight of AgCl 4.78
Number of moles of AgCl = = = 0.03 mol
molar massof AgCl 143.5
This shows that three Cl ions are ionizable in the complex.

148
 

Chapter 09: Coordination Compounds

1.2  1022
44. Mol of Cl– ions = = 0.02 mol
6.022  1023
100  0.1
Mol of COCl3.6H2O = = 0.01 mol
1000
0.02
1 mole complex produces =
0.01
= 2 mol Cl– ions
–
There are two Cl ions as primary valence in the given complex. Hence, the formula of the given complex
will be [Co(H2O)5Cl]Cl2.H2O.
45. A mixture of three parts of concentrated hydrochloric acid and one part of concentrated HNO3 is known as
aqua regia.
Gold (Au) dissolves in aqua regia to form the complex ion, [AuCl4].
Au + 4H+ + NO 3 + 4Cl   AuCl4  + NO + 2H2O


Gold Nitrate Chloride Tetrachlorido Nitric Water

ion ion aurate (III) oxide
ion

Hints to Evaluation Test

9. The magnitude of o (CFSE in octahedral field) will be minimum for [CoF6]3− as F− is the weakest ligand
among the other given ligands.
11. The complex [Co(NH3)5 Cl]Cl2 contains in all three chlorine atoms.
Dissociation of [Co(NH3)5 Cl]Cl2 gives two chloride ions in the solution.
[Co(NH3)5Cl]Cl2  [Co(NH3)5Cl]2+ + 2Cl–
2
 fraction of Cl– ion precipitated by AgNO3 solution =
3

13. Cl + en +
Cl
en Co en Co
Cl
en
Cl
Trans-[CoCl2(en)2]+ Cis-[CoCl2(en)2]+
Optically inactive Optically active
15. Configuration after [NiCl4]2– complex formation is
3d 4s 4p

        

sp3

19.
a a
a b b a
M M
M
a b b a
a ba
a
Cis-d-form Cis-l-form
Mirror
Trans form of M(aa)2b2 does not show optical isomerism.

149
 
Textbook
Chapter No. Chapter 5: Electrochemistry

05 Electrochemistry

Hints

 Moles of copper deposited on passing of

Classical Thinking 9650 coulombs
9650
= = 0.05 moles
1000k 2  96500
9. Molar conductivity,  =
C
24. At cathode:
1000  6.3  102
= Ni2+ + 2e–  Ni
0.1
 2F will deposit 1 mole of Ni.
= 630 ohm1 cm2 mol1 0.1  1
 0.1 F will deposit = = 0.05 mol Ni
1 2
10. Molar conductivity  ,
Molarity
25. Fe3+ + 3e  Fe
Lower the concentration, higher will be molar  3 F will deposit 1 mole (i.e., 56 g) of Fe
conductivity. So, molar conductivity will be 0.6  56
maximum for 0.001 M HCl solution. So, 0.6 F will deposit = = 11.2 g
3
11. The expression for the variation of the molar
26. 
Ag (aq)  e   Ag(s)
conductivity () of strong electrolytes with
concentration (c) is  = 0  a C 1 Faraday i.e., 96500 C will deposit 108 g of
where ‘a’ is constant and ‘0’ is the molar Ag.
conductivity at zero concentration or infinite  9650 C will deposit 10.8 g of Ag
dilution. 27. Cu2+ + 2e  Cu
14. 0 (NaBr) = 0 (NaCl) + 0 (KBr) – 0 (KCl) To deposit 1 mole of Cu, 2 F i.e.,
= 126 + 152  150 = 128 S cm2 mol1 2  96500 coulombs of electricity is required.
 Coulombs of electricity is required
 50 = 2  96500 C = 193000 C
15. α= c = = 0.2
0 250 = 1.93  105 C
 = 0.2  100 = 20 % 28. Salt bridge prevents the mixing of the two
16. Cell constant = k  R solutions in the half cells.
= 0.002765  400 = 1.106 m1 30. Zn(s) + 2Ag  (1 M)  Zn 2  (1 M) + 2Ag(s)
21. The charge of one mole electrons is The two half cell reactions are:
96500 coulombs (C). It is referred to as one Zn(s)  Zn 2  (1 M) + 2e
faraday (1 F). [ Ag  (1 M) + e  Ag(s)]  2
3+
22. The balanced equation for the reduction of Cr Therefore, Zn is oxidised and acts as negative
to Cr is Cr3aq  + 3e–  Cr(s) electrode (anode) whereas, Ag+ ions are reduced
The equation shows that 1 mole of Cr3+ is and acts as positive electrode (cathode).
reduced to Cr by 3 moles of electrons. Hence the cell representation is
For reduction of 5 moles of Cr3+, 15 moles of Zn(s) | Zn2+ (1 M) || Ag+ (1 M) | Ag(s)
electrons will be required. 31. The electrode potential and the cell potential
23. In CuSO4 solution, the reduction reaction of Cu depend on concentrations of solutions, pressures
can be given as, of gases and the temperature.
Cu2+ + 2e  Cu 32. According to IUPAC convention, standard
 To deposit 1 mole of Cu, 2 F i.e., potential of an electrode is taken as the standard
2  96500 coulombs of electricity is required. reduction potential.
105
 

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.
151
 

MHT-CET Triumph Chemistry (Hints)

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. AgCN + R  X 
 RNC + AgX 


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

152
 

Chapter 10: Halogen Derivatives

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.
 HX
71. CnH2n + 1X   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
2-Methylbut-1-ene (20 %)

Br
CH3  CH = CH  CH3
alc. KOH
75. CH3  CH  CH2  CH3 But-2-ene (major)
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.

153
 

MHT-CET Triumph Chemistry (Hints)

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.
 +2  + 
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

154
 

Chapter 05: Electrochemistry

13. When molten metal chloride undergoes 19. Eocell  Eocathode  Eoanode = EoCo  EoMn
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  Cl 2 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 
2 PCl2
= 96.15 g mol1
2
14. 2H+ + 2e  H2 0.0592 Cl   Mg 2  
log10   
o
= Ecell –
molesof product 1 2 1
(mole ratio)1 = 
=
molesof e 2 o 0.0592
= Ecell – log10 [Cl–]2 [Mg2+]
Ca2+ + 2e  Ca 2
molesof product 1
(mole ratio)2 = =
molesof e 2 21. Eocell  Eocathode  Eoanode
W1 W2
= EAg  ESn  0.800V  0.136 V = 0.936 V
o o

 mole ratio 1  M1  mole ratio 2  M 2
W1 2 1 The cell potential is given by
  0.0592 V [Sn 2 ]
W2 40 20 Ecell = Eocell  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 = Eoel  log
=  mole ratio Hg 2  :  mole ratio Hg 2  : n [Zn 2  ]
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 2
Zn(s) + Cu (aq)  Zn (aq)
2
 Cu (s)
cathode (+) at extreme right.
At 298 K,
2 2
18. Cu (s) | Cu (aq) 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.

107
 

MHT-CET Triumph Chemistry (Hints)

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
 CH3 – CH – CH2Br
Isobutylene Isobutyl bromide

19. In presence of peroxide, Anti-Markovnikov’s product is the major product formed.

Ph–CH = CH2 + HBr  H2 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.

156
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Chapter 10: Halogen Derivatives

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

157
 

MHT-CET Triumph Chemistry (Hints)

 At cathode; Cu2+ + 2e  Cu W1 18

2 moles of electron give 1 mole of Cu. 1
2
 58.5 13  27
0.01
 0.01 mole of electron will give = = 0.005 W1 
18 58.5
  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
Au 3  |Au
of mass of Al, Ag, Mg deposited will be
1 1 1 E = 0.15 V
Sn 4  |Sn 2 
: : =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
W1 W2
2Ag  2Ag+ + 2e (Oxidation at anode)
 Zn+2 + 2e  Zn (Reduction at cathode)
 mole ratio 1  M1  mole ratio 2  M 2
8 W2
 2Ag + Zn+2  2Ag+ + Zn
1
 32 1  108
4 (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
Ecell =  1.562  log10
Aluminium chloride : AlCl3 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  M1  mole ratio 2  M 2 = 1.562 + 0.0296 =  1.5324 V
110
 

Chapter 10: Halogen Derivatives

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  electrons of benzene
due to which C – Cl bond acquires double bond character. Hence, reactivity decreases.
159
 

MHT-CET Triumph Chemistry (Hints)

Br Br Br
CH3
anhydrous AlCl3
62. 2 + 2CH3I  + + 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.

Competitive Thinking
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.

160
 

Chapter 10: Halogen Derivatives

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) (B)
 
HCl
  
HCl


1-Chloro-1-methylcyclohexane 1-Chloro-1-methylcyclohexane

161
 

Chapter 05: Electrochemistry

Hints to Evaluation Test

l 1.5cm  E  E
2. Cell constant = = = 2.0 cm–1 Zn 2  / Zn Mg 2  / Mg
a 0.75cm 2
Zn cannot reduce Mg2+. Mg and Zn will reduce
5. The balanced equation for the reduction of Zn2+ Fe but not oxidise Fe since their E values are
to Zn is lesser than Fe.
–
Zn 2aq  + 2e  Zn(s) 13. Electrolytic conductivity of a solution decreases
The equation shows that 1 mole of Zn is 2+ with decrease in concentration of solution.
reduced to Zn by 2 moles of electrons (i.e., 2 F). 17. Cell constant = k  R
Therefore, for 3 moles of Zn2+, 6 F of electricity = 0.00141 Ω–1 cm–1 × 604 Ω
will be required. = 0.8515 cm–1
6. More negative the reduction potential, higher 18. Zn + Fe2+  Zn2+ + Fe
will be the reducing property. Since Zn has  Zn 2  
0.0592
more negative reduction potential than the other E = E  log10
given options, Zn will be the strongest reducing 2  Fe 2  
agent. 0.0592  Zn 2  
E = E + log10
Cell constant 0.5 2  Fe 2  
9. k= = = 1  102
R 50 0.0592 102
1000  = 0.2905 + log10 3
 = 2 10
C = 0.32 V
1000  1  102 At equilibrium,
 = = 10 ohm1 cm2 mol–1
1 0.0592
 E = log10 K = 0.0296 log10 K
2
10. Oxidation state of X and Y are X3+ and Y2+
0.32
respectively.  log10 K =
0.0296
X3+ + 3e–  X 0.32
molesof product 1  K = 10 0.0296
(mole ratio)1 = =
molesof e 3
19. Oxidation at anode:
Y2+ + 2e–  Y Cd(s)  Cd2+ + 2e–
molesof product 1 Reduction at cathode:
(mole ratio)1 = =
molesof e 
2 Sn2+ + 2e–  Sn(s)
M1 1 Eocell  Eocathode  Eoanode
 (Given)
M2 2
Eocell = ESn
o
 ECd
o
= – 0.136 – (–0.403) = 0.267 V.
W1 W2
 ΔG = – nF Ecell
o
 mole ratio 1  M1  mole ratio 2  M 2
n=2
W1  mole ratio 1  M1 13 1 1
    ΔG = 2 mole   96500 C / mol e   0.267 V
W2  mole ratio 2  M 2 12 2 3
= – 51531 V C = – 51531 J = – 51.53 kJ

11. Eocell  Eocathode  Eoanode 20. Cu 2aq  + 2e–  Cu(s)

Eocell  EoAu  EoCd = (1.500 V) – (–0.403 V) 1 mol

Mole ratio =
= 1.903 V 2 mol e
I  A  × t s 
W=  mole ratio × MCu
12. E
Zn 2  / Zn
= 0.76 V 96500  C / mole  
E
Mg 2  / Mg
= 2.37 V = 2 × 965 × 60 × 1  63.5 = 38.1 g
96500 2
E 2
Fe / Fe
= 0.44 V
E  E  E 2
Mg 2  / Mg Zn 2  / Zn Fe / Fe
2+
 Zn will reduce Fe
113
 

Chapter 10: Halogen Derivatives

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)

163
 

MHT-CET Triumph Chemistry (Hints)

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

164
 

Chapter 10: Halogen Derivatives

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

41. 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.
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  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).

Hints to Evaluation Test

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)

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MHT-CET Triumph Chemistry (Hints)

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

C2 H5  OH
+ NaCN  

Br Br
4-Bromobenzyl 4-Bromobenzyl
chloride cyanide

+ −
NH2 N2Cl Br

NaNO2  HCl
12. 
280 K
 
CuBr / HBr
Sandmeyers
 + N2
reaction

Benzene Bromobenzene
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)

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Chapter 10: Halogen Derivatives

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.
21. 
CH3CH2OH + SOCl2   C2H5Cl + HCl  + SO2
Ethyl alcohol Thionyl Ethyl Sulphur
chloride chloride dioxide
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.

167
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Textbook
MHT-CET
Chapter No.Triumph Chemistry (Hints)

11 Alcohols, Phenols and Ethers

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

168
 

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 

H2SO4
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.
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MHT-CET Triumph Chemistry (Hints)

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
Ketone R3 R3 X
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

+ O2  naphthenate 

dil.HCl
 + CH3 – C – CH3
423 K
Acetone
Cumene Cumene Phenol
(Isopropylbenzene) hydroperoxide

SO3Na OH

 i NaOH
52. 
 
 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 2 SO 4
C6H5COOC2H5
Benzoic acid Ethyl alcohol Ethyl benzoate

170
 

Chapter 11: Alcohols, Phenols and Ethers

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).
CH3  CH = CH  CH3
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

171
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MHT-CET Triumph Chemistry (Hints)


85. Nitration reaction of phenol is aromatic electrophilic substitution reaction. It involves attack of NO 2 , an
electrophile. – NO2 replaces H  atoms of phenol ring. Hence, it is an electrophilic substitution.

OH
O2N NO2

87. C6H5OH 

conc. HNO3

conc. H 2SO 4
Phenol
NO2
Picric acid (2,4,6-Trinitrophenol)

88. Phenol does not react with dilute H2SO4. It reacts only with conc. H2SO4. The products depend on the
temperature at which the reaction is carried out. This reaction takes place at atmospheric pressure.
OH
SO3H

OH 
293 K

o-Phenolsulfonic acid
H2SO4
OH

Phenol

373 K


SO3H
p-Phenolsulfonic acid

89. Reimer-Tiemann reaction involves the formation of salicylaldehyde from phenol.

OH ONa OH
CHO CHO
+ CHCl3 
 NaOH,340K
dil. HCl
 NaCl

Phenol Salicylaldehyde

91. OH  CrO3

or Na 2Cr2O7 /H2SO4
 O O

Phenol p-Benzoquinone

OH OH

92. + 3H2 Ni

433 K


Phenol Cyclohexanol

OH


93. + Zn   + ZnO

Phenol Benzene

94. Dehydration of alcohols gives ethers.

95. At 140 °C or 413 K, C2H5OH on heating with conc. H2SO4 gives diethyl ether.
C2H5OH 
conc. H 2SO 4
 CH3CH2 – O – CH2CH3
140  C
Ethanol Diethyl ether

172
 

Chapter 11: Alcohols, Phenols and Ethers

96. C2H5Br + C2H5ONa 
 NaBr
 C2H5 O  C2H5
Ethyl Sodium Diethyl ether
bromide ethoxide

98. CH3ONa + Br  CH3  CH3  O  CH3 + NaBr

Sodium Dimethyl ether
methoxide (Symmetrical ether)

CH3 CH3

CH3  C  ONa + CH3Br  CH3  C  OCH3 + NaBr

CH3 CH3
Sodium tert-butyl methyl ether
tert-butoxide (Unsymmetrical ether)

OH ONa OCH3

99. 
NaOH
 
CH 3 I
 + NaI

Phenol Sodium Anisole

phenoxide

100. In the Williamson’s synthesis, alkoxide/phenoxide ion acts as the nucleophile.

C2H5 – Cl + Na+O– CH – CH3  C2H5 – O – CH – CH3 + NaCl

Ethyl chloride
CH3 CH3
Sodium Ethyl isopropyl
isopropoxide ether

101. The O-atom in ether contains two lone pairs of electrons.

103. CH3 – O – CH3 + H2O 

dil.H2SO4

 2CH3 – OH
Methoxymethane Methanol

104. R  O  R + H2O 

dil.H 2SO4
 , pressure
 R  OH + R OH
Mixed
ether
Two different alcohols

106. CH3OC2H5 + HI 

hot
CH3I + C2H5OH
Ethyl methyl Methyl iodide Ethyl alcohol
ether

With hot conc. HI, ethers give an alkyl iodide and alcohol. The iodide is usually formed with the smaller
alkyl group. The bigger alkyl group forms the alcohol.

107. Since A and B are same, the two alkyl groups in the reactant ether must be same.
e.g. CH3  O  CH3  hot HI
 2CH3I + H2O
Simple ether A and B


108. CH3 – O – CH3 + 2HI   2CH3I + H2O
Dimethyl Methyl
ether iodide

110. (CH3)3C – O – CH3+ HI 

Hot
(CH3)3C – I + CH3 – OH
tert-Butyl methyl tert-Butyl Methyl
ether iodide alcohol

173
 

MHT-CET Triumph Chemistry (Hints)

113. Methyl phenyl ether (anisole) undergoes bromination with bromine in acetic acid to form p-bromoanisole
(major product) and o-bromoanisole (minor product).
OCH3 OCH3 OCH3
Br

Br2 / CH 3 COOH
+

Methyl phenyl Br o-Bromoanisole

ether (Anisole)
p-Bromoanisole

OCH3 OCH3 OCH3

NO2
conc.HNO3  conc.H 2SO 4
114.   +

Anisole NO2
4-Nitroanisole 2-Nitroanisole
(major) (minor)

115. Ethyl alcohol is used as an antifreeze for automobile radiators because it lowers down the melting point of
water.

121. H2C = CH – OH
(Ethenol)

O OH

122. C6H5 – C – CH3 

i.LiAlH 4

 C6H5 – CH – CH3
ii.H
Acetophenone Secondary alcohol

Critical Thinking
3. Glycols are dihydric alcohols (having two hydroxyl groups). Ethylene glycol is the first member of this
series.
CH2OH
|
CH2OH
Ethylene glycol

4. (I) 1 1 (II) 1 1 (III) 1 1

CH2 CH  CH2 HO  CH2 CH2 OH CH3 CH2 CH2 OH
Ethylene glycol n-Propyl alcohol
OH OH OH (Two 1 carbon atoms, but only one 1
Glycerol alcoholic group)

6. In case of tertiary alcohols, (OH) group should be attached to tertiary carbon atom.
(A) CH3CH2  CH  CH2  CH3 (B) CH2  CH  CH2
| | | |
OH OH OH OH
Pentan-3-ol (Secondary alcohol) Propane-1,2,3-triol (Trihydric alcohol)

CH3 OH CH3 CH3

| | | |
(C) CH3  C  CH2  CH3 (D) CH3 – CH2 – CH – CH – CH – CH3
| 4,5-Dimethylhexan-3-ol (Secondary alcohol)
OH
2-Methylbutan-2-ol (Tertiary alcohol)

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Chapter 11: Alcohols, Phenols and Ethers

7. In allylic and benzylic alcohols, the  OH group is attached to sp3 hybridized carbon atom while in vinylic
alcohols, the OH group is attached to sp2 hybridised carbon atom.
10. Anisole (C6H5 – O – CH3) is an aromatic ether as well as mixed ether.
11. An alcohol contains –OH functional group. Since, (B), (C) and (D) does not have an –OH group, they cannot
be alcohols. So, correct answer is (A).
12. The structure of crotonyl alcohol is H3CCH = CHCH2OH. Hence, its IUPAC name is but-2-en-1-ol.
16. The structure of o-cresol is OH
CH3

It contains phenolic –OH group.

17. The smaller alkyl group along with oxygen atom is named as alkoxy group.
22. 1 2 3 4 5
CH3 CH2 CH  CH2 CH3

O  CH2 CH2 CH3

3-Propoxypentane

23. CH2Br CH2 – OH

+ 2NaOH(aq) 
Hydrolysis
 + 2NaBr
CH2Br CH2 – OH
1,2-Dibromoethane Ethylene glycol

24. Except ethene, all alkenes on acid catalyzed hydration gives secondary or tertiary alcohols. Ethene gives
ethanol (primary alcohol).

OH
B   6
H 2 O2
25. 6   2
B2 H 6

THF OH
(P) 3 (Q)
26. Alkene  Follows Antimarkownikoff’s rule to form alcohol
i. Hydroboration
ii. Oxidation

Alkene 
Acid catalysed
hydration
 Follows Markownikoff’s rule to form alcohol

O
27. (A) i. LiAlH
CH3 CH2 C  OH 
 
4
ii. H3O
CH3 CH2 CH2 OH
Propanoic acid Propan-1-ol
(primary alcohol)
H
i. LiAlH
(B) CH3 CH2 C = O 
 
4
ii. H3O
CH3 CH2 CH2  OH
Propanal Propan-1-ol
(primary alcohol)

CH3 O CH3
i. LiAlH
(C) CH3 CH  C  O  H 
ii. H O+
4
 CH3 CH  CH2 OH
3
2-Methylpropanoic 2-Methylpropan-1-ol
acid (primary alcohol)

CH3 CH3
i. LiAlH
(D) CH3 C = O 
 
4
CH3 C  OH
ii. H3O
Propan-2-one
H
Propan-2-ol
(secondary alcohol)

175
 

MHT-CET Triumph Chemistry (Hints)

28. LiAlH4 is a strong reducing agent, it will reduce both CHO as well as – COO– group.
29. LiAlH4 selectively reduces the functional group, without reducing the carbon-carbon double bond.
30. (A) CH3COOC2H5  H 2 / Ni
 CH3COOH + C2H5OH
(B) CH3COOH 
(i) LiAlH 4
(ii) H O 
 CH3CH2OH
3

(C) CH3COCH3 

(i) LiAlH 4
(ii) H O 
 CH3CHOHCH3
3

(D) CH3CHO + H2 
Ni
 CH3CH2OH

H  I
31. C =O + C2H5MgI 
Dry
ether
 CH2 O MgI 
H
H  OH
 C2H5 CH2 OH or C3H7OH + Mg
H Ethyl Propan-1-ol OH
Formaldehyde magnesium C2H5
iodide

CH3 CH3 CH3

I
32. CH3 C = O + CH3 Mg  I 
dry ether
 CH3 C  OMgI 
H2O
 CH3 C  OH + Mg
OH
Propanone CH3 CH3
2-Methylpropan-2-ol

33. Ketone gives tertiary alcohol on treatment with Grignard reagent.

R R R OH
C = O + RMgX  R C  OMgX 
RH2O C  OH + Mg
R Grignard R R X
Ketone reagent Tertiary alcohol

+
34. + CH3MgBr 
Dry ether
 [CH3 – CH2 – CH2 – O – MgBr] 
H3O
 CH3 – CH2 – CH2 – OH + Mg(Br)OH
O
Propan-1-ol
Ethylene oxide
(Epoxide)
– + –+
SO3H SO3Na ONa OH

36. 
NaOH
 
NaOH
523 K
 
dil. HCl

Benzene (A) (B) Phenol

sulfonic (C)
acid

37. As compared to alkanes, alcohols have high boiling points. This is because in alcohols, there is inter-
molecular H-bonding leading to association of a large number of molecules. Hence, the boiling point of
n-pentane (B) is the least. Among isomeric alcohols, boiling point depends upon the molecular structure.
Highly branched structures have less efficient packing of molecules which causes the boiling points to
decrease. Hence, the more branched an alcohol, the lower is its boiling point.
38. Increase in the number of –OH group increases intermolecular hydrogen bonding; hence the boiling point
increases. Since, IV does not have any –OH group, it should have the least boiling point. Hence, (C), is the
possible answer.
40. As the size of the alkyl group (or molecular mass) increases, the solubility decreases.
42. Alcohols are soluble in Lucas reagent but the product alkyl chloride is not.
43. Cl  CH2 CH2 O H+; Negative charge on oxygen is dispersed and thus conjugate base is more
stable compared to the conjugate base of ethanol.
176
 

Chapter 11: Alcohols, Phenols and Ethers

44. –OCH3 shows +R effect, which decreases the stability of conjugate base of phenol, i.e., phenoxide ion.
Whereas –Cl and –NO2 group shows electron withdrawing effects, i.e., –I and –R respectively and stabilizes
the phenoxide ion thereby increasing the acidity of phenol.

O O
45. R–C + C2H5OH   R – C
pyridine
+ HCl
Cl OC2H5
Acid chloride Ethanol Ester
O
H
(R – CO)2O + C2H5OH  R  C  OC2H5 + RCOOH
Acid anhydride Ethanol Ester

ROH + HCl   RCl + H2O

2 ZnCl
46.
3ROH + PCl5 R–Cl + POCl3 + HCl

ROH + SOCl2 
reflux
 RCl + HCl  + SO2

47. Alcohols react with concentrated HCl in presence of ZnCl2 (Lucas reagent) to form alkyl halides.
R – OH + HCl 
ZnCl2
anhydrous
 R – Cl + H2O
Alkyl halide
This reaction proceeds through the formation of carbocation. More stable the carbocation greater is the order
of reactivity. Benzyl alcohol forms the benzyl cation which is stabilised by resonance. The presence of
electronegative F in the chain destabilizes the carbocation. Closer the electronegative atom to the carbon
with positive charge, more unstable the carbocation. Hence, stability of cation formed is in the order,
(iv) > (iii) > (ii) > (i).

H2C CH2
O – + – +
48. CH3CHOH 
PBr3
 CH3CHBr 
Mg
ether
 CH3CH Mg Br CH3CHCH2CH2OMgBr

CH3 CH3 CH3 CH3

(I) (II) (III) H3O+

HO – Mg – Br + CH3CHCH2CH2OH
CH3
(IV)
49. In the reaction carbocation formed is primary, which gets converted to tertiary which is more stable;

Hence, the product formed is CH3

50. HO CH3 CH3 CH3 CH3

B
B2 H6 
HO

H 2 SO 4
   
H 2 O2 /OH

51. Tertiary alcohols are not easily oxidised. On oxidation with strong oxidising agents at high temperature tertiary
alcohol undergoes breaking of C-C bonds and gives a mixture of carboxylic acids. These acids contain less
number of carbon atoms than the starting tertiary alcohol.
52. Reagent (A) should be conc. H2SO4 followed by hydrolysis as the reaction is addition of water molecule.
Reagent (B) should be an oxidising agent as the reaction is oxidation reaction.
C5H10 
conc. H 2 SO 4 ,H 2 O
Hydration
 C5H11OH 
CrO3
 CH3(CH2)3CHO

177
 

MHT-CET Triumph Chemistry (Hints)

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
log10
100
= 0.03466 min1  2t1/2 = 50 min
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 =
ks 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

122
 

Chapter 06: Chemical Kinetics

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.
123
 

MHT-CET Triumph Chemistry (Hints)

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

74. H3C  CH  O  CH  CH3 + H2O 

dil.H2SO4

 2CH3 CH  CH3
2-Isopropoxypropane Propan-2-ol

OCH3 OCH3
Br2 in CH3 COOH
75.  

Anisole
Br
p-Bromoanisole
(Major product)

OH O CH3
77. CH3 CH  CH3 
K 2 Cr2 O7
dil.H2SO4
 CH3 C  CH3 
CH3 MgI
H2O
 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.

 CH3CN 
H3O
80. CH3Br 
alc.KCN
 CH3COOH 
LiAlH 4
CH3CH2OH

CH3CH2CH2OH   CH3CH = CH2   CH3 – C  CH

conc. H 2SO 4
81. 160 180  C
Br2
CH3 – CH – CH2 
Alc . KOH

(X) Propyne
Br Br
(Z)
(Y)

OH OH OH
COONa COOH OCOCH3
H+ / H2O
82. i. NaOH
ii. CO 2 /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.
180
 

Chapter 11: Alcohols, Phenols and Ethers

Competitive Thinking
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

H3C  C = CH2 + H2O 
H
 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 / H2O or H3O

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 H2O
 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

 CH3 CH  CH3
(i) CH3MgBr /dry ether
CH3CHO 
(ii) H+ /H O
2
Acetaldehyde Propan-2-ol
(2 alcohol)

181
 

MHT-CET Triumph Chemistry (Hints)

8. H3C CH3 H3C CH3
CH C–O–O–H OH
H3C CH3


O2
 H
H
2O
 +
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 CO O
20. 
3 2
Conc.H2SO4
 + 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.
182
 
Textbook
Std. XII:No.
Chapter Triumph Chemistry

07 Elements of Groups 16, 17 and 18

Hints

22. The size of F atom is smaller than Cl atom. As a

Classical Thinking result, there are strong inter electronic
repulsions in the relatively small 2p orbitals of
4. Copper pyrites formula: CuFeS2 fluorine and therefore, the incoming electron
(Sulfide ion S2–) does not experience much attraction. Thus,
fluorine has less negative electron gain enthalpy
Gypsum formula: than chlorine. Therefore, the correct decreasing
CaSO4.2H2O order of magnitude of electron gain enthalpy is
Epsom salt formula: (Sulfate ion SO24  ) given as, Cl > F > Br > I.
MgSO4.7H2O 23. The ionisation enthalpy of chlorine is greater
Baryte formula: than iodine as ionisation enthalpy decreases
BaSO4 down the group due to increase in the atomic
size.
5. Galena (PbS); Zinc blende (ZnS)
24. The ionisation enthalpy decreases down the
7. Halogens are very reactive due to high group due to increase in the atomic size.
electronegativities. 25. Argon is a group 18 element (noble gas). It has
9. Radon is a decay product of radium (226Ra). no tendency to accept electrons because of the
stable electronic configuration and thus have
12. 18Ar: [Ne] 3s2 3p6 ; 16S:[Ne] 3s2 3p4 large positive electron gain enthalpy.
2 5 10 2 4
17Cl: [Ne] 3s 3p ; 34Se: [Ar] 3d 4s 4p
27. Metallic character increases down the group
13. Across a period, atomic and ionic radii decrease thus, polonium is a metal whereas, sulfur is a
because atomic number increases with nonmetal and selenium, tellurium are
consequent increase in effective nuclear charge metalloids.
(Zeff). 28. Fluorine and chlorine are gases whereas iodine
15. i. The atomic radius increases down the is a solid at room temperature.
group, as a result of increase in the 32. Oxygen shows –2, –1, and +2 oxidation states
number of quantum shells. while other elements show –2, +2, +4, +6
ii. The ionisation enthalpy decreases down oxidation states.
the group due to increase in the atomic
36. Hydrogen fluoride is a liquid (b.p. 293 K) due to
size.
strong hydrogen bonding while other hydrogen
iii. The electronegativity decreases down the
halides are gases.
group.
37.
17. The ionisation enthalpy decreases down the Example Oxidation state of oxygen
group due to increase in the atomic size. H2O –2
20. On moving down the group, atomic size OF2 +2
increases. Larger the size of an atom, lesser is Na2O2 –1
the attraction between the nucleus and H2O2 –1
outermost electron. Hence it is easier to remove
38. Most electronegative fluorine shows only –1
electron from it. Therefore, as atomic size
oxidation state. Chlorine, bromine and iodine
increases, ionization enthalpy decreases.
show –1, +1, +3, +5 and +7 oxidation states.
1 Chlorine and bromine also exhibit +4 and +6
Ionisation enthalpy 
atomic radius oxidation states.
126
 

MHT-CET Triumph Chemistry (Hints)

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.

CH3CH2CH = CH2 + HBr   CH3CH2CH2CH2Br   CH3(CH2)3OCH2CH3

H O
36. 2 2
Anti  Markownikoff 's
C 2 H 5 ONa

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
Sodium CH3
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, -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 -hydrogen from CH3 and CH2– groups respectively as given below:

H Cl
   
elimination
H3C O N a + H2C  C – CH2 – CH2 – CH3  
 H2C = C – CH2 – CH2 – CH3 + CH3OH + NaCl
Sodium
methoxide CH3 CH3
2-Chloro-2-methylpentane 2-Methylpent-1-ene
(b)

H Cl CH3
    elimination
H3C O N a + H  C  C – (CH3)2  
 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 

H2SO4
CH3 CH  CH3 
H2 O
 CH3 CH  CH3 K 2 Cr2 O 7
  CH3 C  CH3
Propylene Propan-2-ol Propanone
OSO3H (B) (C)
Isopropyl hydrogen
sulphate
(A)

184
 

Chapter 11: Alcohols, Phenols and Ethers

Hints to Evaluation Test

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

+ CH3–C–O–C–CH3 
H
 Acetic acid
Salicylic acid Aspirin
(Acetyl salicyclic acid)

OH O

5. 
Na 2 Cr2 O7
H2SO4


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  C2 H5 MgI I
(c) CH2O   ii  H2 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)

185
 

MHT-CET Triumph Chemistry (Hints)

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 H3C OSO3H H3C OH

 , H2 O
14. C = CH2 + H2SO4  C 
 H2SO4
 C
H3C (cold and CH3 CH3
H3C H3C
Isobutylene conc.)
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

186
  Chapter 12: Aldehydes, Ketones and
Textbook
Chapter No. 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

13. CH3CH2CH CHO

CH3
2-Methylbutanal
or
-Methyl butyraldehyde

14. Oxaldehyde (Glyoxal): CHO – CHO

IUPAC name: Ethanedial
15. Benzene-1,2-dicarbaldehyde: Phthalaldehyde;
CHO

CHO
2-Methylbenzaldehyde: o-Tolualdehyde
CHO

CH3
187
 

MHT-CET Triumph Chemistry (Hints)

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. O 3
CH3  CH2  C = CH2 
ii. Zn / H 2 O
Butanone Methanal
CH3
2-Methylbut-l-ene

28. HC  CH + H2O 

40% H 2SO 4
1% HgSO 4
 CH3CHO
Acetylene Acetaldehyde

188
  Chapter 12: Aldehydes, Ketones and
Carboxylic Acids
O

29. H3C – C  CH + H2O 

40% H 2SO 4
1% HgSO 4
 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 2SO 4
1% HgSO4
 CH3CHO
Acetaldehyde

(D) CH3COCl + H2 

Pd-BaSO 4
 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

NaOH 
43. 
CH3CH2CH2COOC2H5  
 CH3CH2CH2COONa 
H3 O
 CH3CH2CH2COOH
 C2 H5 OH

Ethyl butanoate Sodium butanoate Butanoic acid

189
 

MHT-CET Triumph Chemistry (Hints)

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 COOH

KMnO4 / dil. H2SO4


KMnO4 / dil. H2SO4

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
O + CH3MgBr  
(i) Dry ether
46. C (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 
+ Mg(OH)Br

H3 O

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.
190
  Chapter 12: Aldehydes, Ketones and
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 – C H 2 + H2O
Acetone
[Fe(CN)5NO]2– + CH3 – CO – C H 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

72. CH3  C  CH3 +  CH3  C  O

HO  CH2 
dry HCl
 H
CH2
Acetone CH2 O
CH2
HO  CH2 CH2
Propylene glycol Cyclic ketal

H H H

H  C+ = O + CH3 – MgCl dry
ether

 H  C OMgCl 


73.
H
HOH
 H  C  OH + Mg(OH)Cl
Formaldehyde Methyl
(X) magnesium chloride CH3 CH3
Adduct Ethyl alcohol

74. CH3CHO + H2NNHC6H5  CH3CH = N  NHC6H5

Acetaldehyde Phenylhydrazine Acetaldehyde phenylhydrazone

191
 

MHT-CET Triumph Chemistry (Hints)

75. X is semicarbazide (NH2 – NH – CONH2).

O + H2N – NH – CONH2 

 H2O
 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 -H atoms. The nucleophile formed by the
removal of a proton from the -C attacks the carbonyl carbon of the second molecule, to form a -hydroxy
aldehyde or ketone.
2CH3 – C – H 
dil NaOH
 H3C – CH – CH2 – C – H

O OH O
Acetaldehyde Aldol product
(2 molecules)

H
    

79. H – C – C – H + H – CH2 – C – H  dil.N
 aO H
 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

80. CH + CH2  C  CH3 
10% NaOH
 CH  CH2  C  CH3
O H OH

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 -hydrogen atoms.

82. Cannizzaro reaction is given by aldehydes which do not have -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

192
  Chapter 12: Aldehydes, Ketones and
Carboxylic Acids

H O

C C CH2 – OH
84. 2 O O– K+
   

KOH in M eOH

+

Benzaldehyde Potassium benzoate Phenylmethanol /benzyl alcohol

H
O O
C CH2 – OH
O
85. H–C–H + 
i. conc.NaOH
 + H – C – OH
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

H 2 N  NH2
C = O 
 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
+ HO  NO2 
conc. H2SO4
 + 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.

193
 

MHT-CET Triumph Chemistry (Hints)

40. 42.
Element Nature of oxide Element Type
Calcium Basic (A) Carbon Non-metal
Zinc Amphoteric (B) Neon Noble gas
Carbon Acidic (C) Sodium Alkali metal
Sulphur Acidic (D) Tellurium Metalloid

Hints to Evaluation Test

5. 11. Perchloric acid, HClO4

Compound Oxidation state of xenon Oxidation state of ‘Cl’ = +7
XeOF4 +6
13. Let ‘x’ be the oxidation number of sulphur. S8 is
XeO3 +6 the elemental form of sulphur. Hence, oxidation
XeF6 +6 state is zero.
XeF4 +4 In S2F2, 2x  2 = 0
XeF2 +2  2x = 2
x=1
7. Acidic character of hydrides of group 17
In H2S, 2 + x = 0
elements increases down the group. Thus, HF is
least acidic in nature. x=2

8. Peroxydisulfuric acid, H2S2O8 14. The noble gas which forms maximum number
of compounds is Xe.
O O e.g. XeF2 , XeOF2 . XeF4 , XeOF4 . XeF6 , XeO3 .

S S 18. Most electronegative fluorine shows only –1

O O–O O oxidation state. Chlorine, bromine and iodine
OH OH show –1, +1, +3, +5 and +7 oxidation states.
Chlorine and bromine also exhibit +4 and +6
Thiosulfuric acid, H2S2O3 oxidation states.
S

S
HO
O
OH
Sulfurous acid, H2SO3

S
HO
HO O

Disulfuric acid or pyrosulfuric acid, H2S2O7

O O

S S
O O O
OH HO
9. Acidic oxides: Cl2O7
Amphoteric oxides: Al2O3
Neutral oxides: CO, NO
10. SO2 is highly soluble in water and its solution in
water is called sulfurous acid (H2SO3).

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  Chapter 12: Aldehydes, Ketones and
Carboxylic Acids
4. 2 3 4 5
H5C2 CH CH CH2 CH3
1
CHO CH3
2-Ethyl-3-methylpentanal

5. Crotonaldehyde is an ,unsaturated aldehyde represented as follows:

CH3  CH = CH  CHO
But-2-enal
(Crotonaldehyde)

7. (CH3)2CH–COOH
Common name: -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

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MHT-CET Triumph Chemistry (Hints)

22. Hydration of alkynes takes place in accordance with the Markovnikov’s rule.
CH3  CH2  C ≡ C  H + H  OH 
40% H 2 SO 4
 Tautomerism

CH3  CH2  C = CH3  CH3  CH2  C  CH3
i. 1% HgSO 4

But-1-yne
OH O
But-l-en-2-ol Butanone

ii. CH3  C ≡ C  CH3 + H  OH 

40% H 2SO 4
1% HgSO4
 CH3  CH = C  CH3 Tautomerism

 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

CH3  CH  C ≡ C  H + H  OH 
40% H 2 SO 4
1% HgSO 4
 CH3  CH  C = CH2 Tautomerism

 CH3  CH  C  CH3
3-Methylbut-1-yne
OH O
3-Methylbutan-2-one

iv. Hex-3-yne to hexan-3-one:

CH3  CH2  C  C  CH2  CH3 + HOH   CH3  CH2  CH = C  CH2  CH3
40% H 2SO 4
1% HgSO4

Hex-3-yne
OH
Hex-3-en-3-ol

CH3  CH2  CH2  C  CH2  CH3

Tautomerism



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   C6H5 – CHO + NH4Cl
SnCl2 , HCl H3O

Benzonitrile Benzanimine hydrochloride Benzaldehyde


(III) C6H5 – C  N + C6H5 – MgBr   C6H5 – C = NMgBr 
dry ether H3O
 C6H5 – CO – C6H5 + NH3 + Mg(Br)OH

Benzonitrile C6H5 Benzophenone

O
(IV) + C6H5COCl 
Anhyd..AlCl3
 C + HCl
Benzoyl chloride
Benzene Benzophenone

196
  Chapter 12: Aldehydes, Ketones and
Carboxylic Acids

O O

28. CH3  C  N + H2O 

Hydrolysis
 CH3  C  NH2 
H2O
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. H2SO4

H3C HOOC
p-Xylene
Terephthalic acid

O O
X
31. R  Mg  X 
CO 2
dry ether
 R  C  OMgX 
H2 O
Dil.HCl
R  C  OH + Mg
Grignard Carboxylic acid OH
reagent

32. C O + CH3CH(CH3) CH(CH3) MgBr 

ether
 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

33. C6H5MgBr 

(i) Dry CO 2 /dry ether
 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
 CH3 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.
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MHT-CET Triumph Chemistry (Hints)

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

 CH3  CH  C = CH2 CH3  CH  C  CH3

40%H2SO4 Tautomerism
CH3  CH  C ≡ C  H + H  OH 
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.

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  Chapter 12: Aldehydes, Ketones and
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 3 CH
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
50. CH3 – CH – CH3  CH3 – C – CH3 
NH 2 OH
 (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 -H atoms in presence of dilute alkali undergoes aldol condensation to give a
-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

56. CH3 – C = O + CH3 – C = O 

dil.NaOH
 CH3 – C – C – C = O
Acetaldehyde Acetaldehyde
OH H
Acetaldol

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MHT-CET Triumph Chemistry (Hints)

57. 
CH3CHO 
dil.KOH
 CH3 – CH – CH2 – C – H 
 H2 O
 CH3 – CH = CH – C – H
Acetaldehyde
OH O O
,-Unsaturated aldehyde

58. Acetaldehyde does not show Cannizzaro reaction as it has -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
+ HO  NO2 
conc. H2SO4
 + 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.
67. C2H5OH + CH3COOH 
Conc H 2SO4
 CH3COOC2H5
Ethanol Acetic acid Ethyl acetate
It is called esterification reaction.
68. RCOOH + C2H5OH 
conc.H 2SO 4
 RCOOC2H5 + H2O

COOH COCl
69.

+ SOCl2   + SO2  + HCl 
O2N NO2 O2N NO2
3,5-Dinitrobenzoic acid 3,5-Dinitrobenzoyl chloride

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  Chapter 12: Aldehydes, Ketones and
Carboxylic Acids

70. HCOOH + PCl5   HCOCl + POCl3 + HCl
Formic Formyl
acid chloride
– 
71. CH3Cl 
KCN
 CH3CN 
H2 O
 CH3COOH 
NH3
 CH3COO NH 4 

 CH3CONH2 + H2O
 KCl

+
72. CH3  C  N 
H
H2 O
P2 O5 , 
 CH3COOH   (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  
74. C CH C CH3
H3C
Mesityl oxide
(,-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

Competitive Thinking

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.
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MHT-CET Triumph Chemistry (Hints)

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 2SO 4
 CH3 – C – CH2 – CH3 + H2O
Butan-2-ol Ethyl methyl ketone
(Butanone)

12. CH3  CH2  C  CH 

aq.H2SO4
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).

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MHT-CET Triumph Chemistry (Hints)

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
 = 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  = n(n  2) BM,
iodide ion is converted into iodate.
Where n = number of unpaired electrons.  
2M nO 4 + H2O + I  2MnO2 + 2OH + IO 3
When n = 2;  = 2(2  2) = 8 = 2.84 BM
 Magnetic moment 2.84 BM is given by Ni2+. 25. In acidic medium:
+ – 2+
M nO 4 + 8H + 5e  Mn + 4H2O
12. Magnetic moment () = n  n  2  BM (i) FeC2O4 ⇒ 1 mol oxalate ion and 1 mol
ferrous ion:
Number Calculated Oxalate ion:
Outer
of value of +
2M nO 4 + 5C 2 O 24  + 16H  2Mn
2+
Ion electronic
unpaired Magnetic
configuration + 8H2O + 10CO2
electrons moment
 2
1 mol C 2 O 4 ≡ mol M nO 4
2
Co3+ 3d6 4 24 BM 5
Cr3+ 3d3 3 15 BM Ferrous ion:
2+ + 2+
Fe3+ 3d5 5 35 BM 2M nO 4 + 10Fe + 16H  2Mn
Ni2+ 3d8 2 + 10Fe3+ + 8H2O
8 BM
3+ 2+
 1 mol Fe2+ ≡ 1 mol M nO 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 C 2 O 24  ≡ 2 mol M nO 4
Mn2+ (3d5) : 5 unpaired electrons 5
Now, 1 mol Fe2(C2O4)3 ≡ 3 mol C 2 O 24 
14. CuSO4 will be absorbing orange-red colour and 6
emits out blue colour.  3 mol C 2 O 24  ≡ mol M nO 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 M nO 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
Ti3+  [Ar] 3d1 = 2161
5 5 5 5
Mn2+  [Ar] 3d5 = 10
Due to absence of unpaired electrons, Sc3+ ion 5
will be colourless. = 2 mol
136
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MHT-CET Triumph Chemistry (Hints)

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 -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 -hydrogen atom.
HCHO, (CH3)3CCHO and CCl3CHO do not contain -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.

204
  Chapter 12: Aldehydes, Ketones and
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).

205
 

MHT-CET Triumph Chemistry (Hints)

O

48. CH3COOH + CH3OH 

Conc.H 2SO 4
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
 O 
H2O
 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.

206
 
Textbook
MHT-CET
Chapter No.Triumph Chemistry (Hints)

09 Coordination Compounds

Hints

Classical Thinking
2. In a complex, metal ion is Lewis acid and ligand is Lewis base.
6.
O O

O=C O O C=O
O=C C=O
H2C CH2 CH2 CH2

N CH2 CH2 N
Ethylenediamine tetraacetate
(EDTA)

7. Ca2+ forms an octahedral complex with just one molecule of EDTA as it has four donor oxygen atoms and
two donor nitrogen atoms in each molecule.
8. Oxalate can bond metal atom through two oxygen atoms
– –
O O
C–C
O O
9. Ammonia, ethylenediamine and water are neutral ligands. Nitrate  NO2  is a negatively charged ligand.
11. Let the oxidation number of Fe be ‘x’. As CN– is a negative ligand, charge on it is –1. Thus, the oxidation
number can be calculated as:
x + 6  (–1) = – 4
 x = +2
12. CO is neutral molecule, hence the oxidation state of central metal atom (Ni) is zero.
14. en is a bidentate ligand. Hence, the coordination number of the central metal ion = 2  number of bidentate
ligands = 2  3 = 6
16. Carnalite is double salt. Its chemical formula is KCl.MgCl2.6H2O.
18. Inner sphere is known as the first sphere or coordination sphere and the outer sphere is known as the second
sphere or the ionization sphere.
19. Secondary valencies and are non ionizable. Number of secondary valencies is equal to the coordination
number. Secondary valencies have a fixed spatial arrangement around the metal ion. Secondary valencies for
a metal ion are satisfied by either by anions or neutral ligands.
21.  [Co(NH3)6]3+ + 3Cl–
[Co(NH3)6]Cl3 

(4 ions)

24. The complex ion carries a net positive charge; hence, a cationic complex. Also, it consists of one type of
ligand only, i.e., H2O. Therefore, it is also a homoleptic complex.

138
 

MHT-CET Triumph Chemistry (Hints)

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.
CH3COOH + NaHCO3  CH3COONa + CO2 + H2O
Acetic Sodium Sodium
acid bicarbonate acetate

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  H2SO4
Cl  CH 
66. ii. SOCl2
 32
Y

Cd

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 NH2
Δ
 H2O


Ammonium salt Benzamide

of benzoic acid

208
  Chapter 12: Aldehydes, Ketones and
Carboxylic Acids
68. O
CH3 C  OH CH3


Alkaline KMnO4 , Δ
dil HCl
 
Sodalime
Δ
 
CH3Cl
Anhy.AlCl3


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

69. 
NaBH 4
OH 
PBr3
 Br 
Mg / Ether

CHO
Hex-3-ynal Hex-3-yn-1-ol 1-Bromohex-3-yne

+
MgBr 
CO2
 COO– 
H
COOH
Hept-4-ynoic acid

NaBH4 attacks only carbonyl group selectively without affecting the carbon-carbon double bond.

70. All the given reactions can be categorised as elimination reactions.

(I) (CH3)3C–CH(OH)–CH3 
Conc. H 2SO 4
1,2-Methyl shift
(CH3)2C = C(CH3)2
(-H 2 O)

(II) (CH3)2CH–CH(Br)– CH3 

Alc.KOH
 (CH3)2C=CH–CH3
- +
(III) (CH3)2CH–CH(Br)– CH3 
(CH3 )3 O K
 (CH3)2CH–CH=CH2

(IV) (CH3)2C(OH)–CH2CHO   (CH3)2C=CHCHO
Saytzeff rule: In the dehydrohalogenation or in the dehydration, the alkene formed by the elimination has
greater number of alkyl groups attached to the doubly bonded carbon atom.
Reaction (I): Involves the 1,2-methyl shift, as carbocation formed during the course of reaction undergoes
rearrangement to form more stable highly substituted alkene. Thus, forms a Saytzeff product.
Reaction (II): Involves a simple dehydrohalogenation reaction, which is in accordance with Saytzeff rule.
Reaction (III): It’s an example of elimination reaction in presence of bulky base potassium tert-butoxide. In
this case, base abstracts hydrogen from less hindered site of a substrate molecule which is in contrast with
the Saytzeff rule.
Reaction (IV): The product of dehydration is highly substituted α,β-unsaturated compound.
Thus, only reaction (III), will not produce Saytzeff product.

Hints to Evaluation Test

CHO
1. + CH3  NH2  CH = NCH3 + H2O
Methylamine
Benzaldehyde Substituted imine
(Schiff’s base)


2. C2H5 I 
alc.KOH
 CH2 
Br2
CCl4
 CH2  Br 
KCN
 CH2  CN 
H3 O
 CH2  COOH

CH2 CH2  Br CH2  CN CH2  COOH

(X) (Y) Succinic acid
(A)
209
 

MHT-CET Triumph Chemistry (Hints)

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 
CH3 Cl
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 -hydrogen. Hence, C6H5CHO and HCHO.

11. CO2 + C3H7MgBr 

i. dry ether
+ C3H7COOH + Mg(Br)OH
ii. H /H 2 O

12. Formaldehyde does not contain 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
R  C = O + ROH  
Dry HCl Dry HCl
16. C 
 
 C
R OH
H OR H OR
H Acetal
Hemiacetal
Aldehyde

210
  Chapter 12: Aldehydes, Ketones and
Carboxylic Acids
17. CH3  CH  CH3 
K 2 Cr2 O7
H 2SO 4
 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)

211
 Textbook
Chapter No.

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. 100  C
RX + alc. NH3 
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

212
 

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

CH3 – C – NH2 + 4[H] 

LiAiH4 /ether
or Na/C2H5OH
 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.
213
 

MHT-CET Triumph Chemistry (Hints)

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 X
R – NH2 
 HX
R X
 R2NH 
 HX
 R X
R3N 
 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.

CH3  Br
Et–NH2 
 HBr
CH3  Br
 (Et)2NH 
 HBr
CH3  Br
 (Et)3N 
 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)

214
 

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.

CH3 – CH2 – NH2 + HNO2   CH3 – CH2 – OH + N2  H2O

i. NaNO2 / HCl, 273K
62. ii.H O 3
Ethylamine Ethanol

67. C6 H5 N 2 Cl 

H2 O
283 K
 C6H5 – OH + N2 + HCl
Benzenediazonium chloride Phenol (X)

69. C6H5 – N 2 X– 

HBF4
 C6H5 – N 2 BF4 
Aq. NaNO 2 / Cu

C6H5 – NO2 + N2  + BF3
Benzenediazonium Nitrobenzene
halide
 
 
70. Ph – N2 Cl 
HBF4 
 Ph – N2 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)

215
 

MHT-CET Triumph Chemistry (Hints)

49. (I) [Fe(CN)6]3–
Configuration of central metal ion after complex formation:
3d 4s 4p

        

d2sp3
(III) [COF6]3–
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.
144
 

Chapter 13: Amines


82. C2H5NH2 
HNO 2 / 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
-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 CH3  N
NH
n-Propylamine (1 amine) CH3 CH3
CH3 Ethylmethylamine
Isopropylamine Trimethylamine
(2 amine) (3 amine)
(1 amine)

8. (CH3)2CH– NH2
Common name: Isopropylamine ; IUPAC name: Propan-2-amine

CH3
2 1
9. CH3 – N – CH – CH3

3CH3
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.
217
 

MHT-CET Triumph Chemistry (Hints)

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 

LiAlH4 in ether
 C2H5  NH2 
C 2 H5 Br
 (C2H5)2NH 
C 2 H5 Br
 (C2H5)3N
Nitroethane Ethylamine Diethyl Triethyl
(X) amine amine
(Y) (Z)

14. CH3  NO2 

Fe/ HCl
CH3  NH2 
C 2 H5 Br
 C2H5–NH–CH3 
C 2 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)

(H3C)2  CH  CN   (H3C)2CH  CH2 – NH2

Na /C2 H5OH
or LiAlH4
2-Methylpropan-1-amine
(Y)

16. C2H5  Cl 

Alc.AgCN

 C2H5N  C 
Na / C 2 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
degradation
Acetamide Methylamine
(Amide) (Amine)
[2 C-atoms] [1 C-atom]

218
 

Chapter 13: Amines

O

C  NH2 NH2

19. + Br2 + 4NaOH  + Na2CO3 + 2NaBr + 2H2O

(aqueous
Benzamide or alcoholic) Aniline
(X)
O = C – NH2 CH2NH2


LiAlH4 /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.
219
 

MHT-CET Triumph Chemistry (Hints)

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

   
C6H5  N 2 X  C6H5  N 2 X   C6H5OH
H PO H2 O
38. (i) 3 2
H2O
C6H6 (ii) 283 K
   
C6H5  N 2 X   C6H5F
i.HBF4
(iii) ii. 
(iv) C6H5  N 2 X 
CH3 CH 2 OH
 C6H6
 
C6H5  N 2 X   C6H5NO2
i.HBF4
(v) ii. ,aq.NaNO2 /Cu

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.
+ – 
OH  
OH
N  NCl + 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 / C 2 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 / C 2 H5 OH
H2N – H2C – (CH2)4 – CH2 – NH2
1,4-Dichlorobutane Hexane-1,6-diamine
(1)

 CH3CH2CONH2   CH3CH2NH2

 Br2 / KOH
(D) CH3CH2COOH 
NH 3
 CH3CH2COONH4  (Hoffmann bromamide )
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.

220
 

Chapter 13: Amines

Competitive Thinking
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 
 H2O
 NK+
CO CO
Phthalimide Potassium salt of phthalimide –KBr

COOH CO
+ 
H3C(CH2)3NH2 
H / H 2 O or OH / H 2 O
+ 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

221
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MHT-CET Triumph Chemistry (Hints)

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 + 
NH3 
+
 CH3COONH4   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 NaNO 2  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


NaNO 2 / HCl
 
CuCN / KCN

18. 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. 
NaNO 2 , HCl
 KI / 

273  278 K  N 2 ,  KCl

Aniline Benzenediazonium Iodobenzene

chloride (Z)

222
 

Chapter 13: Amines

NH2 N 2 Cl 

0 5 C
21. + NaNO2 + 2HCl   + 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

HNO 2
273 K

Phenol
 N=N OH
HCl

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
NH2 NH – C – CH3 NH – C – CH3 NH2

27. 
(H3 CCO)2O
Pyridine / 
  Br2
H3 CCOOH
 
H

Aniline Acetanilide
Br Br
(A) p-Bromoacetanilide p-Bromoaniline
(B) (C)
223
 

MHT-CET Triumph Chemistry (Hints)

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  NH 3 , 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 

 pH  9  10  
6 5 2

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 

NaNO 2  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.

224
 

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
  
C 2 H 5 OH

273278 K   
KMnO4

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. H3PO2


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


KMnO4 / OH
 
H 2 O / H 3 PO 2 / CuCl
Re duction 273 – 278 K
Oxidation
(Diazotisation)
o-Bromobenzoic o-Bromotoluene N 2 Cl 
acid (R) Diazonium
salt

225
 

MHT-CET Triumph Chemistry (Hints)

Hints to Evaluation Test

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 

15. 
NaNO 2 , HCl
273  278 K
 
CH3 CH 2 OH


Aniline Benzenediazonium Benzene

chloride (Z)

   
C6 H5  N 2 X  C6 H5  N 2 X   C6H5OH
H PO H2 O
18. (A) 3 2
H2O
C6H6 (B) 283 K
   
C6 H5  N 2 X   C6H5F
i.HBF4
(C) ii. 
(D) C6 H5  N 2 X 
CuBr / HBr
 C6H5Br

226
 

Chapter 13: Amines

19. CH3 – CO – NH2 
NaOH / Br2
Hoffmann's bromamide
 CH3 – NH2
degradation
Acetamide Methylamine
(Amide) (Amine)

O O O

C C C
– +
20. NH 
Alc.KOH
 N K 
CH3 CH 2 Br
N CH2CH3
 H2 O
C 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)

227
 Textbook
Target
Chapter No.Publications Pvt. Ltd. Std. XII : Triumph Chemistry

14 Solid State

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

228
 

Chapter 14: Solid State

23.  , HI
CHO(CHOH)4CH2OH   CH3(CH2)4CH3
Glucose n-Hexane

24. Carbonyl group (–CHO) in glucose reacts with hydrogen cyanide (HCN) and hydroxylamine (NH2OH) to
form glucose cyanohydrin and glucoxime respectively.
25. Glucose gets oxidised to a six carbon monocarboxylic acid called gluconic acid on reaction with bromine
water which is a mild oxidizing agent.

CHO CHO O O

26. (CHOH)4 + 5(CH3CO)2O  (CH – O – C – CH3)4 + 5CH3 – C – OH

Acetic Acetic acid
CH2OH anhydride CH2 – O – C – CH3
Glucose
O
Glucose pentaacetate

27. CHO COOH

(CHOH)4 
Dil.HNO3
[O] (CHOH)4

CH2OH COOH
Saccharic acid
Glucose (X)

CHO COOH COOH

(CHOH)4 + [O] 2   (CHOH)

Br water
4 
Dil.HNO3
[O]
 (CHOH)4

CH2OH CH2OH COOH

Glucose Gluconic acid
Saccharic acid
(Y)
(Z)

28. Fisher projection formula of glucose:

1
CHO
* 2
H OH
HO * 3 H
H * 4 OH
H * 5
OH
6
CH2OH
(Glucose)

29. CHO CHO CHO CHO CHO

H OH HO H HO H
H OH HO H HO H HO H OH
H
H OH HO H
CH2OH CH2OH H OH CH2OH
CH2OH
D-Glyceraldehyde L-Glyceraldehyde D-Threose
L-Ribose
(I) (II) CH2OH (IV) (V)
D-Glucose
(III)

30. The lower side of the ring is called α-side and the upper side is the β-side. Thus, the α-anomer has its
anomeric –OH group on the α-side (i.e., lower side), whereas the β-anomer has its anomeric –OH group on
the β-side (i.e., upper side) of the ring.
229
 

MHT-CET Triumph Chemistry (Hints)

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.
 +2  + 
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

154
 

Chapter 10: Halogen Derivatives

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.
155
 

MHT-CET Triumph Chemistry (Hints)

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.
NH 2  OH
O = CH(CHOH)4CH2OH   OH – N = CH –(CHOH)4CH2OH
Glucose Oxime
(X)
 , HI
CHO(CHOH)4CH2OH   CH3(CH2)4CH3
Glucose n-Hexane
(Y)

8. CHO COOH CHO COOH

(CHOH)4 
Dil.HNO3
[O] (CHOH)4 (CHOH)4 + [O]  

Br2 water
(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 -D-glucopyranose is linked to C-4 of another -D-glucopyranose molecule by
glycosidic linkage.
(B) In cellulose, C-1 of one -D-glucopyranose is linked to C-4 of another -D-glucopyranose molecule
by glycosidic linkage.
(C) In sucrose, C-1 of -D-glucopyranose is linked to C-2 of -D-fructofuranose by glycosidic linkage.
(D) In lactose, C-1 of -D-galactopyranose is linked to C-4 of -D-glucopyranose by glycosidic linkage.
16. -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
232
 

Chapter 14: Solid State

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
-Amino acid -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. -Helix structure of proteins is formed when the chain of -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.
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MHT-CET Triumph Chemistry (Hints)

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.

Competitive Thinking
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 -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 -D-(+)-glucose.

HO 1C* H
H 2C* OH
HO 3C* H O

H 4C* OH

H 5C*
6
CH2OH
-D-(+)-Glucose

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Chapter 14: Solid State

7. Sucrose is a disaccharide of -D-glucopyranose and -D-fructofuranose.
8. Maltose is a disaccharide made of -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 -D-glucose units
(B) Sucrose Disaccharide having -D-glucose and -D-fructose units
(C) Cellulose Polysaccharide having -D-glucose units
(D) Lactose Disaccharide having -D-galactose and -D-glucose units
12. In maltose, C-1 of one -D-glucopyranose molecule is linked to C-4 of another -D-glucopyranose
molecule by glycosidic linkage.
In lactose, C-1 of -D-galactopyranose molecule is linked to C-4 of -D-glucopyranose molecule by
glycosidic linkage.
In cellulose, C-1 of one -D-glucopyranose molecule is linked to C-4 of another -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 -D-glucopyranose molecule is
linked to C-4 of another -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.
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MHT-CET Triumph Chemistry (Hints)

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
Mass of water 72g
 Volume of water = = = 72 cm3 = 0.072 dm3
Density of water 1g / cm 3

38. Fibrous proteins are insoluble in water.

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Chapter 14: Solid State

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 H2N 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.

Hints to Evaluation Test

2. Lactose is obtained by the condensation of one molecule of -D-galactopyranose and one molecule of
-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
-D-Galactose -D-Glucose
-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. NH3+  CH2  COO
Dipolar ion
(Zwitter ion or internal salt)

CHO COOH

15. (CHOH)4 + [O] 

Bromine
water
 (CHOH)4

CH2OH CH2OH
Glucose Gluconic acid

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Textbook
MHT-CET
Chapter No.Triumph Chemistry (Hints)

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   H2O
 [ NH ( CH2)5 CO ]n
533543 K
H2C CH2
(Nylon 6)
CH2 – CH2
 
-Caprolactam

47. Nylon 6 is prepared from cyclic monomer i.e., -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

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 

Chapter 10: Halogen Derivatives

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)

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MHT-CET Triumph Chemistry (Hints)

8. Teflon is a chain growth polymer.
nCF2 = CF2 
Polymerization
 –– CF2 – CF2 ––
n
Tetrafluoroethylene Teflon

9. Elastomers are soft and stretchy and are hence used in making rubber bands.
11. Thermoplastic polymers: PVC, Polythene, Polystyrene

12. The natural rubber has weak intermolecular forces (van der Waals forces of attraction) and is an example of
an elastomer.

13. Thermosetting polymers are cross linked polymers while thermoplastic polymers are either linear or
branched chain polymers.
14. Thermosetting polymers are rigid due to extensive covalent bonding by covalent bonds formed in the
moulds during hardening/setting process while hot.
16. Buna-S is a copolymer whereas polystyrene, nylon 6 and nylon 6,6 are homopolymers.

17. Polyisoprene is natural rubber.

19. (I) By increasing amount of sulfur, the rubber can be hardened.
(IV) When the amount of sulfur is raised to 40-45%, ebonite is obtained.
29. Natural rubber has the cis-configuration (cis-1,4-polyisoprene) at every double bond.

30. Correct representation of neoprene is

 CH2 C = CH  CH2 
Cl
n
34. Critical degree of polymerization is lower for those containing strong intermolecular forces such as
hydrogen bonding. Nylon 6 is a polyamide polymer, and has strong intermolecular hydrogen bonding as
inter molecular forces. Hence, nylon 6 has lowest critical degree of polymerization.
35. Non-biodegradable polymers are those polymers which are not degraded by microorganisms.
PHBV and nylon 2-nylon 6 are biodegradable polymers.
36. PHBV is a copolymer of two bifunctional -hydroxy carboxylic acids
40. In the polymer PHBV, both the monomers chiral.
* *
HO – CH – CH2 – COOH HO – CH – CH2 – COOH

CH3 CH2CH3
(3-Hydroxybutanoic acid) (3-Hydroxypentanoic acid)

41. DNA is deoxyribose nucleic acid and it is a polymer of nucleotides. ATP is adenosine triphosphate and is a
biomolecule. Cellulose is a polysaccharide whereas proteins are polypeptide chains.
42. Letter ‘N’ in Buna-N stands for one of its monomer  nitrile (acrylonitrile).

43. Teflon–thermally stable linear polymer of tetrafluoroethene.

45. Polytetrafluoroethene (teflon) is formed from tetrafluoroethylene, which does not show geometric
isomerism. In all other polymers, the monomers show geometric isomerism.

Competitive Thinking
2. Dacron is a condensation polymer formed by polymerisation of terephthalic acid and ethylene glycol while
neoprene and teflon are addition polymers. Acrylonitrile is a monomer of polyacrylonitrile.
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MHT-CET Triumph Chemistry (Hints)

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

164
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MHT-CET Triumph Chemistry (Hints)

Hints to Evaluation Test

1. nH2N CH2 COOH + nNH2 ( CH2 )5 COOH 

Polymerization
 C CH2 NH C (CH2 )5NH
n
Glycine -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
nCH2 = CHCN  
Polymerisation
H2O2
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.

242
 Textbook
Chapter No.

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)

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Textbook
MHT-CET
Chapter No.Triumph Chemistry (Hints)

11 Alcohols, Phenols and Ethers

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

168
 
Chapter 16: Green Chemistry
and Nanochemistry
18.
(A) CHO CHO COOH COOH



Deprotection of


C6 H5CH2 Cl
protection of
 [O]
 OH group

OH  OH group OCH2C6H5 OCH2C6H5 OH

m-Hydroxybenzoic acid
m-Hydroxybenzaldehyde

(B) O O

NH2 NH – C – CH3 NH – C – CH3 NH2

 3 2
CH CO O / Base 
   
H (Deprotection

 Acetic acid solvent  
Br2
(Pr otection of  NH 2 ) of  NH2 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 

(Pr otection of  NH 2 )
 Conc.HNO3  Conc H2SO4
 288 K
 
H (Deprotection
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.

Hints to Evaluation Test

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].

245
 

Organic Reactions:
MHT-CET Triumph Chemistry (Hints)

Compilation of organic reaction based MCQs

Hints

1. 3CH3  CH2  CH = CH2 

i) BH3  THF, 273K
ii) 3H 2 O 2
 3CH3  CH2  CH2  CH2  OH + B(OH)3
But-1-ene Butan-1-ol
‘A’ ‘B’
PCC H

3CH3  CH2  CH2  C = O + 3H2O
Butan-1-al
‘C’
2. As the compound ‘A’ is a linear chain compound with molecular formula C5H10O2 and gives brisk
effervescence of CO2 when treated with saturated aqueous NaHCO3 solution, it is a carboxylic acid with
5 carbons. (i.e. CH3  CH2  CH2  CH2  COOH, pentanoic acid).
CH3  CH2  CH2  CH2  COOH 
i. Cl2 / Re d P
ii. H 2 O
 CH3  CH2  CH2  CH  COOH + HCl

Pentanoic acid Cl
‘A’ 2-Chloropentanoic acid
CH2  CH3 ‘B’
Chiral isomer  H  C* COOH
of pentanoic
acid CH3
2-Methylbutanoic acid
2,2-Dimethylpropanoic acid is the isomer of pentanoic acid but it is achiral. Hence, option (C) is incorrect
and option (A) is correct.
3. As the compound ‘A’ reacts instantaneously with the ‘Lucas reagent’ (conc. HCl + anhydrous ZnCl2), it is a
tertiary alcohol consisting of four carbons [as it gives ‘B’ (C4H9Cl)].
CH3 CH3 CH3
H3C  C  OH 
conc.HCl  anhydrous ZnCl2
room temperature
 H3C  C  Cl 
aq. KOH

 H3C  C  OH

CH3 CH3 CH3

2-Methylpropan-2-ol 2- Chloro-2-methylpropane 2- Methylpropan-2-ol
‘A’ ‘B’ ‘A’

4. CH3  CH2  Br + Na  O  CH3  

 NaBr
 CH3  CH2  O  CH3
1-Bromoethane 1-Methoxyethane
OR ‘B’
Ethyl bromide
‘A’
Name of the reaction : Williamson’s synthesis
Br  CH3  CH = CH  CH3
alc. KOH But-2-ene (Major product-80%)
5. CH3  CH  CH2  CH3 ‘B’
KBr,
sec-Butyl bromide H2O H2C = CH  CH2  CH3
OR But-1-ene (Minor product-20%)
2-Bromobutane ‘C’
‘A’

246
 

Organic Reactions
+
OH ONa OH
CHO CHO
6. + CHCl3 
 NaOH, 340K
dil. HCl
 NaCl

Phenol Salicylaldehyde
‘A’

Name of the reaction: Reimer-Tiemann reaction.

Phenol is weak acid. Hence, it turns blue litmus paper red. Phenol forms ferric phenoxide when treated with
aq. FeCl3 solution. Ferric phenoxide is violet coloured complex.
3C6H5OH + FeCl3  (C6H5O)3Fe + 3HCl
Phenol (aq.) Ferric phenoxide
(violet)
H

N NH HCl 
H / H2 O O
7. + 2[H] 
SnCl2 / dil.HCl
Stephen reaction  NH4 Cl


Benzonitrile Benzyl Benzaldehyde

‘A’ imine hydrochloride ‘C’
‘B’

H H
O2N
O + HO  NO2 
conc. H2SO4
 O + H2O

‘C’ m-Nitrobenzaldehyde

H H

8. H  C = O + CH3  Mg  I 
i.  , dry ether
ii.H  / H O
 H  C  CH2  OH 
CH2 N2
 , HBF4
 CH3  CH2  O  CH3 + N2 
2
Methyl 1-Methoxyethane
Formaldehyde magnesium H ‘C’
‘A’ iodide Ethan-1-ol
‘B’

CH3

H3C – C – H OH
9. O
i.Cobalt naphthenate,
423 K / OH 
+ O2 ii.dil.H 2SO 4 , 
+ CH3  C  CH3

(Air) Phenol Acetone

Cumene
‘B’
(Isopropyl benzene)
‘A’ conc. HNO3
 +
conc. H2SO4

OH
O2N NO2

+ 3H2O
NO2
Picric acid
(2,4,6-Trinitrophenol)

247
 

MHT-CET Triumph Chemistry (Hints)

10. CH3  CH2  CH2  Br + KOH 
 KBr
 CH3  CH2  CH2  OH 
conc..H 2SO 4
443 K
 CH3  CH = CH2 + H2O
n-Propyl bromide aq. Propan-1-ol Prop-1-ene
OR ‘B’ ‘C’
1-Bromopropane
‘A’

11. Crossed aldol condensation will follow the mechanism as given below.
H
 

OH

CHO  
 CHO + O 
H3CO

H O H OH

HOH H

 
 + OH 
H3CO CHO H3CO CHO

+
OH2
H
 H2O
 

H3CO CHO H3CO CHO

12. Benzenediazonium chloride (prepared by diazotisation of aniline) is coupled with -naphthol to give
Benzene azo--naphthol. The reaction is called as ‘azo coupling’.
NH2 N   NCl

0 5 C
+ NaNO2 + 2HCl 
Diazotisation
 + 2H2O + NaCl
Sodium
Aniline nitrite Benzenediazonium
chloride

N+  NCl N=N
OH OH
+ 
Azo coupling
alkaline

medium

-naphthol Benzene azo--naphthol

Cl OH

13. 
Dow process


Chlorobenzene Phenol
‘X’

OH OH OH
NO2
2 + 2HNO3  
room temperature
 + + 2H2O

Phenol (dil.) NO2

o-Nitrophenol
(Major product) p-Nitrophenol
‘Y’ (Minor product)
‘Z’

248
 

Organic Reactions
14. i. Wurtz Fittig reaction of two molecules of bromobenzene gives diaryl compound.
ii. Bromine is deactivating and ortho-para directing group in case of an electrophilic substitution
reaction. The para-substituted product is major product as it is less sterically hindered.

15. As the mixed ether on heating with dil.H2SO4 gives methanol and ethanol, it is ethyl methyl ether.
CH3 – O – CH2 – CH3 + H2O 
dil.H 2SO 4
 , pressure
 CH3 – OH + CH3  CH2  OH
Ethyl methyl ether Methanol Ethanol

Molecular mass of ethyl methyl ether = 60 g mol1

Molecular mass of ethanol = 46 g mol1
The yield of ethanol obtained = 80% = 1.5 g
100
 100% yield of ethanol will be = 1.5 
80
= 1.875 g
1.875g
 Number of moles of ethanol (100% yield) =
46 g mol1

= 0.04 mol
Since, 1 mol of ethanol will be formed from 1 mol of ether.
 0.04 mol of ethanol will be formed from 0.04 mol of ether.
 0.04 mol of ethyl methyl ether = 0.04  60 = 2.4 g of ether

16. Phenol gives benzene, when treated with zinc dust.

OH


+ Zn   + ZnO

Phenol Benzene
‘M’ ‘N’

When benzene is treated with CO and HCl under high pressure in the presence of anhydrous AlCl3 and
CuCl, it gives benzaldehyde and the reaction is called as ‘Gatterman-Koch formylation’.

CHO
CO, HCl
Anhydrous AlCl3  CuCl


Benzene Benzaldehyde
‘N’ ‘Q’

17. Esters are partially reduced to aldehydes with DIBAL-H in toluene followed by acid hydrolysis.
O
||
CH3(CH2)5  C  OCH3 
i) DIBAL -H in toluene
ii) H O
 CH3(CH2)5CHO + CH3OH
3
Methyl heptanoate Heptan-1-al Methanol

Esters are completely reduced to alcohols with LiAlH4 followed by acid hydrolysis.

O
||
CH3(CH2)5  C  OCH3 
i) LiAlH 4
ii) H O
 CH3(CH2)5CH2OH + CH3OH
3
Methyl heptanoate Heptan-1-ol Methanol

249
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MHT-CET Triumph Chemistry (Hints)

18. Butyronitrile undergoes Stephen reaction in the presence of SnCl2 and dil. HCl followed by acid hydrolysis
to give butyraldehyde (buttery odour).
H
|
CH3  CH2  CH2  C  N + 2(H)  i) SnCl2 / dil.HCl
ii) H O   CH3  CH2  CH2  C = O + NH4Cl
3

Butyronitrile Butyraldehyde
‘A’ ‘B’
Butyraldehyde on treatment with HCN in the presence of small amount of base gives butyraldehyde
cyanohydrin.
H H
CH3  CH2  CH2  C = O + HCN 
OH
CH3  CH2  CH2  C  OH
Butyraldehyde CN
‘B’
Butyraldehyde cyanohydrin
‘C’
19. Propanamide undergoes Hoffmann bromamide degradation in the presence of bromine and alcoholic NaOH
to yield ethanamine i.e., compound ‘B’.
O
CH3  CH2  C  NH2 + Br2 + 4NaOH  CH3  CH2  NH2 + Na2CO3 + 2NaBr + 2H2O
Propanamide Ethanamine
‘A’ ‘B’
Ethanamine reacts with valeraldehyde in the presence acid catalyst to give corresponding substituted imine
i.e., Schiff base.
H

CH3  CH2  NH2 + CH3  CH2  CH2  CH2  CHO 
H
CH3  CH2  CH2  CH2  C = N  CH2  CH3
Ethanamine Valeraldehyde Substituted imine
‘B’ (Schiff base)
‘C’
20. Mendius reduction of -phenylpropionitrile in the presence of sodium and ethanol gives
-phenylpropylamine (‘B’).

CH2  CH2  C  N + 4[H] 

Na / ethanol
 CH2  CH2  CH2  NH2

-phenylpropionitrile -phenylpropylamine
‘A’ ‘B’

Compound ‘B’ undergoes Hoffmann’s exhaustive methylation when heated with excess of methyl iodide to
give tetrasubstituted ammonium iodide.

CH2  CH2  CH2  NH2 + CH3  I CH2  CH2  CH2  N+ (CH3)3 I

‘B’ excess Trimethyl--phenylpropylammonium

iodide
‘C’
21. Hoffmann methylation of N-methylaniline gives N,N-dimethylaniline i.e., compound ‘A’. (CH3  I is not
used in excess amount hence, no exhaustive methylation occurs). Nitrosation of ‘A’ gives compound ‘B’.
H
N  CH3 + CH3  I 

H I
 N(CH3)2

N-methylaniline N,N-dimethylaniline
‘A’

NaNO 2  HCl
N(CH3)2 
273  278 K
O=N N(CH3)2 + H2O + NaCl

‘A’ 4-Nitroso-N, N-dimethylaniline

‘B’

250
 

Organic Reactions
22. Benzene undergoes Gatterman Koch formylation in the presence of CO, HCl, anhydrous AlCl3 and CuCl to
give benzaldehyde which on treatment with formaldehyde in the presence of conc. NaOH gives benzyl
alcohol and sodium formate. In this crossed Cannizzaro reaction, one of the aldehydes is formaldehyde.
Hence the reaction yields exclusively sodium formate.

CHO CH2OH


CO, HCl
anhydrous AlCl3 ,
 
HCHO
conc. NaOH
 + HCOO Na+
CuCl

Benzene Benzaldehyde Benzyl alcohol Sodium formate

‘A’ ‘B’ ‘C’ ‘D’

23. Phenol when treated with bromine water gives white precipitate of 2,4,6-tribromophenol.

OH OH
Br Br
'Y'

 (3 Br2 )
Bromine water
+ 3HBr

Phenol Br
2,4,6-Tribromophenol

24. 2-Bromobutane when treated with NaI in the presence of dry acetone gives 2-Iodobutane (Finkelstein
reaction). 2-Iodobutane when boiled with moist Ag2O (in situ generation of AgOH) gives Butan-2-ol.

Br I OH

CH3  CH2  CH  CH3 

NaI, dry acetone
Finkelstein
 CH3  CH2  CH  CH3 
moist Ag 2 O

CH3  CH2  CH  CH3
reaction
2-Bromobutane 2-Iodobutane Butan-2-ol
‘A’ ‘B’ ‘C’

Butan-2-ol (compound ‘C’) has one chiral carbon atom. OH

n
Number of optical isomers = 2
C*
H5C2 H
where, n = number of chiral carbon atoms.
CH3
 For Butan-2-ol, number of optical isomers = 21 = 2

25. In an addition reaction of an unsymmetrical alkene, the negative part of the reagent (Cl) adds to the carbon
with less number of hydrogen atoms (Markownikoff’s rule).

CH2  CH = CH2 CH2  CH  CH3

+ HCl  Cl

‘A’

Addition of magnesium metal to the compound ‘A’ in dry ether gives Grignard reagent i.e., ‘B’.

CH2  CH  CH3 CH2  CH  CH2

Cl Mg
+ Mg 
dry ether

Cl
‘A’ Grignard reagent
‘B’

251
 

MHT-CET Triumph Chemistry (Hints)

113. Methyl phenyl ether (anisole) undergoes bromination with bromine in acetic acid to form p-bromoanisole
(major product) and o-bromoanisole (minor product).
OCH3 OCH3 OCH3
Br

Br2 / CH 3 COOH
+

Methyl phenyl Br o-Bromoanisole

ether (Anisole)
p-Bromoanisole

OCH3 OCH3 OCH3

NO2
conc.HNO3  conc.H 2SO 4
114.   +

Anisole NO2
4-Nitroanisole 2-Nitroanisole
(major) (minor)

115. Ethyl alcohol is used as an antifreeze for automobile radiators because it lowers down the melting point of
water.

121. H2C = CH – OH
(Ethenol)

O OH

122. C6H5 – C – CH3 

i.LiAlH 4

 C6H5 – CH – CH3
ii.H
Acetophenone Secondary alcohol

Critical Thinking
3. Glycols are dihydric alcohols (having two hydroxyl groups). Ethylene glycol is the first member of this
series.
CH2OH
|
CH2OH
Ethylene glycol

4. (I) 1 1 (II) 1 1 (III) 1 1

CH2 CH  CH2 HO  CH2 CH2 OH CH3 CH2 CH2 OH
Ethylene glycol n-Propyl alcohol
OH OH OH (Two 1 carbon atoms, but only one 1
Glycerol alcoholic group)

6. In case of tertiary alcohols, (OH) group should be attached to tertiary carbon atom.
(A) CH3CH2  CH  CH2  CH3 (B) CH2  CH  CH2
| | | |
OH OH OH OH
Pentan-3-ol (Secondary alcohol) Propane-1,2,3-triol (Trihydric alcohol)

CH3 OH CH3 CH3

| | | |
(C) CH3  C  CH2  CH3 (D) CH3 – CH2 – CH – CH – CH – CH3
| 4,5-Dimethylhexan-3-ol (Secondary alcohol)
OH
2-Methylbutan-2-ol (Tertiary alcohol)

174
 

Organic Reactions
OH OH
H2C CH2 CH2
OH

+ HCHO 
Polymerisation
High pressure  ,
CH2 CH2
Phenol Formaldehyde
‘B’
H2C CH2 CH2
OH OH
Bakelite

30. CH3  CH2  Br + NH3 (alc.) H
 CH3 COOH
 CH3  CH2  NH2 + HBr
Ethyl bromide Ethanamine
‘P’
HNO2
(NaNO2 + HCl)
273 – 278 K
CH3  CH2  OH + N2  + H2O + NaCl
Ethanol
‘Q’
Molecular weight of CH3  CH2  OH = 46 g mol1.
H2SO4
31. CH3 (CH 2 ) 10 CHO 
i) NaBH 4
  CH3 (CH 2 )10 CH 2OH
ii) H / H 2 O
Lauryl aldehyde Lauryl alcohol
‘X’

CH3 (CH 2 ) 10 CH 2OSO3 Na +  CH (CH ) CH OSO H

NaOH
3 2 10 2 3
Sodium lauryl sulphate Lauryl hydrogen sulphate
‘Z’ ‘Y’
(Anionic detergent)

O
+
SO3 Na
Hydrophobic tail Hydrophilic head

32. Polythene can be prepared by polymerisation of ethene which in turn can be prepared by passing vapours of
ethanol over heated alumina (Al2O3) at 623 K.
CH3  CH2  OH 
Al2 O3
623 K
 CH2 = CH2 
Polymerisation
300 C,
 CH2  CH2
 H2 O 1000 atm, O2 n
Ethanol Ethene Polythene
34. When but-2-ene is treated with conc. HCl, 2-chlorobutane is obtained.
CH3  CH = CH  CH3 + HCl  CH3  CH  CH2  CH3
But-2-ene
Cl
1 2-Chlorobutane
Molar mass of But-2-ene = 56 g mol
Molar mass of 2-chlorobutane = 92.5 g mol1
Given weight of but-2-ene = 5.6 g
5.6 g
 Number of moles of but-2-ene = = 0.1 mol
56 g mol1
0.1 mol of but-2-ene will give 0.1 mol of product i.e. 2-chlorobutane.
 Mass of 2-chlorobutane obtained will be = 0.1  92.5 = 9.25 g
However, yield of the reaction is 50%
50
 Mass of 2-chlorobutane obtained = 9.25  = 4.625 g
100

253
 MHT-CET 2020
14th October 2020

Hints

1. The sp3 hybrid orbitals from oxygen and 1s atomic orbitals from two hydrogen atoms are involved during
the formation of two O−H bonds.
O (Z = 8): 1s2 2s2 2p4 ; H (Z = 1): 1s1
2s 2p 1s

    

sp3

4. From ideal gas equation, PV = nRT

At constant pressure, V  T
V1 T1

V2 T2
2 273

4 T2
T2 = 546 K = 273 C
7. Sixteen stereoisomers are possible due to the presence of 4 asymmetric C-atoms.
No. of optical isomers = 2n (where n is the number of asymmetric C-atoms)
= 24 = 16
8. Lithium crystallizes in bcc structure.
3
For bcc cell, r = a = 0.4330 a
4
= 0.4330 × 351 pm
= 151.983 pm
2
9. For fcc type of unit cell, r = a = 0.3535 a
4
127.6
∴ a= = 360.96 ≈ 361 pm
0.3535
10. For a given unit cell of aluminium,
a = 4 Å = 4  10–8 cm,
Density of Al = 2.7 g cm–3,
Mass of the element Al = 27 g/mol
Mn
Density (ρ) = 3
a NA
2.7g cm 3  (4 10 –8 )3 cm3  6.022  1023 atom mol1
n=
27g mol1
n = 3.85 ≈ 4 atoms
11. C = 1 mol L–1, R = 0.082 L⋅atm⋅K−1⋅mol−1, T = 300 K
 = CRT
= 1 mol L–1× 0.082 L⋅atm⋅K−1⋅mol−1 × 300 K
= 24.6 atm
254
  MHTCET - 14 Oct. 2020
Hints
Massof solute
13. Percentage by mass = 100
Massof solution
From the given data,
1.25
0.25   100 (Mass of solution = Mass of solute (x) + Mass of solvent (y))
1.25  y
25 1.25
  100
100 1.25  y
On solving we get, y = 498.75 g

14. 2C(s) + 3H2(g)   C2H6(g)

rH = ΣΔf H products   ΣΔ f Horeactants
o

= –2x1 – 3x2 + x3

16 1
16. Number of moles of O2 =  mole
32 2

x
Bond energy =  2x kJ
1/ 2
o
17.  om(CaCl2 ) = λ + 2λo 
Ca 2+ Cl

= 119 Ω–1 cm2 mol–1 + 2 × 71 Ω–1 cm2 mol–1

= 261.0 Ω–1 cm2 mol–1

l
18. Cell constant   =   R
a
= 0.0112  cm–1  55.0  = 0.616 cm1
–1

19. Rate = k[A]2 [B]1 [C]0

Order of a reaction = sum of the exponents of the concentration terms
=2+1=3
20. Given reaction: 4NH3 + 5O2 → 4NO + 6H2O
d NH3 
Rate of disappearance of NH3 =  = 3.6 × 10–3 M/s.
dt
1 d NH3  1 d[O2 ] 1 d[NO] 1 d H2O
Rate =  =– = =
4 dt 5 dt 4 dt 6 dt

1 d H2O 1 d NH3 
Rate of formation of H2O = =
6 dt 4 dt
d H2O 6
= × 3.6 × 10–3 M/s = 5.4 × 10–3 M/s
dt 4

21. The order of reactivity of halogens towards hydrogen is: F2 > Cl2 > Br2 > I2.
22. Due to the absence of d-orbital, F can not expand its valency and does not form polyhalides like Br and I.
Example: (IF7)
24. On passing, SO2 through acidified K2Cr2O7 solution, potassium dichromate is reduced to chromic sulphate.
The reaction involves reduction of chromium from Cr+6 (orange) to (Cr3+) green.
K2Cr2O7 + 2H2SO4 + 3SO2 → 2Cr2(SO4)3 + K2SO4 + H2O
26. Due to poor shielding of 4f electrons (i.e., negligible screening effect of ‘f’ orbitals), increased effective
nuclear charge is experienced and the valence shell is pulled slightly towards nucleus. This results in the
lanthanoid contraction.
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MHT-CET Triumph Chemistry (Hints)

27. Let x be the oxidation state of Cr in K3[Cr(C2O4)3].
Since, the overall charge on the complex is 0, the sum of oxidation states of all elements in it should be
equal to 0.
+3 + x + 3(–2) = 0
x = +3.
Hence, the oxidation state of Cr in K3[Cr(C2O4)3] is +3.
28. In heteroleptic complexes, a metal is attached to more than one kind of donor atoms or groups.
The complexes in which the complex ion carries a net positive charge are called cationic complexes.
 [Co(NH3)4Cl2]2+ + 2Cl–
[Co(NH3)4Cl2]Cl 
[Pt(NH3)2Cl2] is a neutral complex.
29. Hexamine cobalt(III) chloride [Co(NH3)6]Cl3 is a cationic complex. In this coordination number of cobalt is
6 and it is homoleptic complex.
31. H3C – CH – CH2 – Br 
Zn, Δ
H3C – CH = CH2 
HBr
 H3C – CH – CH3 
Na
 CH3 CH3
Alcohol Ether

Br Propene Br H3C – CH – CH – CH3

Propylene dibromide (A) 2-Bromopropane 2,3-Dimethylbutane
(1,2-Dibromopropane) (B) (C)
32. OH OH OH
OH HO OH
OH

HO OH
CH3
Catechol Pyrogallol Phloroglucinol p-Cresol
(Benzene-1,2-diol) (Benzene-1,2,3-triol) (Benzene-1,3,5-triol) (4-Methylphenol)

33. A secondary alcohol is dehydrated by heating with 60% H2SO4 at 373 K.

  
CH3CHCH2CH3 
60% H2SO4
373K
 CH3CH = CHCH3 + CH2 = CHCH2CH3
But-2-ene But-1-ene
OH (Major product) (Minor product)
Butan-2-ol

34. CH3  CH2 – O – CH2  CH2 CH2 Cl

Common name: 3-Chloropropyl ethyl ether
IUPAC name: 3-Chloro-1-ethoxypropane
35. The electron withdrawing carboxyl group (–COOH) is a deactivating and meta directing group, in
aromatic carboxylic acids.
COOH COOH

Conc.HNO3

Conc.H2SO4
 + H2O
NO2
Benzoic acid m-Nitrobenzoic acid

36. Common name: Mesityl oxide

IUPAC name: 4-Methylpent-3-en-2-one

O
37. The order of boiling point is 1 > 2 > 3 for isomeric amines.
38. 
CH3 – CH3 + HO – NO2   CH3 – CH2 – NO2 
LiAlH4 /ether
 CH3 – CH2 – NH2
Ethane Nitroethane Ethanamine
(A) (B)

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  MHTCET - 14 Oct. 2020
Hints
39. The reaction of glucose with hydroxylamine gives an oxime.
CHO CH = N  OH
NH2  OH
(CHOH)4 
 (CHOH)4 + H2O
CH2OH CH2OH
Glucose Glucoxime

40. HO – CH2

H2N  CH  COOH
Serine

42. Melamine-formaldehyde polymer is used in the manufacture of crockeries.

Molar mass of carbon in 1 mole of urea
43. Mass percentage of carbon in urea = × 100
Molar mass of urea
12
= × 100
60
= 20%
44. Terpineol, Chloroxylenol: Antiseptics
Penicillin: Antibiotic
45. Ununhexium (Uuh) is now designated as livermorium (Lv).
46. When bauxite is heated with NaOH solution, the aluminum oxide present in bauxite reacts with NaOH to
form water soluble sodium meta aluminate (NaAlO2).
The reaction is as follows:
Al2O3.2H2O(s) + 2NaOH(aq) → 2NaAlO2(aq) + 3H2O(l)
47. Bithionol has a property of reducing bad odour resulting from bacterial decomposition on body. Hence it is
used as deodorants in medicated soaps or powders.
48. In R, S configuration system of nomenclature if a group contains multiple bonds, the doubly or triply bonded
atoms are counted as two or three of those atoms, respectively.
The carbonyl group C = O is considered to have two carbon-oxygen bonds, one actual and one with
theoretical oxygen atom called phantom atom. This can be represented as follows:
OH OH

C=O  CO

(O) (C)

49. The dry distillation of only calcium formate by thermal decomposition yields the product methanal.
O

HCO O
Ca 

Drydistillation
 HCH + CaCO3
HCO
Methanal
O (Formaldehyde)
Calcium formate

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MHT-CET Triumph Chemistry (Hints)

50. Balz-Schiemann reaction involves replacement of diazonium group by –F.
N 2 X  N 2 BF4 F


HBF4
   + BF3 + N2
Benzenediazonium Benzenediazonium Fluorobenzene
halide fluoroborate

258